JP2021144869A - Conductive laminate and conductive laminated tape - Google Patents

Abstract

To provide a conductive laminate and a conductive laminated tape which can achieve both conductivity and various characteristics of insulating properties on the surface and blackness while being small in the total thickness and thin.SOLUTION: A conductive laminate has a conductive layer having facing first main surface and second main surface, a black adhesive layer provided on the first main surface of the conductive layer and an insulating part provided on the black adhesive layer. The conductive layer is a metallic foil, and the insulating part has an insulating resin layer and a black ink layer. On the surface of the conductive laminate positioned on the first main surface side of the conductive layer, brightness L* regulated by a CIE L*a*b* color system is 20 or more and 27 or less, chromaticity a* is -2 or more and 2 or less, and chromaticity b* is -2 or more and 2 or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a conductive laminate and a conductive laminate tape.

The conductive laminated body and the conductive laminated tape in which the conductive adhesive layer is provided on the laminated body (hereinafter, the conductive laminated body and the conductive laminated tape may be generally referred to as a conductive laminated body or the like. ) Is for shielding unnecessary leaked electromagnetic waves radiated from electrical and electronic devices, for shielding harmful spatial electromagnetic waves generated by other electric and electronic devices, for grounding to prevent electrostatic charge, etc. It is used in.

Conductive laminates and the like are required to have a small total thickness and a thin thickness as electrical and electronic devices become smaller and thinner. Further, the conductive laminate or the like has an insulating property on one surface in order to have high electromagnetic wave shielding property in addition to high conductivity and to prevent short circuit due to contact with other members. Is required.

Furthermore, in recent years, electrical and electronic devices have been improved in appearance and internal design, display image quality, image visibility, etc., and in particular, the color of electronic components built inside the device has been unified to black. Attempts have been made to improve the internal design. For this reason, the conductive laminate used in the part where such internal design is required has black design such as jet blackness and matteness so as to give a sense of unity in synchronization with the black color of the black electronic component. It is required to have high surface blackness such as shielding property. In the present specification, the surface blackness of the conductive laminate or the like is a physical property that is mainly visible from the surface side having the insulating property of the conductive laminate or the like.

For example, Patent Document 1 describes a base base material in which metal layers are formed on both sides of a resin film, a light-shielding insulating layer provided on a first main surface of the base base material, and a second base material. A conductive sheet having a conductive adhesive layer provided on the main surface of the above is disclosed. The conductive sheet disclosed in Patent Document 1 uses a black resin layer formed of an insulating resin colored with a black colorant as a light-shielding insulating layer.

Further, in Patent Document 2, an adhesive tape having a colored layer on one surface of a polyethylene terephthalate film and a transparent adhesive layer on the other surface is bonded to the first main surface of a soft aluminum base material. , A sheet in which another transparent pressure-sensitive adhesive layer is provided on a second main surface of a soft aluminum base material is disclosed.

Japanese Unexamined Patent Publication No. 2014-58108 JP-A-2017-8262

The conductive sheet disclosed in Patent Document 1 has a structure in which a base base material has a resin film interposed between two metal layers, and the thickness of each metal layer is small. Therefore, it is difficult for the conductive sheet to sufficiently obtain conductivity and electromagnetic wave shielding property, particularly electromagnetic wave shielding property. Then, in order to improve these characteristics, the thickness of the metal layer must be increased, and it is difficult to achieve both improvement of conductivity and electromagnetic wave shielding property and thinning of the conductive sheet. There is a problem that there is. Further, in the conductive sheet disclosed in Patent Document 1, a black resin layer, which is a light-shielding insulating layer, is directly formed on the metal layer. However, in order to have high insulation and surface blackness, the thickness of the black resin layer must be increased, achieving both improvement of surface insulation and surface blackness and thinning of the conductive sheet. There is a problem that it is difficult to do.

In the sheet disclosed in Patent Document 2, the surface blackness is guaranteed only by the colored layer, and since the thickness thereof is thin, it is difficult to obtain sufficient surface blackness. Further, in order to improve the above characteristics, the thickness of the colored layer must be increased, and there is a problem that it is difficult to achieve both the improvement of the surface blackness and the thinning of the conductive sheet. ..

The present invention has been made in view of the above circumstances, and it is possible to achieve both conductivity and electromagnetic wave shielding properties, as well as surface insulation and blackness properties, while having a small total thickness and thinness. It is an object of the present invention to provide a possible conductive laminate and conductive laminate tape.

The present invention is a conductive laminate having a conductive layer having a first main surface and a second main surface facing each other, and a black pressure-sensitive adhesive layer provided on the first main surface of the conductive layer. And an insulating portion provided on the black pressure-sensitive adhesive layer, the conductive layer is a metal foil, and the insulating portion has an insulating resin layer and a black ink layer, and the conductive layer. ^{The brightness L * defined by the CIE L *} a ^* b ^* color system on the surface of the conductive laminate located on the first main surface side of the above is 20 or more and 27 or less, and the chromaticity a ^* is Provided is a conductive laminate having -2 or more and 2 or less and a chromaticity b ^{* of -2 or more and 2 or less.}

Further, the present invention has the above-mentioned conductive laminate and the above-mentioned conductive pressure-sensitive adhesive layer, and the above-mentioned conductive pressure-sensitive adhesive layer is on the above-mentioned second main surface of the above-mentioned conductive layer constituting the above-mentioned conductive laminate. Provided is a conductive laminated tape provided in.

According to the present invention, a conductive laminate and a conductive laminate capable of achieving both conductivity, electromagnetic wave shielding property, surface insulation property, and blackness property while being small and thin in total thickness. Tape can be provided.

It is the schematic sectional drawing which shows an example of the conductive laminated body of this invention. It is the schematic sectional drawing which shows the other example of the conductive laminated body of this invention. It is the schematic sectional drawing which shows an example of the conductive laminated tape of this invention. It is the schematic sectional drawing which shows the other example of the conductive laminated tape of this invention. It is a figure which shows the outline of the sample used for the measuring method of the electromagnetic wave shielding characteristic. It is a figure which shows the outline of the measurement method of the electromagnetic wave shield characteristic.

Hereinafter, the conductive laminated body and the conductive laminated tape of the present invention will be described respectively.

I. Conductive Laminate The conductive laminate of the present invention has a conductive layer having a first main surface and a second main surface facing each other, and a black pressure-sensitive adhesive provided on the first main surface of the conductive layer. It has a layer and an insulating portion provided on the black pressure-sensitive adhesive layer, the conductive layer is a metal foil, and the insulating portion has an insulating resin layer and a black ink layer.

The conductive laminate of the present invention has a layer structure in which an insulating portion having a black ink layer and an insulating resin layer, a black adhesive layer, and a metal foil as a conductive layer are laminated in this order. Although it is small in thickness and thin, it can exhibit high conductivity, high electromagnetic wave shielding property, and high surface insulation property. Further, according to the present invention, since the conductive laminate has the above-mentioned laminated structure, the brightness L ^* , the chromaticity a ^* and b ^* of the surface of the conductive laminate on the insulating portion side are set within the predetermined ranges, respectively. And can enhance the blackness.

In other words, the conductive laminate of the present invention is defined by the ^{CIE L *} a ^* b ^* color system of the surface of the conductive laminate located on the first main surface side of the conductive layer. The brightness L ^* is 20 or more and 27 or less, the chromaticity a ^* is -2 or more and 2 or less, and the chromaticity b ^* is -2 or more and 2 or less.

According to the present invention, it is possible to provide a conductive laminate capable of achieving both conductivity, electromagnetic wave shielding property, surface insulation property and blackness property while having a small total thickness and thinness. Can be done.

More specifically, according to the conductive laminate of the present invention, by having the above-mentioned layer structure, the black color exhibited by the black ink layer and the black pressure-sensitive adhesive layer in the insulating portion which is the outermost layer overlaps in a plan view. Even if the total thickness of the conductive laminate is small, the surface blackness can be highly exhibited. In particular, when a metal foil is used as the conductive layer, the color density and hue of the black color exhibited on the surface of the conductive laminate are easily affected by the color of the metal foil, and black design properties such as jet blackness and matte feeling can be exhibited. It will be difficult. On the other hand, according to the present invention, the blackness is ensured by the two layers of the black ink layer and the black adhesive layer, and the black color of the two layers overlaps, so that the influence of the color of the metal foil can be suppressed. , The surface blackness, especially the black design such as jet blackness and matte feeling can be enhanced. Further, according to the conductive laminate of the present invention, the insulating portion has a black ink layer that contributes to surface blackness and an insulating resin layer that contributes to insulation as separate layers, thereby enhancing the surface blackness. At the same time, high insulation can be ensured, and further, by using a metal foil as the conductive layer, good electromagnetic shielding properties can be exhibited even if the total thickness is small.

Here, in the present invention, the surface blackness of the entire conductive laminate is expressed by overlapping two layers of the black ink layer and the black adhesive layer, but as a method of expressing the surface blackness. For example, a method in which a black ink layer is directly formed on the conductive layer and expressed as a single layer of the black ink layer is also conceivable. However, in this method, not only the surface blackness but also the surface insulation must be ensured by the black ink layer, and even if the total thickness of the conductive laminate can be reduced and the surface blackness can be improved, it is desired. It may be difficult to show surface insulation. Further, in order to improve the insulating property, the thickness of the black ink layer must be increased, and it may be difficult to reduce the total thickness of the conductive laminate.

As another method for developing the surface blackness, a method of adding a black colorant in the insulating resin layer for ensuring the insulating property without providing the black ink layer or the black adhesive layer can be considered. However, in this method, it is necessary to increase the amount of the black colorant added in order to develop the surface blackness, and the conductivity of the colorant may reduce the insulating property of the insulating resin layer. Further, when a large amount of colorant is added, it becomes difficult to stretch the insulating resin layer to a desired thickness, and the thickness of the insulating resin layer becomes large. Therefore, the total thickness of the conductive laminate can be reduced. It can be difficult.

As described above, depending on the method for expressing the surface blackness, the thinning of the entire laminate may be hindered, or the physical properties such as conductivity, insulation, and shielding characteristics may be deteriorated, while the thinning or thinning may be performed. If an attempt is made to satisfy the required characteristics such as conductivity, insulation, and shield characteristics, there is an adverse effect that sufficient surface blackness cannot be obtained. As a result of diligent studies by the present inventors in order to eliminate such adverse effects, an insulating portion having a black ink layer and an insulating resin layer, a black pressure-sensitive adhesive layer, and a metal foil as a conductive layer have been formed. By forming a layer structure in which the layers are laminated in this order, the total thickness is small and thin, and it is possible to achieve both conductivity, electromagnetic wave shielding property, surface insulation property, and blackness property. It came to complete the body.

The conductive laminate of the present invention has an insulating portion having a black ink layer and an insulating resin layer, a black adhesive layer, and a conductive layer in this order. Hereinafter, each layer will be described.

In the conductive laminate of the present invention, the surface of the conductive laminate located on the first main surface side of the conductive layer may be referred to as the insulating portion side surface of the conductive laminate. Further, the surface of the conductive laminate located on the second main surface side of the conductive layer may be referred to as the surface of the conductive laminate on the conductive layer side.

(Conductive layer)
The conductive layer in the present invention is a layer that bears the conductivity of the conductive laminate. In the present invention, the conductive layer is a metal foil. Here, the metal foil is a layer made of metal, and is a foil having a thickness of metal at a micro level. Since the conductive layer of the conductive laminate of the present invention is a metal foil, it can exhibit high electromagnetic wave shielding properties as compared with a graphite sheet, a metal vapor deposition film, or the like.

The metal foil is not particularly limited as long as it is a foil made of a desired metal material, and examples thereof include copper foil, aluminum foil, nickel foil, and stainless steel foil. Among them, copper foil is most preferable from the viewpoint of excellent conductivity and electromagnetic wave shielding characteristics.

Further, the copper foil may be an electrolytic copper foil or a rolled copper foil, but it is excellent in adhesiveness when it is used as a black adhesive layer to be bonded to a conductive layer or a conductive laminated tape described later. , Electrolytic copper foil is the best.

The thickness of the conductive layer may be as long as the conductive laminate of the present invention can exhibit desired conductivity. Specifically, the thickness of the conductive layer is preferably 15 μm or more, preferably 20 μm or more. It is preferable, and the thickness is preferably 40 μm or less, preferably 35 μm or less. More specifically, the thickness of the conductive layer is preferably 15 μm or more and 40 μm or less, and preferably 20 μm or more and 35 μm or less. By setting the thickness of the conductive layer within the above range, the conductivity and the electromagnetic wave shielding property can be satisfactorily exhibited even if the total thickness of the conductive laminate is small. If the thickness of the conductive layer exceeds the above range, it may be difficult to reduce the thickness of the conductive laminate, while if it is less than the above range, it may be difficult to obtain conductivity or electromagnetic wave shielding property. There is.

The ten-point average surface roughness Rz of the conductive layer is preferably 2.0 μm or less. When the surface roughness Rz of the conductive layer is within the above range, it is attached to the black adhesive layer to be bonded to the conductive layer or to the second main surface of the conductive layer when forming a conductive laminated tape to be described later. This is because the adhesiveness can be sufficiently exhibited to the conductive pressure-sensitive adhesive layer and the insulating pressure-sensitive adhesive layer of the thin film to be combined. The ten-point average surface roughness Rz of the conductive layer is more preferably 0.01 μm or more and 0.1 μm or more, and the Rz is 2.0 μm or less, 1.5 μm or less, 1.3 μm or less, 1. It is 1 μm or less and 0.9 μm or less.

The arithmetic average roughness Ra of the conductive layer is preferably 0.01 μm or more and 1.0 μm or less, more preferably 0.01 μm or more and 0.7 μm or less, and further preferably 0.05 μm or more and 0.3 μm or less. By setting the arithmetic average roughness Ra of the conductive layer within the above range, the black adhesive layer to be bonded to the conductive layer or the second main surface of the conductive layer when the conductive laminated tape described later is formed. This is because the adhesiveness can be sufficiently exhibited to the conductive pressure-sensitive adhesive layer and the insulating pressure-sensitive adhesive layer of the thin film to be bonded.

The ten-point average surface roughness Rz and the arithmetic average roughness Ra of the conductive layer refer to the values specified in JIS B0601: 2013, and using HANDYSURF + manufactured by Tokyo Precision Co., Ltd., any three locations on the surface of the conductive layer (each vertical). Surface measurement is performed on a range of 50 μm × 50 μm in width), and the average value of the three points obtained by the measurement is defined as the ten-point average surface roughness Rz and the arithmetic average roughness Ra of the conductive layer.

(Black adhesive layer)
The black pressure-sensitive adhesive layer in the present invention is a layer that is arranged between the conductive layer and the insulating portion and that adheres the conductive layer and the insulating portion. In the conductive laminate of the present invention, in addition to the black ink layer of the insulating portion, the pressure-sensitive adhesive layer for bonding the conductive layer and the pressure-sensitive adhesive layer is black, and the black ink layer and the black pressure-sensitive adhesive layer are viewed in plan view. By overlapping with the agent layer, it is possible to enhance the surface blackness, particularly the black design, which is visible from the surface on the insulating portion side. As a result, it is possible to suppress an increase in the total thickness of the conductive laminate due to the improvement in surface blackness.

The black pressure-sensitive adhesive layer contains at least a black pigment and a pressure-sensitive adhesive component. The pressure-sensitive adhesive component is not particularly limited, and for example, an acrylic pressure-sensitive adhesive composition, a rubber-based pressure-sensitive adhesive composition, a silicone-based pressure-sensitive adhesive composition, a urethane-based pressure-sensitive adhesive composition, a polyester-based pressure-sensitive adhesive composition, and a styrene-diene block. Known such as copolymerization type pressure-sensitive adhesives, vinyl alkyl ether type pressure-sensitive adhesive compositions, polyamide-based pressure-sensitive adhesive compositions, fluorine-based pressure-sensitive adhesive compositions, creep property-improved pressure-sensitive adhesive compositions, and radiation-curable type pressure-sensitive adhesive compositions. The pressure-sensitive adhesive composition of the above can be appropriately selected and used. The pressure-sensitive adhesive component can be used alone or in combination of two or more.

Among them, it is preferable to include an acrylic pressure-sensitive adhesive composition as a pressure-sensitive adhesive component, and the acrylic pressure-sensitive adhesive composition uses a (meth) acrylic polymer (acrylic copolymer) as a base polymer and is crosslinked as necessary. Adhesive reliability is such that the (meth) acrylic pressure-sensitive adhesive composition contains appropriate additives such as an agent, a pressure-imparting agent, a softening agent, a plasticizing agent, a filler, an anti-aging agent, and a coloring agent. It is preferable because it is expensive.

The (meth) acrylic polymer is a polymer containing a (meth) acrylic acid alkyl ester monomer as a main component, and is a monomer (copolymerization) capable of copolymerizing with a (meth) alkyl ester, if necessary. It is prepared by using a sex monomer). That is, the acrylic polymer may be a homopolymer or a copolymer.

Examples of the (meth) acrylic acid alkyl ester constituting the (meth) acrylic polymer include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, and isopropyl (meth) acrylic acid. N-butyl acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Isodecyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, (meth) C1-20 alkyl esters of (meth) acrylates such as heptadecyl acrylate, octadecyl (meth) acrylate, nonadecil (meth) acrylate, and eicosyl (meth) acrylate [preferably C4-18 alkyl (meth) acrylate (direct). Chain-shaped or branched-chain-shaped alkyl) ester] and the like. The (meth) acrylic acid alkyl ester can be appropriately selected depending on the desired adhesiveness and the like. The (meth) acrylic acid alkyl ester can be used alone or in combination of two or more. Those containing 30% or more of butyl acrylate are preferable because they have excellent adhesiveness and heat resistance.

Examples of the copolymerizable monomer copolymerizable with the above (meth) alkyl ester include carboxyl groups such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Containing monomer or its anhydride; Sulphonic acid group-containing monomer such as sodium vinyl sulfonate; Aromatic vinyl compound such as styrene and substituted styrene; Cyan group-containing monomer such as acrylonitrile; Ethylene, propylene, butadiene and the like Olefins; Vinyl esters such as vinyl acetate; Vinyl chloride; Amido group-containing monomers such as acrylamide, metaacrylamide, N-vinylpyrrolidone, N, N-dimethyl (meth) acrylamide; Hydroxyalkyl (meth) acrylate , Hydroxyl group-containing monomers such as glycerin dimethacrylate; amino group-containing monomers such as (meth) aminoethyl acrylate, (meth) acryloylmorpholine; imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide; Epoxy group-containing monomers such as glycidyl acrylate and methyl glycidyl (meth) acrylate; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate, as well as triethylene glycol di (meth) acrylate and diethylene glycol di. (Meta) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimerol propantri (meth) Examples thereof include polyfunctional copolymerizable monomers (polyfunctional monomers) such as acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and divinylbenzene. The copolymerizable monomer may be used alone or in combination of two or more. As the copolymerizable monomer, a modifying monomer having a functional group such as a carboxyl group can be preferably used. Those containing 0.5 to 4.0% of acrylic acid are preferable because they have excellent adhesiveness and heat resistance.

The weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 300,000 or more, 500,000 or more, 600,000 or more, and the weight average molecular weight (Mw) is preferably 1.2 million or less, 1 million or more. Below, it is 900,000 or less. More specifically, the weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably in the range of 300,000 to 1.2 million, more preferably in the range of 500,000 to 1,000,000, and 600,000 to 900,000. Within the range is more preferable. When the weight average molecular weight (Mw) of the (meth) acrylic polymer is within the above range, the black pressure-sensitive adhesive layer exhibits good adhesiveness and heat resistance to the conductive layer and the insulating portion even if it is thin. can do.

The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC). More specifically, it can be obtained by measuring with the following GPC measuring conditions by the polystyrene conversion value using "SC8020" manufactured by Tosoh Corporation as a GPC measuring device.
(GPC measurement conditions)
-Sample concentration: 0.5% by weight (tetrahydrofuran solution)
-Sample injection volume: 100 μL
-Eluent: tetrahydrofuran (THF)
・ Flow velocity: 1.0 mL / min
-Column temperature (measurement temperature): 40 ° C
-Column: "TSKgel GMHHR-H" manufactured by Tosoh Corporation
・ Detector: Differential refractometer

Unless otherwise specified, the weight average molecular weight (Mw) in the present specification is a value measured by the above method and conditions.

The black pressure-sensitive adhesive layer in the present invention exhibits black color by containing a black colorant. Examples of the black colorant include organic black pigments, inorganic black pigments, and black dyes. The black colorant may be used alone or in combination of two or more. Further, the black colorant preferably has low insulating property or conductivity. This is because the conductivity of the black pressure-sensitive adhesive layer can be lowered and the surface insulation of the conductive laminate can be improved.

Examples of inorganic black pigments include carbon black (furness black, channel black, acetylene black, thermal black, lamp black, etc.), graphite, copper oxide, manganese dioxide, aniline black, perylene black, titanium black, cyanine black, activated carbon, etc. Examples thereof include ferrite, magnetite, chromium oxide, iron oxide, molybdenum disulfide, chromium complex, and composite oxide-based black dye. Examples of the organic black pigment include aniline black, azo pigment, anthraquinone organic black pigment and the like. Among them, carbon black is preferable as the black colorant because it is excellent in light-shielding property and dispersibility and can exhibit high concealing property by overlapping the black ink layer and the black pressure-sensitive adhesive layer.

The content of the black colorant in the black pressure-sensitive adhesive layer is not particularly limited, and can be an amount capable of exhibiting a desired surface blackness by overlapping with the black ink layer. For example, the total amount of the black pressure-sensitive adhesive layer (100). In mass%), it is preferably 1% by mass or more and 50% by mass or less, more preferably 4% by mass or more and 40% by mass or less, and further preferably 10% by mass or more and 35% by mass or less. When the content of the black colorant in the black pressure-sensitive adhesive layer is within the above range, the black pressure-sensitive adhesive layer can exhibit the insulating property and the adhesiveness to the insulating part and the conductive layer even if the thickness is thin, and further, the black ink layer and the black ink layer can be exhibited. It is possible to enhance the surface blackness due to the overlap of the above.

The black pressure-sensitive adhesive layer preferably contains a tack-imparting resin in order to improve the adhesive strength. Since the black pressure-sensitive adhesive layer contains the pressure-sensitive adhesive resin, the tensile strength and the tensile breaking strength can be increased. Therefore, by appropriately adding the pressure-sensitive adhesive resin according to the (meth) acrylic polymer used, the conductivity of the present invention can be increased. The tensile strength and tensile breaking strength of the sex laminate can be adjusted. Examples of the tackifier resin include rosin-based resins such as rosin and rosin ester compounds; terpene-based resins such as diterpene polymers and α-pinene-phenol copolymers; aliphatic (C5) and aromatic (C5) and aromatic resins (C5). Petroleum resins such as C9); other examples include styrene-based resins, phenol-based resins, and xylene resins. The tackifier resin may be used alone or in combination of two or more.

Among them, when the black pressure-sensitive adhesive layer contains a (meth) acrylic polymer containing n-butyl (meth) acrylate (in other words, n-butyl (meth) acrylate) as a main monomer component, it is referred to as a rosin resin. It is preferable to mix and contain a styrene resin. This is because by using these two types of tackifier resins in combination, it becomes easier to achieve both thinning of the black pressure-sensitive adhesive layer and adhesive strength.

The black pressure-sensitive adhesive layer preferably contains a tack-imparting resin that is liquid at room temperature in order to increase the initial adhesive strength. Examples of the tackifier resin that is liquid at room temperature include a liquid resin that is a tackifier resin that is solid at room temperature, and low molecular weight liquid rubbers such as process oils, polyester-based plasticizers, and polybutenes. A terpene phenol resin is particularly preferable. Commercially available products include YP-90L manufactured by Yasuhara Chemical Co., Ltd. The amount of the tackifier resin added is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer.

The tackifier resin is preferably contained in the range of 10 parts by mass to 70 parts by mass, and more preferably in the range of 20 parts by mass to 60 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. By setting the amount of the tackifier resin in the above range, the adhesive strength of the black pressure-sensitive adhesive layer can be improved.

The gel fraction of the black pressure-sensitive adhesive layer is not particularly limited, but is preferably in the range of 5 to 95% by mass. This is because even if the black pressure-sensitive adhesive layer is thin, sufficient adhesiveness is likely to be exhibited. Above all, the gel fraction of the black pressure-sensitive adhesive layer is more preferably in the range of 10 to 70% by mass, and even more preferably in the range of 15 to 50% by mass.

The gel fraction is expressed as a percentage of the original mass by immersing the cured black pressure-sensitive adhesive layer in toluene and measuring the mass of the insoluble matter remaining after being left for 24 hours after drying.
Gel fraction (mass%) = [(mass of black adhesive layer after toluene immersion) / (mass of black adhesive layer before toluene immersion)] × 100

The storage elastic modulus of the black pressure-sensitive adhesive layer at 25 ° C. ^{is preferably 1 × 10 4} or more and 5 × 10 ⁵ Pa or less, and ^{more preferably 3 × 10 4} or more and 1 × 10 ⁵ Pa or less. By setting the storage elastic modulus of the black pressure-sensitive adhesive layer within the above range, it becomes easy to achieve both wettability (initial tack), adhesiveness, and processability even if the film is a thin film.

The storage elastic modulus of the black pressure-sensitive adhesive layer at 25 ° C. can be measured by a viscoelasticity tester. More specifically, it can be obtained by measuring under the following measurement conditions using a viscoelasticity tester (Ares 2kSTD) manufactured by TA Instruments Japan Co., Ltd. as a viscoelasticity tester.
・ Test piece thickness: 2 mm
・ Frequency: 1Hz
・ Compressive load: 40-60g

In the present specification, the storage elastic modulus of the black pressure-sensitive adhesive layer and the other pressure-sensitive adhesive layers at 25 ° C. is a value measured by the above method and conditions unless otherwise specified.

The (meth) acrylic polymer can be prepared by a conventional polymerization method such as a solution polymerization method, an emulsion polymerization method, or an ultraviolet irradiation polymerization method.

The thickness of the black pressure-sensitive adhesive layer is preferably 0.5 μm or more, 1 μm or more, 1.5 μm or more, and the above thickness is preferably 5 μm or less, 3 μm or less, 2.5 μm or less. More specifically, the thickness of the black pressure-sensitive adhesive layer is preferably 0.5 μm or more and 5 μm or less, preferably 1 μm or more and 3 μm or less, and most preferably 1.5 μm or more and 2.5 μm or less. .. By setting the thickness of the black pressure-sensitive adhesive layer within the above range, the blackness of the black pressure-sensitive adhesive layer alone is improved, and it becomes easy to achieve both adhesive strength and thinness as a conductive laminate. .. In particular, when the conductive laminate of the present invention is used for an electromagnetic wave shield for electronic parts, it becomes easy to achieve both the required adhesive strength and thinness.

The black pressure-sensitive adhesive layer preferably has low conductivity or exhibits insulating properties. This is because by lowering the conductivity of the black pressure-sensitive adhesive layer, the insulating property of the surface of the conductive laminate on the insulating portion side can be improved. Specifically, the surface resistivity of the black adhesive layer ^{is preferably 1 × 10 9} Ω / □ or more, more preferably 1 × 10 ¹⁰ Ω / □ or more, and 1 × 10 ¹¹ Ω / □ or more. □ It is more preferable that it is equal to or more than □. When the surface resistivity of the black pressure-sensitive adhesive layer is within the above range, the black pressure-sensitive adhesive layer can exhibit high insulating properties, and the insulating properties exhibited by the insulating portion can be further enhanced. This makes it possible for the conductive laminate of the present invention to exhibit higher insulating properties on the surface on the insulating portion side. The larger the surface resistivity of the black adhesive layer, the better, but in general, 1 × 10 ¹⁸ Ω / □ or less, 1 × 10 ¹⁶ Ω / □ or less, 1 × 10 ¹⁴ Ω / □ or less, 1 × 10 ¹² It can be Ω / □ or less.

The surface resistivity of the black adhesive layer refers to the value measured according to JIS-K6911, and the black adhesive layer is used using a resistivity meter (Advantest digital ultra-high resistance / micro ammeter R8340, TR42 box). Can be measured by applying a voltage of 500V.

The concealment rate of the black adhesive layer is not particularly limited as long as it can exhibit the desired surface blackness due to the overlap with the black ink layer described later, but it is preferably 20% or more, preferably 30% or more. More preferably, it is more preferably 40% or more. Further, the higher the shielding rate of the black pressure-sensitive adhesive layer is, the more preferable it is, and the upper limit thereof can be 100%. This is because by setting the concealment rate of the black pressure-sensitive adhesive layer within the above range, it is possible to suppress the deterioration of the blackness of the surface of the conductive laminate due to the color of the conductive layer.

The concealment rate of the black adhesive layer can be measured by the following method. The black adhesive layer was attached to the white and black surfaces of the concealment rate test paper (manufactured by Nippon Test Panel Industry Co., Ltd.), and was attached to the white and black surfaces by the color measuring method specified in JIS-Z-8722. Of the tristimulus values of the black pressure-sensitive adhesive layer, the Y value indicating the brightness is measured. Using a colorimetric gloss meter "CM-3500d" (manufactured by Minolta Co., Ltd.), the standard light C in the 2 degree field of view is measured. The concealment rate can be measured by applying the measured Y value to the following formula.
Concealment rate (%) = (Y value of the black adhesive layer attached to the black surface / Y value of the black adhesive layer attached to the white surface) × 100%

The black pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive in which a black colorant is dispersed on a conductive layer or a resin film. Examples of the coating method include gravure coating, comma coating, bar coating, die coating, lip coating, screen coating and the like. Of these, a gravure coating is preferable for coating a thin film, and a microgravure coating is the most preferable.

(Insulation part)
The insulating portion in the present invention is a layer provided on the first main surface of the conductive layer via the black pressure-sensitive adhesive layer. Further, the insulating portion bears one outermost layer of the conductive laminate of the present invention. The insulating portion in the present invention has an insulating resin layer and a black ink layer.

In the conductive laminate of the present invention, the stacking order of the insulating resin layer and the black ink layer of the insulating portion is not limited, and the black ink layer and the insulating resin layer are arranged in this order from the black adhesive layer side. The insulating resin layer and the black ink layer may be laminated in this order from the black pressure-sensitive adhesive layer side.

FIG. 1 is a schematic cross-sectional view showing an example of the conductive laminate of the present invention, showing an example in which the insulating resin layer and the black ink layer are laminated in this order from the black pressure-sensitive adhesive layer side. There is. The conductive laminate 10 of the present invention illustrated in FIG. 1 has a conductive layer 1 having a first main surface and a second main surface facing each other, and a black color provided on the first main surface of the conductive layer 1. It has a pressure-sensitive adhesive layer 2 and an insulating portion 3 provided on the black pressure-sensitive adhesive layer 2 and having an insulating resin layer 4 and a black ink layer 5. The conductive layer 1 is a metal foil and is a black pressure-sensitive adhesive. The insulating resin layer 4 and the black ink layer 5 are laminated in this order from the layer 2 side.

Further, FIG. 2 is a schematic cross-sectional view showing another example of the conductive laminate of the present invention, in which the black ink layer and the insulating resin layer are laminated in this order from the black adhesive layer side. An example is shown. The conductive laminate 10 of the present invention illustrated in FIG. 2 is provided on a conductive layer 1 having a first main surface and a second main surface facing each other and the first main surface of the conductive layer 1. It has a black adhesive layer 2 and an insulating portion 3 provided on the black adhesive layer 2 and having an insulating resin layer 4 and a black ink layer 5. The conductive layer 1 is a metal foil and has a black adhesive. The insulating resin layer 4 and the black ink layer 5 are laminated in this order from the agent layer 2 side.

Above all, in the insulating portion, it is preferable that the insulating resin layer and the black ink layer are laminated in this order from the black adhesive layer side. By arranging the black ink layer on the surface of the insulating resin layer opposite to the conductive layer side, the black ink layer is located on the outermost side of the conductive laminate and overlaps with the black adhesive layer. This is because the black ink layer makes it possible to further adjust the surface blackness of the conductive laminate.

The insulating resin layer constituting the insulating portion in the present invention is not particularly limited, and examples thereof include a resin film exhibiting known insulating properties. Specific examples thereof include polyester film, polyimide film, polyamide film, polyurethane film, and polyolefin film. Among them, a polyester film or a polyimide film is preferable because it is thin and maintains insulating properties, and it is hard to tear and exhibits strength, and a polyester film is particularly preferable because it can be made thinner and has excellent insulating properties.

The thickness of the insulating resin layer is not particularly limited as long as it can exhibit the desired insulating property, but is preferably 1 μm or more, 1.5 μm or more, and 2 μm or more. The thickness can be preferably 5 μm or less, 4.5 μm or less, 4 μm or less, 3.5 μm or less, 3 μm or less, and 2.5 μm or less. More specifically, the thickness of the insulating resin layer is preferably 1 μm or more and 5 μm or less, more preferably 1 μm or more and 3 μm or less, and most preferably 1.5 μm or more and 2.5 μm or less. This is because when the thickness of the insulating resin layer is within the above range, high insulating properties can be easily exhibited.

Further, the black ink layer constituting the insulating portion in the present invention contains at least a black pigment and a binder resin. The black ink layer is formed by black ink in which a known black pigment is dispersed in a resin varnish.

The black pigment may be used alone or in combination of two or more. Further, the black pigment preferably has low insulating property or conductivity. This is because the conductivity of the black ink layer can be lowered and the surface insulation of the conductive laminate can be improved.

As the black pigment, a known material can be used, and it may be an organic black pigment or an inorganic black pigment. Examples of inorganic black pigments include carbon black (furness black, channel black, acetylene black, thermal black, lamp black, etc.), graphite, metal oxides (chromium oxide, iron oxide, copper oxide, etc., manganese dioxide, etc.), aniline. Examples thereof include black, perylene black, titanium black, cyanine black, activated carbon, ferrite, magnetite, molybdenum disulfide, chromium complex, and composite oxide-based black pigment. Examples of the organic black pigment include aniline black, azo pigment, anthraquinone organic black pigment and the like.

Above all, the black ink layer preferably contains at least one black pigment of carbon black and an azo pigment. This is because carbon black is preferable because it can enhance the blackness. Further, the azo pigment is preferable because it can improve the insulating property. Above all, it is more preferable to contain both carbon black and azo pigments.

The content of the black pigment may be any amount as long as it can exhibit the desired blackness, particularly the black design property, by overlapping the black ink layer and the black pressure-sensitive adhesive layer. For example, in the total amount (100% by mass) of the black ink layer. It is preferably 1% by mass or more and 95% by mass or less, preferably 10% by mass or more and 90% by mass or less, and preferably 20% by mass or more and 80% by mass or less. This is because the black ink layer can exhibit a desired surface blackness by setting the content of the black pigment in the above range.

As the binder resin, a known resin used for ink can be applied, and one type may be used alone or two or more types may be used in combination. Examples of the binder resin include polyurethane resin, polyester resin, acrylic resin, vinyl chloride-vinyl acetate copolymer resin, nitrocellulose resin and the like. Among them, polyurethane resin or polyester resin is preferable because it has excellent adhesion, and polyurethane resin is more preferable because it has good flexibility and adhesion to the insulating resin layer.

The polyurethane resin is obtained by a polycondensation reaction of a diisocyanate compound, a polyol compound, a low molecular weight chain extender, and the like, and is a highly flexible and elastic resin having a large number of urethane bonds in the molecule. The polyurethane resin used as the binder resin preferably has a weight average molecular weight in the range of 1,000 to 500,000, more preferably in the range of 30,000 to 100,000.

Examples of the diisocyanate compound for forming the polyurethane resin include methylene diisocyanate, isopropylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and carboxyl groups of dimeric acid. Chain aliphatic diisocyanates such as dimerge diisocyanate substituted with isocyanate group; cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-di (isocyanatemethyl) cyclohexane, methylcyclohexanediisocyanate Cyclic aliphatic diisocyanate such as, dialkyldiphenylmethane diisocyanate such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate such as 4,4'-diphenyltetramethylmethane diisocyanate, 1,5-naphthylene diisocyanate, 4,4 '-Diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylisocyanate, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethyl Aromatic diisocyanates such as xylylene diisocyanate; amino acid diisocyanates such as lysine diisocyanates can be mentioned. The above polyisocyanate compounds including these diisocyanate compounds are used alone or in combination of two or more.

Examples of the polyol compound for forming the polyurethane resin include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols and the like. Examples of the polyether polyols include polyethylene glycol obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran and the like, polypropylene glycol, polyoxytetramethylene ether glycol and the like. Examples of polyester polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and pentanediol. Saturated or unsaturated low molecular weight glycols such as 3-methyl-1,5-pentanediol, 1,6-hexanediol, octanediol, 1,4-butinediol, dipropylene glycol, bisphenol A, hydrogenated bisphenol A, etc. And dibasic acids such as adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, glycolic acid, pimelic acid, azelaic acid, sebacic acid, sveric acid or these. Examples thereof include compounds obtained by dehydration condensation of an acid anhydride or the like corresponding to the above.

In addition to the black pigment and binder resin described above, the black ink layer can contain known materials used in general-purpose ink compositions. Known materials include, for example, dispersants such as cellulose-based resins; various isocyanate-based curing agents; particle-based blocking inhibitors such as silica, calcium carbonate, calcium phosphate, talc, urethane beads, acrylic beads, and silicone beads, and polyethylene. Examples thereof include anti-blocking agents such as wax (PE wax), fatty acid amides, fatty acid esters, and organic compound-based blocking inhibitors such as higher fatty acids.

The thickness of the black ink layer may be a size that enables the desired black design to be exhibited by overlapping with the black adhesive layer, and specifically, the thickness of the black ink layer is preferably 1 μm or more. , 1.2 μm or more, 1.5 μm or more, and the thickness is preferably 3 μm or less, 2.5 μm or less, 2 μm or less. More specifically, the thickness of the black ink layer is preferably 1 μm or more and 3 μm or less, more preferably 1 μm or more and 2 μm or less, and more preferably 1.2 μm or more and 2 μm or less. This is because by setting the thickness of the black ink layer within the above range, both thin thickness and surface blackness can be achieved.

The concealment rate of the black ink layer is not particularly limited as long as it can exhibit a desired surface blackness by overlapping with the black adhesive layer described above, but is preferably 70% or more, and is preferably 80% or more. More preferably, it is more preferably 90% or more. Further, the higher the shielding rate of the black ink layer is, the more preferable it is, and the upper limit thereof can be 100%. By setting the hiding ratio of the black ink layer within the above range, it is possible to suppress the influence of the color of the conductive layer from appearing on the surface of the conductive laminate, and it becomes easier to control the blackness.

The concealment rate of the black ink layer can be measured by the same method as the method for measuring the concealment rate of the black adhesive layer.

The insulating portion in the present invention may be provided with a matte layer in addition to the black ink layer and the insulating resin layer described above. By providing the matte layer, the ^{physical characteristics of the lightness L *} , the chromaticity a ^* , the chromaticity b ^* , and the 60 ° gloss value can be adjusted. In particular, it is preferable to provide a matte layer for adjusting the 60 ° gloss value.

The matte layer is a layer containing a resin binder and fine particles. Examples of the fine particles include general-purpose fine particles such as silica, calcium carbonate, and barium sulfate. Further, as the resin binder, a resin commonly used for the matte layer can be used. Above all, the matte layer preferably has silica particles dispersed in a urethane resin.

The thickness of the matte layer is not particularly limited as long as it can exhibit a desired function, and is preferably 0.3 μm or more, 0.4 μm or more, and 0.5 μm or more. The thickness of the matte layer may be a size that does not significantly affect the total thickness of the conductive laminate, and is preferably 3 μm or less, 2 μm or less, and 1.5 μm or less. More specifically, the thickness of the matte layer is preferably 0.3 μm or more and 3 μm or less, and more preferably 0.5 μm or more and 1.5 μm or less.

When the insulating portion further has a matte layer, the insulating portion may have the insulating resin layer, the black ink layer, and the matte layer laminated in this order from the black adhesive layer side. The black ink layer, the insulating resin layer, and the matte layer may be laminated in this order from the black pressure-sensitive adhesive layer side. Above all, in the insulating portion, it is preferable that the insulating resin layer, the black ink layer, and the matte layer are laminated in this order from the black pressure-sensitive adhesive layer side. This is because the surface blackness of the conductive laminate can be further adjusted by overlapping with the black pressure-sensitive adhesive layer with the black ink layer and the matte layer.

The total thickness of the insulating portion in the present invention is preferably 3 μm or more and 10 μm or less, more preferably 4 μm or more and 8 μm or less, and even more preferably 5 μm or more and 7 μm or less. By setting the total thickness of the insulating portion within the above range, it is possible to exhibit the physical properties of the insulating portion and the blackness in a well-balanced manner.

The insulating portion in the present invention preferably has a surface resistivity of 1 × 10 ⁹ Ω / □ or more, more preferably 1 × 10 ¹⁰ Ω / □ or more, and 1 × 10 ¹¹ Ω / □ or more. Is more preferable. When the surface resistivity of the insulating portion is in the above range, the conductive laminate of the present invention can maintain higher insulating properties on the surface on the insulating portion side. The larger the surface resistivity of the insulating part, the better, but in general, 1 × 10 ¹⁸ Ω / □ or less, 1 × 10 ¹⁶ Ω / □ or less, 1 × 10 ¹⁴ Ω / □ or more, 1 × 10 ¹² Ω / □ It can be as follows.

The surface resistivity of the insulating part refers to the value measured according to JIS-K6911, and 500V was applied to the black adhesive layer using a resistivity meter (Advantest digital ultra-high resistance / micro ammeter R8340, TR42 box). It can be measured by applying the voltage of.

The insulating portion in the present invention is obtained by applying a black ink in which a black pigment is dispersed in a binder resin to the surface of a resin film as an insulating resin layer to form a black ink layer. As the coating method, a known and commonly used coating method can be used, and the coating method is not particularly limited, but the gravure coating method is most preferable.

When the insulating portion in the present invention further has a matte layer on the black ink layer, the matte layer contains a matting agent (matte agent) in which fine particles such as silica are dispersed in a resin binder. It can be formed by applying a surface treatment agent to the surface of the black ink layer.

(Conductive laminate)
The conductive laminate of the present invention preferably has a total thickness of 20 μm or more, more preferably 25 μm or more, and even more preferably 30 μm or more. The total thickness is preferably 40 μm or less, more preferably 38 μm or less, and even more preferably 36 μm or less. More specifically, the conductive laminate of the present invention preferably has a total thickness of 20 μm or more and 40 μm or less, more preferably 25 μm or more and 38 μm or less, and more preferably 30 μm or more and 36 μm or less. By setting the total thickness of the conductive laminate within the above range, it is possible to achieve both conductivity and electromagnetic wave shielding properties, as well as surface insulation and blackness properties, while the total thickness is small and thin. be able to.

The conductive laminate of the present invention has the above-mentioned layer structure, and the surface of the conductive laminate located on the first main surface side of the conductive layer (that is, the surface on the insulating portion side of the conductive laminate). CIE L ^* a ^* b ^{* The hue L *} , chromaticity a ^* , and chromaticity b ^* specified in the color system show predetermined values, so that the hue of the conductive layer is suppressed and the conductivity is conductive. The surface of the laminate on the insulating portion side is excellent in color density and hue, and can exhibit a high-quality black color. As a result, the conductive laminate of the present invention can exhibit excellent surface blackness, particularly black design, while satisfactorily satisfying conductivity, insulation, electromagnetic wave shielding, etc., while being thin. can.

The conductive laminate of the present invention has a brightness L ^{* defined by the CIE L *} a ^* b ^* color system on the surface of the conductive laminate located on the first main surface side of the conductive layer. It may be 20 or more, preferably 21 or more, 21.5 or more, 22 or more, and 22.5 or more. The brightness L ^* may be 27 or less, preferably 25 or less, 24 or less, and 23 or less. More specifically, the brightness L ^* may be 20 or more and 27 or less, particularly preferably 21 or more and 25 or less, further preferably 21.5 or more and 24 or less, and even more preferably 22 or more and 23 or less. The conductive laminate of the present invention can exhibit a black design property excellent in jet blackness as a conductive laminate when the ^{brightness L *} measured from the surface on the insulating portion side is within the above range, and can be used as a black component. It is possible to create a sense of unity with the black color exhibited by black parts when used in combination.

The conductive laminate of the present invention has a chromaticity a ^{* defined by the CIE L *} a ^* b ^* color system on the surface of the conductive laminate located on the first main surface side of the conductive layer. May be -2 or more, preferably -1.5 or more, -1 or more, -0.5 or more, and 0 or more. The chromaticity a ^* may be 2 or less, preferably 1.5 or less, 1 or less, and 0.5 or less. More specifically, the chromaticity a ^* may be -2 or more and 2 or less, preferably -1 or more and 1 or less, and more preferably -0.5 or more and 0.5 or less. ^{The conductive laminate of the present invention can exhibit excellent black design as a conductive laminate when the chromaticity a *} measured from the surface on the insulating portion side is within the above range, and can be used in combination with a black component. It is possible to create a sense of unity with the black color exhibited by the black parts.

The conductive laminate of the present invention has a chromaticity b ^{* defined by the CIE L *} a ^* b ^* color system on the surface of the conductive laminate located on the first main surface side of the conductive layer. May be -2 or more, preferably −1.5 or more, -1 or more. The chromaticity b ^* may be 2 or less, preferably 1.5 or less, 1 or less, 0.5 or less, and 0 or less. More specifically, the chromaticity b ^* may be -2 or more and 2 or less, preferably -2 or more and 0 or less, -1.5 or more and 0.5 or less, -1.5 or more and 0 or less, -1 or more. It is 0 or less. ^{The conductive laminate of the present invention can exhibit excellent black design as a conductive laminate when the chromaticity b *} measured from the surface on the insulating portion side is within the above range, and can be used in combination with a black component. It is possible to create a sense of unity with the black color exhibited by the black parts.

The conductive laminate of the present invention has a brightness L ^{* defined by the CIE L *} a ^* b ^* color system on the surface of the conductive laminate located on the first main surface side of the conductive layer. It may be 20 or more and 27 or less, the chromaticity a ^* is -2 or more and 2 or less, and the chromaticity b ^* is -2 or more and 2 or less. Among them, the lightness L ^* is 21 or more and 25 or less and the chromaticity is It is preferable that a ^* is -1 or more and 1 or less, the chromaticity b ^* is -1.5 or more and 0.5 or less, the brightness L ^* is 21.5 or more and 24 or less, and the chromaticity a ^{* is-.} More preferably, it is 0.5 or more and 0.5 or less, and the chromaticity b ^* is -1 or more and 0 or less.

^{The CIE color values (L *} , a ^* , b ^* ) of the conductive laminate of the present invention can be measured according to JIS Z 8722, respectively. Specifically, the value is measured from the surface of the conductive laminate on the insulating side according to the measurement standard JIS Z 8722 with a C spectrum of 2 ° using SPECTROPHOTOMETER CM-5 manufactured by KONICA MINOLTA.

Further, in the conductive laminate of the present invention, the 60 ° gloss value of the surface of the conductive laminate located on the first main surface side of the conductive layer is preferably 1 or more and 5 or less. It is preferably 4 or more, and more preferably 1 or more and 3 or less. In the conductive laminate of the present invention, when the 60 ° C. gloss value measured from the surface on the insulating portion side is within the above range, the glossiness is suppressed and the excellent matte design can be exhibited as the conductive laminate. When used in combination with black parts, it can suppress the conspicuousness due to the glossiness and give a sense of unity with the black color exhibited by the black parts.

The 60 ° gloss value is the glossiness measured at a set angle of 60 ° with respect to the surface of the conductive laminate on the insulating portion side according to JIS Z 8741. The measurement can be performed using a commercially available measuring device (for example, Cat No. 4563 Micro-TRI-Gloss Meter manufactured by BYK).

Further, the conductive laminate of the present invention has the above-mentioned layer structure, and therefore, although it is thin, the surface (that is, the insulating portion) of the above-mentioned conductive laminate located on the first main surface side of the above-mentioned conductive layer. The side surface) may exhibit high insulation, while the surface of the conductive laminate located on the second main surface side of the conductive layer (that is, the surface on the conductive layer side) may exhibit high conductivity. can.

Electroconductive laminate of the present invention, the surface resistivity of the surface of the electroconductive laminate positioned on the first main surface side of the conductive layer (i.e. the insulating portion side surface) is 1 × 10 ⁸ Ω / □ or more It is preferably 1 × 10 ⁹ Ω / □ or more, more preferably 1 × 10 ¹⁰ Ω / □ or more, and even more preferably 1 × 10 ¹¹ Ω / □ or more. When the surface resistivity of the surface on the insulating portion side is within the above range, the conductive laminate of the present invention can exhibit higher insulating properties on the surface on the insulating portion side. The larger the surface resistivity of the surface of the conductive laminate on the insulating side, the more preferable it is, but generally 1 × 10 ¹⁸ Ω / □ or less, 1 × 10 ¹⁶ Ω / □ or less, 1 × 10 ¹⁴ Ω / □ or less. It can be 1 × 10 ¹² Ω / □ or less.

Further, in the conductive laminate of the present invention, the surface resistivity of the surface of the conductive laminate (that is, the surface on the conductive layer side) located on the second main surface side of the conductive layer is 10 mΩ / □ or less. It is preferably 1 mΩ / □ or less, more preferably 0.6 mΩ / □ or less. When the surface resistivity of the surface on the conductive layer side is in the above range, the conductive laminate of the present invention can exhibit higher conductivity on the surface on the conductive layer side. The surface resistivity of the surface of the conductive laminate on the conductive layer side is preferably smaller, but can generally be 0.001 mΩ / □ or more.

The surface resistivity of the insulation side surface and the conductive layer side surface of the conductive laminate refers to the values measured according to JIS-K6911, respectively, using a resistivity meter (Lorester MCP-T600 manufactured by Mitsubishi Chemical Corporation). , A 4-terminal probe can be applied to the surface of the conductive laminate on the insulating portion side or the surface on the conductive layer side for measurement.

(Manufacturing method of conductive laminate)
The method for producing the conductive laminate of the present invention is not particularly limited. Among them, a step of preparing a black ink and a black adhesive, and a step of forming an insulating portion by applying black ink to one surface of an insulating resin layer to form an insulating portion having a black ink layer and an insulating resin layer. A black pressure-sensitive adhesive layer forming step of applying the black pressure-sensitive adhesive to the surface of the insulating portion opposite to the black ink layer to form a black pressure-sensitive adhesive layer, and a conductive layer on the black pressure-sensitive adhesive layer. A manufacturing method including a conductive layer forming step of laminating a metal foil as a base is preferable because it is possible to produce a conductive laminate while suppressing the occurrence of wrinkles and to be excellent in productivity.

In the insulating portion forming step, the method of applying the black ink to the insulating resin layer is not particularly limited as long as the thickness of the black ink layer after drying becomes a desired size, and for example, a gravure coating method or the like can be used. ..

Further, in the black pressure-sensitive adhesive layer forming step, the method of applying the black pressure-sensitive adhesive is not particularly limited as long as the thickness of the black pressure-sensitive adhesive layer after drying becomes a desired size. A known method such as the lip coating method can be used.

(Use of conductive laminate)
Since the conductive laminate of the present invention is thin and has excellent conductivity, insulation, and surface blackness, a conductive pressure-sensitive adhesive layer is provided on the second main surface of the conductive layer as a single unit or as described later. It can be widely applied to applications that require these characteristics. Above all, it can be suitably used for shielding and grounding of thin mobile devices and the like.

II. Conductive Laminated Tape The conductive laminated tape of the present invention has the conductive laminated body described in the above section "I. Conductive Laminated Body" and the conductive pressure-sensitive adhesive layer. , It is provided on the second main surface of the conductive layer constituting the conductive laminate.

According to the conductive laminated tape of the present invention, it is possible to achieve both conductivity, electromagnetic wave shielding property, surface insulation property, and blackness property while being thin and small in total thickness.

(Conductive laminate)
Since the conductive laminate in the present invention is the same as the details described in the above section "I. Conductive laminate", the description thereof is omitted here.

(Conductive adhesive layer)
The conductive pressure-sensitive adhesive layer in the present invention contains a pressure-sensitive adhesive component and a conductive filler.

As the conductive filler, nickel powder, copper powder, silver powder, gold powder, conductive carbon black, metal-plated glass, resin powder and the like can be used. Among them, nickel powder is more preferable because it is excellent in conductivity to a metal foil which is a conductive layer in a conductive laminate, particularly to a copper foil or a stainless steel foil.

The content of the conductive filler in the conductive pressure-sensitive adhesive layer can be an amount capable of exhibiting desired conductivity, and is not particularly limited, but is the total amount (100% by mass) of the conductive pressure-sensitive adhesive layer. ), It is preferably in the range of 0.1% by mass to 80% by mass, preferably in the range of 0.5% by mass to 40% by mass, and most preferably in the range of 0.8% by mass to 10% by mass. preferable. This is because when the content of the conductive filler is within the above range, it is easy to achieve both conductivity and adhesiveness even if the material is thin.

The pressure-sensitive adhesive component constituting the conductive pressure-sensitive adhesive layer is not particularly limited, and for example, acrylic pressure-sensitive adhesive, rubber-based pressure-sensitive adhesive, silicone-based pressure-sensitive adhesive, urethane-based pressure-sensitive adhesive, polyester-based pressure-sensitive adhesive, and styrene-diene block. Appropriately select and use known adhesives such as copolymerization adhesives, vinyl alkyl ether adhesives, polyamide adhesives, fluorine adhesives, creep property improved adhesives, and radiation curable adhesives. Can be done. The pressure-sensitive adhesive component can be used alone or in combination of two or more.

Among them, as the pressure-sensitive adhesive component, an acrylic pressure-sensitive adhesive can be preferably used because of its high adhesive reliability. Acrylic adhesives use (meth) acrylic polymers as adhesive components or main agents, and if necessary, cross-linking agents, tackifiers, softeners, plasticizers, fillers, anti-aging agents, colorants, etc. Appropriate additives are included. The (meth) acrylic polymer is a polymer containing (meth) acrylic acid alkyl ester as the main component of the monomer, and is a monomer (copolymerization) capable of copolymerizing with (meth) alkyl ester as needed. It is prepared by using a sex monomer).

As the acrylic copolymer, an acrylic copolymer containing a (meth) acrylate monomer having 1 to 14 carbon atoms as a main monomer component can be preferably used, and as the (meth) acrylate having 1 to 14 carbon atoms, for example, Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, Examples thereof include monomers such as isooctyl (meth) acrylate, isononyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, and one or more of these are used. Of these, a (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is preferable, and a (meth) acrylate having a linear or branched structure having 4 to 9 carbon atoms is more preferable. Of these, n-butyl acrylate and 2-ethylhexyl acrylate can be preferably used, and these may be used alone or in combination.

The content of the (meth) acrylate having 1 to 14 carbon atoms in the acrylic copolymer is preferably 80% by mass to 98.5% by mass in the monomer components constituting the acrylic copolymer, and is 90% by mass. More preferably, it is from% by mass to 98.5% by mass.

Further, the acrylic copolymer is preferably copolymerized with a highly polar vinyl monomer, and examples of the highly polar vinyl monomer include a vinyl monomer having a carboxyl group, a vinyl monomer having a hydroxyl group, and a vinyl monomer having an amide group. And one or more of these are used. Among them, the carboxyl group-containing monomer can be preferably used because it is easy to adjust the adhesiveness of the pressure-sensitive adhesive to a suitable range.

As the vinyl monomer having a carboxyl group, acrylic acid, methacrylic acid, itaconic acid, maleic acid, (meth) acrylic acid dimer, crotonic acid, ethylene oxide-modified amber acid acrylate and the like can be used, and acrylic acid is used together. It is preferable to use it as a polymerization component.

When a vinyl monomer having a carboxyl group is used, the content thereof is preferably 0.2% by mass to 15% by mass, preferably 0.4% by mass, in the monomer components constituting the acrylic copolymer. It is more preferably 10% by mass, and further preferably 0.5% by mass to 6% by mass. By containing it in the above range, it is easy to adjust the adhesiveness of the pressure-sensitive adhesive to a suitable range.

Examples of the monomer having a hydroxyl group include hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. Meta) Acrylate can be used.

Examples of the monomer having an amide group include N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, acrylamide, N, N-dimethylacrylamide, and the like.

Other highly polar vinyl monomers include sulfonic acid group-containing monomers such as vinyl acetate, ethylene oxide-modified amber acid acrylate, 2-acrylamide-2-methylpropanulphonic acid, 2-methoxyethyl (meth) acrylate, and 2-phenoxyethyl ( Examples thereof include terminal alkoxy-modified (meth) acrylates such as meta) acrylates.

The total content of the highly polar vinyl monomer is preferably 0.2% by mass to 15% by mass, and is 0.4% by mass to 10% by mass in the monomer components constituting the acrylic copolymer. More preferably, it is more preferably 0.5% by mass to 6% by mass. By containing it in the above range, it is easy to adjust the adhesiveness of the pressure-sensitive adhesive to a suitable range.

The weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 500,000 or more, 600,000 or more, and 700,000 or more. The weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 2 million or less, 1.8 million or less, 1.6 million or less, 1.2 million or less, and 1 million or less. By setting the weight average molecular weight (Mw) of the (meth) acrylic polymer within the above range, the conductive pressure-sensitive adhesive layer can have good initial adhesiveness to the conductive layer in the conductive laminate. More specifically, the weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably in the range of 500,000 to 1.2 million, more preferably in the range of 500,000 to 1,000,000.

The (meth) acrylic polymer can be prepared by a conventional polymerization method such as a solution polymerization method, an emulsion polymerization method, or an ultraviolet irradiation polymerization method.

A tackifier resin may be added to the conductive pressure-sensitive adhesive layer in order to improve the adhesive strength. Examples of the tackifier resin include rosin-based resins such as rosin and rosin ester compounds; terpene-based resins such as diterpene polymers and α-pinene-phenol copolymers; aliphatic (C5) and aromatic (C5) and aromatic resins (C5). Examples thereof include petroleum resins such as C9); styrene resins; phenolic resins; xylene resins; and methacrylic resins. Among them, it is preferable to contain a rosin-based resin in order to make it thin and improve the adhesive strength, and it is more preferable to contain a polymerized rosin-based resin. Further, a styrene resin may be mixed and contained in addition to the rosin resin.

Further, in order to increase the initial adhesive strength, it is preferable to mix and use a tackifier resin that is liquid at room temperature. Examples of the tackifier resin that is liquid at room temperature include the liquid resin of the tackifier resin described above, and low molecular weight liquid rubbers such as process oils, polyester-based plasticizers, and polybutenes. A terpene phenol resin is particularly preferable. Commercially available products include YP-90L manufactured by Yasuhara Chemical Co., Ltd.

The amount of the tackifier resin added is preferably in the range of 10 parts by mass to 70 parts by mass with respect to 100 parts by mass of the acrylic copolymer. More preferably, it is in the range of 20 parts by mass to 60 parts by mass. The adhesive strength can be improved by adding the tackifier resin within the above range.

The gel fraction of the conductive pressure-sensitive adhesive layer is not particularly limited, but is preferably 10 to 60% by mass because sufficient adhesiveness is likely to be exhibited even if the thickness is thin, and is preferably 20 to 50% by mass. Is more preferable, and more preferably 25 to 45% by mass.

The gel fraction of the conductive pressure-sensitive adhesive layer is expressed as a percentage of the original mass by immersing the cured conductive pressure-sensitive adhesive layer in toluene and measuring the mass of the insoluble matter remaining after being left for 24 hours after drying. ..
Gel fraction (mass%) = [(mass of conductive pressure-sensitive adhesive layer after immersion in toluene) / (mass of conductive pressure-sensitive adhesive layer before immersion in toluene)] × 100

The storage elastic modulus of the conductive pressure-sensitive adhesive layer at 25 ° C. ^{is preferably 1 × 10 4} or more and 5 × 10 ⁵ Pa or less, and ^{more preferably 2 × 10 4} or more and 1 × 10 ⁵ Pa or less. This is because the storage elastic modulus of the conductive pressure-sensitive adhesive layer at 25 ° C. is within the above range, so that even a thin-film conductive pressure-sensitive adhesive layer can easily achieve both adhesiveness and workability at a high level. The storage elastic modulus of the conductive pressure-sensitive adhesive layer at 25 ° C. is a value measured by the same method and conditions as the method for measuring the storage elastic modulus of the black pressure-sensitive adhesive layer at 25 ° C. described above.

The conductive pressure-sensitive adhesive layer may have a single-layer structure, or may have a multi-layer structure in which conductive pressure-sensitive adhesive layers are provided on both sides of the conductive base material.

Examples of the conductive base material when the conductive pressure-sensitive adhesive layer has a multi-layer structure include a metal foil base material, a base material obtained by plating a wet polyester-based non-woven fabric base material, and the like. Examples of the material of the metal foil include gold, silver, copper, aluminum, nickel, iron, tin and alloys thereof. In addition, examples of the base material obtained by plating the wet polyester-based non-woven fabric base material include those using electroless metal plating as the plating. Examples of the metal to be plated include copper, nickel, silver, platinum, and aluminum, and among them, copper or nickel is preferable from the viewpoint of conductivity and cost. The thickness of the conductive base material is not particularly limited, but can be, for example, 1 μm or more and 50 μm or less.

The thickness of the conductive pressure-sensitive adhesive layer can be such that the conductivity and the pressure-sensitive adhesive can be exhibited, and is preferably 2 μm or more and 60 μm or less, and more preferably 3 μm or more and 10 μm or less. By setting the thickness of the conductive pressure-sensitive adhesive layer within the above range, the total thickness of the conductive laminated tape of the present invention can be reduced, and the conductivity can be further increased.

When the conductive pressure-sensitive adhesive layer has a multi-layer structure, the thickness of the entire multi-layer structure is preferably 3 μm or more and 60 μm or less, and more preferably 5 μm or more and 10 μm or less.

The conductive pressure-sensitive adhesive layer is provided on the second main surface of the conductive layer in the conductive laminate. As illustrated in FIG. 3, the conductive pressure-sensitive adhesive layer 11 may be provided over the entire second main surface of the conductive layer 1 in the conductive laminate 10, as illustrated in FIG. The conductive pressure-sensitive adhesive layer 11 may be provided in a pattern on the second main surface of the conductive layer 1 in the conductive laminate 10. In the latter case, the insulating pressure-sensitive adhesive layer 12 is arranged in the region on the second main surface of the conductive layer 1 where the conductive pressure-sensitive adhesive layer 11 is not arranged, that is, the second of the conductive layer 10. The conductive pressure-sensitive adhesive layer 11 and the insulating pressure-sensitive adhesive layer 12 may be alternately arranged in a pattern on the main surface of the surface. An embodiment in which the conductive pressure-sensitive adhesive layer and the insulating pressure-sensitive adhesive layer are alternately arranged in a pattern is preferable because the adhesiveness can be improved.

When the conductive pressure-sensitive adhesive layer and the insulating pressure-sensitive adhesive layer are alternately arranged in a pattern on the second main surface of the conductive layer, the insulating pressure-sensitive adhesive layer is a conductive pressure-sensitive adhesive layer. It can be the same as the conductive pressure-sensitive adhesive layer except that it does not contain a conductive filler.

(Arbitrary configuration)
The conductive laminated tape of the present invention includes at least the above-mentioned conductive laminated body and conductive pressure-sensitive adhesive layer in the composition, but may include other configurations. For example, a release layer may be further provided on the surface of the conductive pressure-sensitive adhesive layer opposite to the conductive laminate. This is because the conductive laminated tape can be protected by providing the release layer.

As the release layer, a known release layer may be appropriately selected and used. A resin film that has been mold-released is preferable because it has excellent smoothness. Among them, a polyester film is preferable from the viewpoint of excellent heat resistance.

The surface of the peeling layer is preferably peeled in order to impart easy peeling property. Specifically, it is preferable that the surface of the peeling layer is provided with a peeling treatment layer. The peeling treatment layer can be formed by a general-purpose peeling treatment agent used for the peeling layer of the double-sided adhesive tape. Examples of such a stripping agent include silicone-based, fluorine-based, and long-chain alkyl-based stripping agents. The peeling treatment layer may be formed by laminating or coating.

The peeling force of the peeling layer may be appropriately adjusted according to the usage mode and the like, but the peeling force with respect to the conductive laminated tape is 0.01 N / 20 mm to 2 N / 20 mm, preferably 0.05 N / 20 mm to 0.15 N /. It can be 20 mm. This is because it becomes easy to suppress the deformation of the conductive laminated tape when the release layer is peeled off. The peeling force is such that the exposed surface of the conductive adhesive layer of the conductive laminated tape is lined with a PET film having a thickness of 50 μm as a peeling layer, and peeled in the 180 ° direction at a speed of 0.3 m / min to 10 m / min. Can be measured.

(Conductive laminated tape)
The conductive laminated tape of the present invention preferably has a total thickness of 22 μm or more and 100 μm or less, more preferably 25 μm or more and 50 μm or less, and even more preferably 30 μm or more and 45 μm or less. By setting the total thickness of the conductive laminated tape within the above range, it is possible to achieve both conductivity and electromagnetic wave shielding properties, as well as surface insulation and blackness properties, while the total thickness is small and thin. be able to. The total thickness of the conductive adhesive tape referred to in the present specification does not include the thickness of the release layer.

The conductive laminated tape of the present invention has CIE L ^* a ^* b ^* brightness L ^* , chromaticity a ^* , and chromaticity b ^* , which are measured from the surface on the conductive laminated body side, respectively. ^{CIE L *} a ^* b ^{* CIE L * a * b * Brightness L *} and chromaticity a ^* specified by the color system, measured from the surface of the conductive laminate on the insulating side, as described in the section "I. Conductive laminate" above. , It is preferable that the color is within the range of ^{chromaticity b *.}

Further, in the conductive laminated tape of the present invention, the 60 ° gloss value measured from the surface on the conductive laminated body side is the insulating portion side of the conductive laminated body described in the above section "I. Conductive laminated body". It is preferably within the range of the 60 ° gloss value measured from the surface.

^{The CIE color values (L *} , a ^* , b ^* ) and 60 ° gloss value of the conductive laminated tape of the present invention are the CIEs of the conductive laminated body described in the above section "I. Conductive laminated body", respectively. It is a value measured under the same method and conditions as the method for measuring the color value (L ^* , a ^* , b ^{*) and the 60 ° gloss value.}

In the conductive laminated tape of the present invention, the hiding rate measured from the surface on the conductive laminated body side is measured from the insulating portion side surface of the conductive laminated body described in the above section "I. Conductive laminated body". It is preferable that it is within the range of the concealment rate. The concealment rate of the conductive laminated tape is measured by the same method and conditions as the method for measuring the concealment rate measured from the surface of the conductive laminate on the insulating portion side described in the section "I. Conductive laminate" above. The value.

In the conductive laminated tape of the present invention, the surface resistivity measured from the surface on the conductive laminated body side is measured from the insulating portion side surface of the conductive laminated body described in the above section "I. Conductive laminated body". It is preferably within the range of the surface resistivity to be obtained.

Further, in the conductive laminated tape of the present invention, the surface resistivity measured from the surface on the conductive pressure-sensitive adhesive side is preferably 10 mΩ / □ or less, more preferably 1 mΩ / □ or less, and 0.6 mΩ. / □ or less is more preferable. The smaller the surface resistivity measured from the surface of the conductive laminated tape on the conductive adhesive side, the more preferable it is, but in general, it can be 0.001 mΩ / □ or more.

The surface resistivity of the surface on the conductive laminate side and the surface on the conductive adhesive layer side of the conductive laminated tape indicate the values measured according to JIS-K6911, respectively, and the resistivity meter (Lorester MCP manufactured by Mitsubishi Chemical Corporation). -T600) can be used to apply a 4-terminal probe to the surface of the conductive laminated tape on the conductive laminate side or the surface on the conductive adhesive layer side for measurement.

(Manufacturing method of conductive laminated tape)
The method for producing the conductive adhesive sheet of the present invention is not particularly limited. The conductive adhesive sheet of the present invention prepares, for example, a step of preparing the conductive laminate described in the above section "I. Conductive laminate", a conductive pressure-sensitive adhesive containing a conductive filler and a pressure-sensitive adhesive component. Step, a step of forming a conductive pressure-sensitive adhesive layer by applying a conductive pressure-sensitive adhesive on the second main surface of the conductive layer in the conductive laminate so that the thickness after drying becomes a desired size. It can be produced by using the production method having.

Further, the conductive adhesive sheet of the present invention is, for example, a step of preparing a conductive laminate described in the above section "I. Conductive laminate", a conductive pressure-sensitive adhesive containing a conductive filler and a pressure-sensitive adhesive component. A step of preparing, a step of applying a conductive adhesive to both sides of a conductive base material so that the thickness after drying becomes a desired size to form a conductive double-sided adhesive tape, conductivity in the above-mentioned conductive laminate. It can be manufactured by using a manufacturing method including a step of laminating a second main surface of the layer and one pressure-sensitive adhesive layer of the conductive double-sided pressure-sensitive adhesive tape.

The use of the conductive adhesive sheet of the present invention can be the same as the use described in the above section "I. Conductive laminate".

The present disclosure is not limited to the above embodiments. The above-described embodiment is an example, and any object having substantially the same structure as the technical idea described in the claims of the present disclosure and exhibiting the same effect and effect is the present invention. Included in the technical scope of the disclosure.

Examples and comparative examples will be specifically described below.

(Polyurethane resin solution A)
A number obtained by reacting an acid component of adipic acid / terephthalic acid = 50/50 and 3-methyl-1,5-pentanediol in four flasks equipped with a stirrer, a thermometer, a reflux cooler and a nitrogen gas introduction tube. 192.9 parts by mass of a polyester polyol having an average molecular weight (hereinafter referred to as Mn) of 2,000, 15.8 parts by mass of 1,4-butanediol, and 77.9 parts by mass of isophorone diisocyanate were charged under a nitrogen stream. Was reacted at 90 ° C. for 5 hours. Next, 11.0 parts by mass of isophoronediamine, 2.4 parts by mass of di-n-butylamine, and 700 parts by mass of methyl ethyl ketone were further added and reacted at 50 ° C. for 4 hours under a stirring frame to produce a resin. A polyurethane resin solution A having a solid content concentration of 30.0% by mass, a Gardner viscosity U (25 ° C.), an amine value = 0, and a weight average molecular weight of 30,000 was obtained.

(Black ink)
The prepared polyurethane resin solution A was added to 55 parts by mass (NV. 30%) as an organic black pigment (1- {4-[(4,5,6,7-tetrachloro-3-oxoisoindrin-1). -Ilidene) Amino] phenylazo} -2-hydroxy-N- (4'-methoxy-2'-methylphenyl) -11H-benzo [a] carbazole-3-carboxamide) (Near-infrared reflection manufactured by Dainichi Seika Co., Ltd.) 10 parts by mass of the pigment "Chromofine Black A1103" (CAS number: 103621-96-1) and an inorganic filler (Fuji Silicia "Silohobic 704" silane coupling treatment: average particle size 3 by the Coulter counter method .5 μm) in 5 parts by mass, spherical silicone resin beads (“Tospearl 2000B” manufactured by Momentive Performance Materials Co., Ltd .: average particle size 6 μm by the Coulter counter method) in 2 parts by mass, and polyethylene fine powder wax (manufactured by BASF). 2 parts by mass of "Luwax AF29 Micropowerer", 1 part by mass of dispersant ("Sol Spurs 24000GR" manufactured by Lubrizol), 13 parts by mass of methyl ethyl ketone, 9 parts by mass of ethyl acetate, and 5 parts by mass of isopropyl alcohol. And 5 parts by mass of propylene glycol monomethyl ether were added and wet-dispersed in a sand mill for about 1 hour to obtain a mixture. Hexamethylene diisocyanate type isocyanurate (manufactured by Sumika Bayer Urethane Co., Ltd.) was added to this mixture. A black ink was prepared by adding 5 parts by mass of a polyisocyanate curing agent "Sumijour N3300") and 40 parts by mass of a diluent ("NH-NT DC solvent" manufactured by DIC Graphics Co., Ltd.).

(Black ink coat film A (insulation part A))
Using a polyester film (F53 Lumirror # 2.0 manufactured by Toray Industries, Inc., thickness: 2.0 μm) as an insulating resin layer, black ink is applied to one surface of the polyester film so that the thickness becomes 1.0 μm after drying. Was coated with a gravure coat and dried at 100 ° C. for 1 minute to obtain a black ink layer.

Next, on the black ink layer, OS-M suede OP varnish manufactured by Dainichiseika Co., Ltd. was used as a matting agent and gravure-coated so that the thickness of the matte ink layer (matte layer) was 0.5 μm. , Dry at 100 ° C. for 1 minute and aged at 40 ° C. for 2 days. As a result, a black ink coat film A (insulating portion A) in which a black ink layer is formed on one side of the polyester film (insulating resin layer) and a matte ink layer (matte layer) is formed on the black ink layer is obtained. rice field. The total thickness of the black ink coat film A was 3.5 μm. The thickness of the black ink layer was measured by cutting the black ink coat film A with a razor and magnifying the cross section 2500 times with a microscope.

(Black ink coat film B (insulation part B))
Insulating resin layer using polyimide film (Toray DuPont "Capton 20EN", thickness: 5.0 μm) instead of polyester film (Toray "F53 Lumirror # 2.0", thickness: 2.0 μm) A black ink layer is formed on one side of the polyimide film (insulating resin layer), and a matte ink layer (matte layer) is formed on the black ink layer in the same manner as the black ink coat film A. A black ink-coated film B (insulating portion B) was obtained. The total thickness of the black ink coat film B was 6.5 μm.

(Preparation of transparent adhesive A)
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a dropping funnel, 97.98 parts by mass of n-butyl acrylate, 2 parts by mass of acrylic acid, and 0.02 parts by mass of 4-hydroxybutyl acrylate. Acrylic acid having a weight average molecular weight of 900,000 was obtained by adding 0.2 parts by mass of azobisisobutyronitrile as a polymerization initiator to an ethyl acetate solution and performing solution polymerization at 80 ° C. for 8 hours in the solution. A system polymer A was obtained.

Next, 5 parts by mass of polymerized rosin ester (trade name "D-135" manufactured by Arakawa Chemical Co., Ltd.) and disproportionated rosin ester (trade name "KE-100" manufactured by Arakawa Chemical Co., Ltd.) are added to 100 parts by mass of acrylic polymer A. ) To 20 parts by mass and petroleum resin (trade name "FTR6100") to 25 parts by mass, and ethyl acetate was further added to prepare an acrylic pressure-sensitive adhesive solution A having a solid content of 40% by mass.

Add 0.8 parts by mass of an isocyanate-based cross-linking agent (trade name "NC40" manufactured by DIC, 40% by mass of solid content) to 100 parts by mass of acrylic pressure-sensitive adhesive solution A (solid content 40% by mass) to make it uniform. The transparent pressure-sensitive adhesive A was prepared by stirring and mixing as described above. The gel fraction of the transparent pressure-sensitive adhesive A was 20% by mass, and the storage elastic modulus at 25 ° C. was 9 × 10 ⁴ Pa.

(Preparation of black adhesive B)
In 100 parts by mass of the acrylic pressure-sensitive adhesive solution A (solid content 40% by mass), a black colorant (DIC Corporation "DICTON Black AR8555", carbon black content: 45% (solid content ratio), resin solid content concentration 49). %) Is added in an amount of 10 parts by mass, and the mixture is uniformly mixed with a stirrer. Further, an isocyanate-based cross-linking agent (trade name "NC40" manufactured by DIC Corporation) is added by 1.2 parts by mass, and the mixture is stirred and mixed so as to be uniform. As a result, the black pressure-sensitive adhesive B was prepared. The gel fraction of the black pressure-sensitive adhesive B was 20% by mass, and the storage elastic modulus at 25 ° C. was 9 × 10 ⁴ Pa.

(Preparation of black adhesive C)
15 parts by mass of a polyester adhesive (DIC Graphics dry laminating adhesive "Dick Dry LX-703VL", solid content 62%) and an isocyanate curing agent (DIC Graphics curing agent "KR-90") , 90% solid content) and 1 part by mass of black colorant (DIC Corporation "DICTON Black AR8555", carbon black content: 45% (solid content ratio), resin solid content concentration 49%) Black adhesive C was prepared by adding and stirring to make it uniform. The gel fraction of the black adhesive C is 90 mass%, the storage elastic modulus of 25 ° C. was 2 × ¹⁰ 5 Pa.

The gel fraction of the various adhesives is expressed as a percentage of the original mass by immersing the various adhesives in toluene and measuring the mass of the insoluble matter remaining after being left for 24 hours after drying.
Gel fraction (mass%) = [(mass of adhesive after immersion in toluene) / (mass of adhesive before immersion in toluene)] x 100

(Preparation of Conductive Adhesive A)
75.0 parts by mass of n-butyl acrylate, 19.0 parts by mass of 2-ethylhexyl acrylate, and 3.9 parts by mass of vinyl acetate in a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a dropping funnel. , 2.0 parts by mass of acrylic acid, 0.1 parts by mass of 2-hydroxyethyl acrylate, 0.1 parts by mass of 2,2'-azobisisobutylnitrile as a polymerization initiator, and 100 parts by mass of ethyl acetate. The acrylic polymer B having a weight average molecular weight of 600,000 was obtained by dissolving in parts by mass, substituting with nitrogen, and polymerizing at 80 ° C. for 12 hours.

Next, 10 parts by mass of polymerized rosin pentaerythritol ester (“Pencel D-135” manufactured by Arakawa Chemical Industries, Ltd., softening point 135 ° C.) and disproportionated rosing lyserin were added to 100 parts by mass of the solid content of the acrylic polymer B. 10 parts by mass of ester (“Super Ester A-100” manufactured by Arakawa Chemical Industries, Ltd., softening point 100 ° C.) is blended, and the solid content concentration of the acrylic polymer is adjusted to 40% by mass using ethyl acetate. Obtained an acrylic pressure-sensitive adhesive solution B.

100 parts by mass of acrylic pressure-sensitive adhesive solution B (solid content concentration 40% by mass) and 0.4% by mass of nickel powder (“NI255T” beaded conductive particles manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., d50: 26.0 μm) 2 parts by mass of an isocyanate-based cross-linking agent (“Barnock NC40” manufactured by DIC Co., Ltd., solid content 40% by mass) as a cross-linking agent, and 70 parts by mass of ethyl acetate as a diluting solvent for 10 minutes using a dispersion stirrer. The conductive pressure-sensitive adhesive A was prepared by mixing.

(Preparation of Insulating Adhesive A)
Dilute acrylic pressure-sensitive adhesive solution B (solid content concentration 40% by mass) with 100 parts by mass and isocyanate-based cross-linking agent (DIC Co., Ltd. "Bernock NC40", solid content 40% by mass) with 2 parts by mass. The insulating pressure-sensitive adhesive A was prepared by mixing 70 parts by mass of ethyl acetate as a solvent with a dispersion stirrer for 10 minutes.

(Manufacturing of Conductive Adhesive Tape A)
The release film A (trade name "PET38 x 1K0" manufactured by Nipper) is coated with the conductive adhesive A so that the thickness becomes 5 μm after drying, and dried at 100 ° C. for 2 minutes to form the conductive adhesive layer A. Then, a conductive adhesive tape A was obtained.

(Manufacturing of Insulating Adhesive Tape A)
The peeling film A (trade name "PET38 x 1K0" manufactured by Nippa Co., Ltd.) is coated with the insulating adhesive A to a thickness of 5 μm after drying, and dried at 100 ° C. for 2 minutes to form the insulating adhesive layer A. Then, an insulating adhesive tape A was obtained.

(Preparation of adhesive C)
4. In a reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, a dropping funnel and a nitrogen gas inlet, 60 parts by mass of n-butyl acrylate, 35.95 parts by mass of 2-ethylhexyl acrylate, and acrylic acid. 0 parts by mass, 0.05 parts by mass of 4-hydroxybutyl acrylate, 0.2 parts by mass of 2,2'-azobisisobutylnitrile as a polymerization initiator, 50 parts by mass of ethyl acetate and 20 parts by mass of n-hexane. Acrylic copolymer C having a weight average molecular weight of 700,000 was obtained by dissolving the parts in a mixed solvent and polymerizing them at 70 ° C. for 8 hours.

Next, with respect to 100 parts by mass of the solid content of the acrylic copolymer C, 20 parts by mass of a polymerized rosin ester resin (“D-125” manufactured by Arakawa Chemical Industry Co., Ltd.) and a disproportionate rosin ester (Arakawa Chemical Industry Co., Ltd.) 10 parts by mass of "A100" manufactured by Co., Ltd.) was added, and the solid content concentration was adjusted to 45% by mass using ethyl acetate to obtain an acrylic pressure-sensitive adhesive solution C.

Next, 100 parts by mass of the acrylic pressure-sensitive adhesive solution C (45 parts by mass of the solid content) and 1.7 parts by mass of the isocyanate-based cross-linking agent (“Barnock NC-40” manufactured by DIC Corporation, 40% by mass of the solid content, ethyl acetate solution) were added. Acrylic adhesive C was obtained by mixing the parts and mixing them with a dispersion stirrer for 10 minutes.

(Example 1)
The black adhesive B is gravure-coated on the polyester film surface of the black ink coat film A so that the thickness becomes 1.5 μm after drying, and dried at 70 ° C. for 2 minutes to form the black adhesive layer B, and then the thickness is 30 μm. The electrolytic copper foil (“CF-PLFA-30” manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) was bonded to the poppy surface and further aged at 40 ° C. for 2 days to obtain a conductive laminate. The Rz of the glossy surface of the electrolytic copper foil was 0.72 μm, and the Ra was 0.11 μm. The Rz of the poppy surface of the electrolytic copper foil was 1.4 μm, and the Ra was 0.23 μm.

(Example 2)
A conductive laminate was prepared in the same manner as in Example 1 except that an electrolytic copper foil having a thickness of 33 μm (“CF-PLFA-33” manufactured by Fukuda Metal Leaf Powder Industry Co., Ltd.) was used instead of the electrolytic copper foil having a thickness of 30 μm. Obtained. The Rz of the glossy surface of the electrolytic copper foil was 0.78 μm, and the Ra was 0.12 μm. The Rz of the poppy surface of the electrolytic copper foil was 1.5 μm, and the Ra was 0.25 μm.

(Example 3)
A conductive laminate was obtained in the same manner as in Example 1 except that the black ink-coated film B was used instead of the black ink-coated film A.

(Example 4)
A conductive laminate was obtained in the same manner as in Example 1 except that a black adhesive C was used instead of the black adhesive B to form a black adhesive layer C having a thickness of 1.5 μm after drying.

(Example 5)
Same as Example 1 except that a rolled copper foil with a thickness of 30 μm (“TCu-O-30” manufactured by Fukuda Metal Leaf Powder Industry Co., Ltd.) was used instead of the electrolytic copper foil “CF-PLFA-30” with a thickness of 30 μm. A conductive laminate was obtained. The surface roughness of the electrolytic copper foil was flat, Rz was 0.6 μm, and Ra was 0.1 μm.

(Example 6)
The conductive pressure-sensitive adhesive layer A of the conductive pressure-sensitive adhesive tape A was bonded to the electrolytic copper foil surface of the conductive laminate of Example 1 and further aged at 40 ° C. for 2 days to obtain a conductive laminated tape. The release film A of the conductive adhesive tape A is peeled off at the time of evaluation, and the release film A is not included in the total thickness of the conductive laminated tape.

(Example 7)
Conductive adhesive tape A and insulating adhesive tape A are alternately bonded to the electrolytic copper foil surface of the conductive laminate of Example 1 with a width of 5 mm, and further aged at 40 ° C. for 2 days to obtain the conductive laminated tape. Got The release film A of the conductive adhesive tape A and the insulating adhesive tape A is peeled off at the time of evaluation, and the release film A is not included in the total thickness of the conductive laminated tape.

(Comparative Example 1)
Acrylic adhesive C is applied onto a release liner (“PET38 × 1A3” manufactured by Nippa Corporation) using a roll coater so that the thickness after drying is 50 μm, and is placed in a dryer at 80 ° C. for 3 minutes. It was dried to form a transparent pressure-sensitive adhesive layer C, which was cured in an environment of 40 ° C. for 48 hours.

Next, the pressure-sensitive adhesive layer was attached to one surface of an electrolytic copper foil base material having a thickness of 35 μm. Next, an adhesive tape having a total thickness of 10 μm (“IL-10BMF” manufactured by DIC Corporation, a black colored layer (thickness: 1.5 μm) / polyethylene terephthalate film (thickness: 4.5 μm) / transparent adhesive layer (thickness:: A conductive laminated tape was produced by laminating a laminated structure of 4 μm) (“/” indicates a laminated interface) on the other surface of the electrolytic copper foil base material.

(Comparative Example 2)
Polyester resin (Unitika Ltd.) using an isocyanate-based curing agent ("Coronate L" manufactured by Nippon Polyurethane Industry Co., Ltd.) on one side of a PET film with a thickness of 5 μm ("Mylar" manufactured by Teijin DuPont Film Co., Ltd.) "UE3220" manufactured by ^{Nippon Co., Ltd.) was applied at a rate of 3 g / m 2} (converted to a dry coating amount), and a soft aluminum foil (1030N-0 material manufactured by Nippon Foil Co., Ltd.) having a thickness of 7 μm was laminated. Similarly, a soft aluminum foil (1030N-0 material, Nippon Foil Co., Ltd.) having a thickness of 7 μm was laminated on the other surface of the PET film to prepare a base base material.

A conductive black adhesive layer is formed by applying an acrylic adhesive containing 10% by mass of carbon black to the peeled PET film so that the dry thickness becomes 5 μm and drying to form a conductive black adhesive layer. The base base material prepared above was laminated on the adhesive layer.

Subsequently, an insulating black ink (an ink in which aniline black is dispersed in a polyester resin) is applied onto the base base material so as to have a drying thickness of 3 μm and dried to form a black ink layer, thereby forming a conductive property. A laminated tape was obtained.

(Comparative Example 3)
A conductive laminate was obtained in the same manner as in Example 1 except that a transparent pressure-sensitive adhesive A was used instead of the black pressure-sensitive adhesive B to form a transparent pressure-sensitive adhesive layer having a thickness of 1.5 μm after drying.

(Comparative Example 4)
The glossy surface of the electrolytic copper foil ("CF-T8G-DK-35" manufactured by Fukuda Metal Leaf Powder Industry Co., Ltd.) with a thickness of 35 μm is gravure-coated with black ink A to a thickness of 4.5 μm and dried at 100 ° C. for 1 minute. Next, an OS-M suede OP varnish manufactured by Dainichi Seika Co., Ltd. was used on the black ink layer, and the thickness of the matte ink layer (matte layer) was 0.5 μm. It was gravure-coated so as to be so that it was dried at 100 ° C. for 1 minute. As a result, a conductive laminate having a layer structure of a matte ink layer (matte layer) / black ink layer / electrolytic copper foil (/ represents a lamination interface). The Rz of the glossy surface of the electrolytic copper foil was 1.4 μm and the Ra was 0.18 μm. The Rz of the popped surface of the electrolytic copper foil was 10.2 μm and the Ra was 1.6 μm. ..

The ten-point average surface roughness Rz and the arithmetic average roughness Ra of the conductive layer used in Examples and Comparative Examples are each based on JIS B0601 and using HANDYSURF + manufactured by Tokyo Seimitsu Co., Ltd. on the surface of the conductive layer. Surface measurement was performed on any three points in the above, and the average value of the three points obtained by the measurement was used.

[evaluation]
The performance of the conductive laminates of Examples and Comparative Examples and the conductive laminated tapes of Examples and Comparative Examples was evaluated by the following measurement methods.

(Thickness)
Using a thickness gauge (DIGIMICRO MFC-101 manufactured by NIKON) in the conductive laminates of Examples 1 to 5 and Comparative Examples 3 to 4, and the conductive laminates of Examples 6 to 7 and Comparative Examples 1 and 2. The total thickness of the conductive laminate portion was measured. Further, for the conductive laminated tapes of Examples 6 to 7 and Comparative Examples 1 and 2, the total thickness including the pressure-sensitive adhesive layer provided on the second main surface of the conductive layer was also measured.

(Thinness)
The thicknesses of the conductive laminates of Examples 1 to 5 and Comparative Examples 3 to 4 and the conductive laminates of Examples 6 to 7 and Comparative Examples 1 and 2 were evaluated according to the following evaluation criteria. ..
〇: 40 μm or less ×: Over 40 μm

(L ^* , a ^* , b ^* )
Using a spectrophotometer (SPECTROPHOTOMETER CM-5 manufactured by KONICA MINOLTA), the conductive laminates of Examples 1 to 5 and Comparative Examples 3 to 4 and the implementation according to the measurement standard JIS Z 8722 with a C spectrum of 2 °. ^{The CIE color values (L *} , a ^* , b ^* ) were measured from the surfaces of the conductive laminated tapes of Examples 6 to 7 and Comparative Examples 1 and 2 on the insulating portion side, respectively.

(60 ° gloss value)
Conductive laminates of Examples 1-5 and Comparative Examples 3-4, as well as Examples 6-7 and Comparative Examples, using KONICA MINOLTA MINOLTA Multi-Gloss 268 at a set angle of 60 ° according to JIS Z 8741. The gloss value (glossiness Gu) was measured from the surface of the conductive laminated tapes 1 and 2 on the insulating portion side.

(Concealment rate of black adhesive layer)
The concealment rate of the black pressure-sensitive adhesive layer in the conductive laminates of Examples 1 to 5 and Comparative Examples 3 to 4 and the conductive laminate tapes of Examples 6 to 7 and Comparative Examples 1 and 2 was measured by the following method. One side of the release film (trade name "PET38 x 1K0" manufactured by Nippa Co., Ltd.) is coated with the black adhesives B and C used in the examples so as to have a thickness of 1.5 μm after drying, and 2 at 70 ° C. It was dried for a minute to form a black pressure-sensitive adhesive layer, and a black pressure-sensitive adhesive tape was obtained. Next, a method for measuring the color specified in JIS-Z-8722 by attaching a black adhesive tape to the white and black surfaces of the concealment rate test paper (manufactured by Nippon Test Panel Industry Co., Ltd.) and peeling off the release film. Then, among the tristimulus values of the black adhesive layer attached to the white surface and the black surface, the Y value indicating the brightness was measured, respectively. Using a colorimetric gloss meter "CM-3500d" (manufactured by Minolta Co., Ltd.), standard light C in a 2 degree field of view was measured, and the measured Y value was applied to the following formula to measure the concealment rate.
Concealment rate (%) = (Y value of the black adhesive layer attached to the black surface / Y value of the black adhesive layer attached to the white surface) × 100%

(Insulation)
Using a resistivity meter (Lorester MCP-T600 manufactured by Mitsubishi Chemical Corporation), the surface of the conductive laminates of Examples 1 to 5 and Comparative Examples 3 to 4 on the insulating side (the surface opposite to the surface on the conductive layer side). ), And a 4-terminal probe is applied to the surface of the conductive laminated tapes of Examples 6 to 7 and Comparative Examples 1 and 2 on the insulating side (the surface opposite to the surface on the conductive adhesive layer side), and the insulating side. The surface resistivity of the surface was measured. It was evaluated according to the following evaluation criteria.
〇: 9.9 × 10 ⁷ Ω / □ or more of the surface resistivity (overload)
^{×: 9.9 × 10 7 Ω /} □ less than the surface resistivity of the

(Conductivity)
Using a resistivity meter (Lorester MCP-T600 manufactured by Mitsubishi Chemical Corporation), apply a 4-terminal probe to the conductive layer side surface of the conductive laminates of Examples 1 to 5 and Comparative Examples 3 to 4, and apply a 4-terminal probe to the conductive layer side surface. The surface resistivity of was measured. Further, in the conductive laminated tapes of Examples 6 to 7 and Comparative Examples 1 and 2, the surface resistivity was measured on the surface on the conductive pressure-sensitive adhesive layer side. It was evaluated according to the following evaluation criteria.
⊚: 0.6 mΩ / □ or less 〇: Exceeds 0.6 mΩ / □, 10 mΩ / □ or less ×: Exceeds 10 mΩ / □

(Electromagnetic wave shielding property)
A test piece 25 having a width of 20 mm and a length of 40 mm was cut out from the conductive laminates of Examples 1 to 5 and Comparative Examples 3 to 4, and the conductive laminate tapes of Examples 6 to 7 and Comparative Examples 1 and 2, respectively. A sample was prepared by installing the aluminum plate 27 having a thickness of 0.5 mm × 20 cm × 20 cm with a slit 26 having a thickness of 5 mm × 20 mm in the center so as to close the slit (FIG. 5). The test piece 25 of the conductive laminated body was allowed to stand on the aluminum plate, and the test piece 25 of the conductive laminated tape was attached to the aluminum plate 27. Next, the above-mentioned sample was installed in a magnetic field shield box 28 (manufactured by Shield Room) in accordance with the Kansai Electronics Industry Promotion Center (KEC) Law. A spectrum analyzer 29 (MS2661C manufactured by Anritsu Co., Ltd.) was installed in a shield box, and the shield characteristics against electromagnetic waves having a frequency of 3 GHz were evaluated according to the following evaluation criteria (FIG. 6).
⊚: 45db or more ○: 40db or more and less than 45db ×: less than 40db

(Adhesiveness)
A PET film having a thickness of 25 μm (Lumirror S10 # 25 manufactured by Toray Industries, Inc.) is attached to the conductive adhesive A of the conductive adhesive tape A to form a sheet having the structure of release film A / conductive adhesive layer A / PET film. Created. Next, this sheet is cut into a width of 20 mm × a length of 100 mm, the release film A is peeled off, and the surface of the conductive laminate of Examples 1 to 5 and Comparative Examples 3 to 4 is formed on the conductive layer side (copper foil). The conductive pressure-sensitive adhesive layer A was laminated, pressurized once with a 2 kg roller, left at 23 ° C. and 50% RH for 1 hour, and peeled off at a speed of 300 mm / min in the 180 ° direction, and the adhesive strength was measured. .. It was evaluated according to the following evaluation criteria.
⊚: 3N / 20mm or more 〇: 1N / 20mm or more and less than 3N / 20mm ×: 1N / less than 20mm

(Adhesive strength of conductive laminated adhesive tape)
A sample in which the conductive adhesive tape A was attached to the conductive layer surface of the conductive laminates of Examples 1 to 5 and Comparative Examples 3 and 4 was left at 23 ° C. and 50% RH for 1 day, and then cut into a width of 25 mm × a length of 100 mm. , Affixed to a SUS plate, pressurized once with a 2 kg roller, left at 23 ° C. and 50% RH for 1 hour, and peeled off at a speed of 300 mm / min in the 180 ° direction, and the adhesive strength was measured. The conductive laminated tapes of Examples 6 and 7 were cut into 25 mm width × 100 mm length as they were, attached to a SUS plate, pressurized once with a 2 kg roller, and then left at 23 ° C. and 50% RH for 1 hour. Then, the adhesive force when peeled off at a speed of 300 mm / min in the 180 ° direction was measured. It was evaluated according to the following evaluation criteria.
⊚: 8N / 25mm or more 〇: 4N / 25mm or more and less than 8N / 25mm ×: less than 4N / 25mm

The results are shown in Tables 1 to 4.

From Tables 1 to 4, the conductive laminates of Examples 1 to 5 and the conductive laminate tapes of Examples 6 to 7 have an insulating portion having a black ink layer and an insulating resin layer, a black pressure-sensitive adhesive layer, and the like. By having a layer structure in which metal foils and metal foils are laminated in this order as a conductive layer, it is possible to exhibit high conductivity, high electromagnetic wave shielding property, and high surface insulation property while being thin and small in total thickness. By having the above-mentioned laminated structure, the lightness L ^* , the chromaticity a ^* and b ^* of the surface of the conductive laminated body on the insulating portion side can be set within the predetermined ranges, respectively, and the surface blackness, particularly the black design property can be improved. It has been shown that it can be enhanced.

1 ... Conductive layer (metal leaf), 2 ... Black adhesive layer, 3 ... Insulating part, 4 ... Insulating resin layer, 5 ... Black ink layer, 10 ... Conductive laminate, 11 ... Conductive adhesive layer, 12 ... Insulating adhesive layer, 20 ... Conductive laminated tape

Claims (12)

It is a conductive laminate
A conductive layer having a first main surface and a second main surface facing each other,
A black pressure-sensitive adhesive layer provided on the first main surface of the conductive layer,
An insulating portion provided on the black adhesive layer and
Have,
The conductive layer is a metal foil and
The insulating portion has an insulating resin layer and a black ink layer, and has an insulating resin layer and a black ink layer.
^{The chromaticity L *} defined by ^{the CIE L *} a ^* b ^* color system is 20 or more and 27 or less on the surface of the conductive laminate located on the first main surface side of the conductive layer. A ^{conductive laminate having a *} of -2 or more and 2 or less and a chromaticity b ^* of -2 or more and 2 or less. The conductive laminate according to claim 1, wherein the insulating resin layer and the black ink layer are laminated in this order from the black pressure-sensitive adhesive layer side. The conductive laminate according to claim 1 or 2, wherein the surface of the conductive laminate located on the first main surface side of the conductive layer has a 60 ° gloss value of 1 or more and 5 or less. The conductive laminate according to any one of claims 1 to 3, wherein the metal foil is a copper foil. The conductive laminate according to claim 4, wherein the copper foil is an electrolytic copper foil. The conductive laminate according to any one of claims 1 to 5, wherein the ten-point average surface roughness Rz of the conductive layer is 2.0 μm or less. The conductive laminate according to any one of claims 1 to 6, wherein the black ink layer has a thickness of 1 μm or more and 3 μm or less. The conductive laminate according to any one of claims 1 to 7, wherein the thickness of the insulating resin layer is 1 μm or more and 5 μm or less. The conductive laminate according to any one of claims 1 to 8, wherein the black pressure-sensitive adhesive layer has a concealment rate of 20% or more. The conductive laminate according to any one of claims 1 to 8, wherein the total thickness of the conductive laminate is 20 μm or more and 40 μm or less. It has the conductive laminate according to any one of claims 1 to 10 and a conductive pressure-sensitive adhesive layer.
The conductive pressure-sensitive adhesive layer is a conductive laminated tape provided on the second main surface of the conductive layer constituting the conductive laminated body. The conductive pressure-sensitive adhesive layer is provided in a pattern on the second main surface of the conductive layer.
The conductive laminated tape according to claim 11, wherein the insulating pressure-sensitive adhesive layer is arranged in a region on the second main surface where the conductive pressure-sensitive adhesive layer is not arranged.

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