TW202200358A - Layered body, electromagnetic wave permeable layered body, and article - Google Patents

Abstract

The present invention relates to a layered body, an electromagnetic wave permeable layered body, and an article equipped with the layered body or the electromagnetic wave permeable layered body. The layered body and the electromagnetic wave permeable layered body each comprise a first base material, an optical functional layer formed on the first base material, and a first pressure sensitive adhesive layer, in this order. A pressure attenuation layer is provided on the surface of the first base material on the opposite side from the optical functional layer. The pressure attenuation layer comprises a second base material and a second pressure sensitive adhesive layer, and has a pressure deformation parameter of 4*10<SP>8</SP> or greater.

Description

Laminate, electromagnetic wave transmissive laminate, and article

The present invention relates to a laminate, an electromagnetic wave-transmitting laminate, and an article.

Conventionally, a member having electromagnetic wave transmittance and metallic luster has both the high-quality appearance brought by the metallic luster and the electromagnetic wave transmittance, so it is suitably used in a device for transmitting and receiving electromagnetic waves. For example, housings in electronic devices such as mobile phones, smart phones, and computers require metallic luster objects that possess both brightness and electromagnetic wave transmittance.

In such electronic devices, it is preferable to use decorations in metallic luster tones to express a sense of luxury. However, when metal is used for the casing part, it is virtually impossible to transmit and receive electromagnetic waves, or it is disturbed. Therefore, in order not to impair the design properties of electronic equipment without interfering with the transmission and reception of electromagnetic waves, a metallic glossy article having both brightness and electromagnetic wave transmittance is required.

Such metallic luster articles are expected to be applied to various devices that require communication, such as car door handles equipped with smart keys and in-vehicle communication devices. Furthermore, in recent years, with the advancement of IoT (Internet of Things) technology, such metallic luster articles are expected to be applied to a wide range of fields such as refrigerators and other household appliances and household appliances that have not previously communicated. Regarding the metallic luster member, for example, Patent Document 1 describes a laminate in which an adhesive layer and a metal vapor-deposited film are laminated in this order on the back side of a transparent substrate from the visible side. [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 3790265

[Problems to be Solved by Invention]

However, since the member described in Patent Document 1 increases the thickness of the base, there are problems in terms of productivity and cost. The invention of the present application has been made in view of the above-mentioned circumstances, and provides a laminated body and an electromagnetic wave-transmitting laminated body having excellent appearance (eg, metallic appearance) while suppressing the strain of reflected light when light is reflected on the surface. [Technical means to solve problems]

In order to solve the above-mentioned problems, the inventors of the present invention have repeatedly conducted intensive studies, and as a result, they have found that by providing the extrusion relief layer, the interface deformation on the visible side of the optical functional layer due to extrusion can be suppressed, and an excellent metallic appearance can be obtained. The laminated body and the electromagnetic wave-transmissive laminated body were obtained, thereby completing the present invention.

The present invention has the following constitution. [1] A layered product comprising, in this order, a first base material, an optically functional layer formed on the above-mentioned first base material, and a first adhesive layer, the first base material being opposite to the above-mentioned optically functional layer The side surface is provided with an extrusion relaxation layer, the extrusion relaxation layer includes a second base material and a second adhesive layer, and the extrusion deformation parameter is 4×10 ⁸ or more. [2] The laminate according to [1], wherein the optical functional layer is a metal layer. [3] The laminate according to [2], further comprising an indium oxide-containing layer between the first base material and the metal layer. [4] The laminate according to [3], wherein the indium oxide-containing layer is provided in a continuous state. [5] The laminate according to [3] or [4], wherein the indium oxide-containing layer contains indium oxide (In ₂ O ₃ ), indium tin oxide (ITO), or indium zinc oxide (IZO) any of them. [6] The laminate according to any one of [2] to [5], wherein the metal layer contains aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), silver (Ag) ), or any of its alloys. [7] The laminate according to any one of [2] to [6], wherein the first base material has light-shielding properties. [8] An electromagnetic wave-transmitting laminate, which is the laminate according to any one of [2] to [7], wherein the metal layer includes a plurality of parts in which at least one part is discontinuous. [9] The electromagnetic wave-transmissive laminate as described in [8], wherein the plurality of parts are formed in an island shape. [10] The electromagnetic wave transmissive laminate according to [8] or [9], wherein the sheet resistance is 100 Ω/□ or more. [11] An article in which the laminate according to any one of [1] to [7] or the electromagnetic wave-transmissive laminate according to any one of [8] to [10] is attached to Obtained as a transparent molded body. [Effect of invention]

According to the present invention, a laminate having an excellent metallic appearance and an electromagnetic wave-transmitting laminate can be provided.

The layered product according to the embodiment of the present invention has a first base material, an optical functional layer formed on the first base material, and a first adhesive layer in this order, and the first base material is opposite to the optical functional layer. The side surface is provided with an extrusion relaxation layer, the extrusion relaxation layer includes a second base material and a second adhesive layer, and the extrusion deformation parameter is 4×10 ⁸ or more.

Hereinafter, one preferred embodiment of the present invention will be described with reference to the accompanying drawings. Hereinafter, for the convenience of description, only suitable embodiments of the present invention are shown, but the present invention is not limited thereto, of course. In addition, in the following description, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit value and an upper limit value.

<1. Basic configuration> The layered product according to one embodiment of the present invention includes, in this order, a first base material, an optical functional layer formed on the first base material, and a first adhesive layer, on the side of the first base material. The surface opposite to the optical function layer is provided with an extrusion relaxation layer, the extrusion relaxation layer includes a second base material and a second adhesive layer, and the extrusion deformation parameter is 4×10 ⁸ or more. The optical functional layer is preferably a metal layer, and the metal layer includes a plurality of parts in which at least one part is discontinuous with each other. Hereinafter, the case where the optical function layer is a metal layer and the laminate is an electromagnetic wave transmissive laminate may be described, but the present invention is not limited to the following description.

FIG. 1 shows a schematic cross-sectional view of an electromagnetic wave transmissive laminate 1 according to an embodiment of the present invention, and FIG. 3 shows an electron microscope photograph of the surface of the metal layer of the electromagnetic wave transmissive laminate 1 according to an embodiment of the present invention. (SEM image). The electromagnetic wave-transmissive laminate 1 in FIG. 1 includes, in this order, a first substrate 10 , a metal layer 12 formed on the first substrate 10 , and a first adhesive layer 13 formed on the metal layer 12 . The surface of the base material 10 on the opposite side to the metal layer 12 is provided with the extrusion relief layer 14. The extrusion relief layer 14 includes the second base material 16 and the second adhesive layer 15 . Moreover, in the electromagnetic wave transmissive laminated body 1, the indium oxide containing layer 11 may be provided between the 1st base material 10 and the metal layer 12.

The metal layer 12 is formed on the first base material 10 . The metal layer 12 includes a plurality of portions 12a. Among the portions 12a in the metal layer 12, at least a portion is in a state of discontinuity with each other, in other words, at least a portion is separated by a gap 12b. Since it is separated by the gap 12b, the sheet resistance of the electromagnetic wave transmissive laminate is increased, and the interaction with the radio wave is reduced, so that the radio wave can be transmitted. The respective portions 12a may be an aggregate of sputtered particles formed by vapor deposition, sputtering, or the like of metal.

In addition, in this specification, "discontinuous state" means the state which isolate|separates from each other by the clearance gap 12b, and is electrically insulated from each other as a result. Through electrical insulation, the sheet resistance is increased, and the required electromagnetic wave transmittance can be obtained. That is, according to the metal layer 12 formed in a discontinuous state, sufficient brightness can be easily obtained, and electromagnetic wave transmittance can also be ensured. The discontinuous form is not particularly limited, and includes, for example, an island-like structure, a cracked structure, and the like. Here, as shown in FIG. 3 , the “island-shaped structure” refers to a structure in which metal particles are independent of each other, and the particles are filled with a slight interval or a part of them in contact with each other.

The cracked structure refers to the structure in which the metal film is broken by cracks. The metal layer 12 of the crack structure can be formed by, for example, providing a metal thin film layer on the base film as the first base material, and bending and extending the metal thin film layer to cause cracks in the metal thin film layer, thereby forming a crack structure. In this case, the metal layer 12 having a cracked structure can be easily formed by providing a brittle layer including a material that lacks elasticity, that is, a material that is prone to cracks by extension, between the base film and the metal thin film layer.

As described above, the discontinuous state of the metal layer 12 is not particularly limited, but from the viewpoint of productivity, it is preferable to have an island-like structure.

The electromagnetic wave transmissivity of the electromagnetic wave transmissive laminate 1 can be evaluated based on, for example, the radio wave transmission attenuation. The radio wave transmission attenuation in the microwave band (5 GHz) is preferably 10 [-dB] or less, more preferably 5 [-dB] or less, and still more preferably 2 [-dB] or less. If it is more than 10[-dB], there is a problem that more than 90% of the radio waves are blocked.

The sheet resistance of the electromagnetic wave transmissive laminate 1 is also related to the electromagnetic wave transmissivity. The sheet resistance of the electromagnetic wave transmissive laminate 1 is preferably 100 Ω/□ or more, and in this case, the electromagnetic wave transmission attenuation in the microwave band (5 GHz) is about 10 to 0.01 [-dB]. The sheet resistance of the electromagnetic wave transmissive laminate 1 is further preferably 200 Ω/□ or more, particularly preferably 600 Ω/□ or more. Moreover, it is especially preferable that it is 1000 Ω/□ or more. The sheet resistance of the electromagnetic wave transmissive laminate 1 can be measured by the eddy current measurement method in accordance with JIS-Z2316-1:2014.

The radio wave transmission attenuation and sheet resistance of the electromagnetic wave transmissive laminate 1 are influenced by the material, thickness, and the like of the metal layer 12 . In addition, when the electromagnetic wave transmissive laminated body 1 includes the indium oxide-containing layer 11 , it is also affected by the material, thickness, and the like of the indium oxide-containing layer 11 .

The compression deformation parameter of the electromagnetic wave transmissive laminate 1 is 4×10 ⁸ or more. From the viewpoint of suppressing extrusion deformation, the extrusion deformation parameter is 4×10 ⁸ or more, preferably 5×10 ⁸ or more, and more preferably 5.5×10 ⁸ or more. Here, the so-called extrusion deformation parameter refers to the ease of deformation as seen from the side of the transparent substrate when the electromagnetic wave transmissive laminate is attached to the transparent substrate via an adhesive, and when a load is applied to the laminate, the extrusion deformation parameter It is one of the indexes indicating the resistance to extrusion deformation of the electromagnetic wave transmissive laminate. The extrusion deformation parameter can be calculated according to the following formula (1). (E _O1 /T _O1 )×(E _S1 ×√T _S1 )×(T _O2 /E _O2 )×E _S2 Formula (1) E _O1 : elastic modulus of the first adhesive layer (MPa) T _O1 : the first 1 Thickness of the adhesive layer (μm) E _S1 : Modulus of elasticity of the first substrate (MPa) T _S1 : Thickness of the first substrate (μm) E _O2 : Modulus of elasticity of the second adhesive layer (MPa) T _O2 : Thickness of the second adhesive layer (μm) E _S2 : Elastic modulus of the second base material (MPa)

<2. The first base material> In the electromagnetic wave transmissive laminated body of this embodiment, as the 1st base material 10, from a viewpoint of electromagnetic wave transmissivity, resin, glass, ceramics, etc. are mentioned. The first base material 10 may be any of a base film, a resin-molded article base, a glass base, or an article to which metallic luster should be imparted, and is preferably a base film. More specifically, as the base film, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polyethylene terephthalate can be used. Vinyl chloride, polycarbonate (PC), cyclic olefin polymer (COP), polystyrene, polypropylene (PP), polyethylene, polycyclic olefin, polyurethane, acrylic resin (PMMA), ABS (Acrylonitrile-Butadiene-Styrene, acrylonitrile-butadiene-styrene) and other homopolymer or copolymer transparent film.

According to these members, there is no influence on brightness or electromagnetic wave transmittance. However, from the viewpoint of forming the indium oxide-containing layer 11 or the metal layer 12 later, those that can withstand high temperatures such as vapor deposition or sputtering are preferred. Therefore, among the above-mentioned materials, for example, polyethylene terephthalene is preferred. Ethylene formate, polyethylene naphthalate, acrylic resin, polycarbonate, cycloolefin polymer, ABS, polypropylene, polyurethane. Among them, from the viewpoint of balancing heat resistance and cost, polyethylene terephthalate, cycloolefin polymers, polycarbonates, and acrylic resins are preferred.

The base film may be a single-layer film or a laminated film. In order to enhance the adhesion with the indium oxide-containing layer 11 or the metal layer 12, the base film may also be subjected to plasma treatment or easy adhesion treatment. The metal layer 12 only needs to be provided on at least a part of the base film, and may be provided on only one side of the base film, or may be provided on both sides.

The base film may be formed with a smooth or anti-glare hard coat layer as needed. By providing a hard coat layer, the scratch resistance of the metal film can be improved. By providing a smooth hard coat layer, the metallic luster can be increased, and conversely, by providing an anti-glare hard coat layer, glare can be prevented. The hard coat layer can be formed by applying a solution containing a curable resin.

As curable resin, a thermosetting resin, an ultraviolet curing resin, an electron beam curing resin, etc. are mentioned. As the kind of curable resin, polyester-based, acrylic-based, urethane-based, acrylic-urethane-based, amide-based, silicone-based, silicate-based, epoxy-based, Various resins such as melamine-based, oxetane-based, and urethane acryl-based resins. One or more of these curable resins can be appropriately selected and used. Among these, an acrylic resin, an acrylic urethane resin, and an epoxy resin are preferable from the viewpoint of high hardness, being able to be cured by ultraviolet rays, and being excellent in productivity.

The first base material may further have light-shielding properties. The method of imparting light-shielding properties is not limited. For example, the light-shielding properties can be adjusted by adding pigments, pigments, and dyes to the base film, or by printing dyes, pigments, and dyes on the base film.

Here, the modulus of elasticity of the first base material can be calculated as follows: a rectangular sample is produced, and a tensile testing machine (manufactured by Minebea, Universal Tensile Compression Testing Machine, device name "Tensile Compression Testing Machine, TCM-1kNB" is used) ”), measured at a tensile speed of 50 mm/min, and calculated the elastic modulus according to the slope of the range where the displacement is less than 5% in the elastic deformation region of the obtained stress-displacement curve.

From the viewpoint of suppressing extrusion deformation, the thickness of the first base material is, for example, 23 μm or more, preferably 50 μm or more, and from the viewpoint of productivity, for example, 250 μm or less, preferably 150 μm the following. The thickness of the 1st base material can be measured, for example using a film thickness gauge (dial gauge).

The metal layer 12 may be formed on the first base material, may be formed on a part of the surface of the first base material, or may be formed on the entire surface of the first base material.

<3. Indium oxide-containing layer> Moreover, in the electromagnetic wave transmissive laminated body 1 of one Embodiment, as shown in FIG. 1, the indium oxide containing layer 11 may be further provided between the 1st base material 10 and the metal layer 12. The indium oxide-containing layer 11 may be directly provided on the surface of the first base material 10 , or may be provided indirectly via a protective film or the like provided on the surface of the first base material 10 . The indium oxide-containing layer 11 is preferably provided in a continuous state, in other words, without a gap, on the surface of the first substrate 10 to which metallic luster is to be imparted. By arranging in a continuous state, the smoothness and corrosion resistance of the indium oxide-containing layer 11, the metal layer 12, or the electromagnetic wave transmissive laminate 1 can be improved, and the indium oxide-containing layer 11 can be easily formed uniformly in-plane.

In this way, the indium oxide-containing layer 11 is further disposed between the first substrate 10 and the metal layer 12 , that is, the indium oxide-containing layer 11 is formed on the first substrate 10 , and the metal layer is formed on the indium oxide-containing layer 11 12, so that it is easy to form the metal layer 12 in a discontinuous state, which is preferable. Although the details of the mechanism are not necessarily clear, it is considered as follows: When sputtered particles obtained by vapor deposition or sputtering of metals form a thin film on the first substrate, the surface diffusivity of the particles on the first substrate will be affected. The shape of the film is affected. When the temperature of the first substrate is higher, the wettability of the metal layer to the first substrate is lower, and the melting point of the material of the metal layer is lower, and the discontinuous structure is more likely to be formed. In addition, it is considered that by providing the indium oxide-containing layer on the first substrate, the surface diffusivity of the metal particles on the surface is promoted, and the metal layer is easily grown in a discontinuous state.

As the indium oxide-containing layer 11, indium oxide (In ₂ O ₃ ) itself can be used, and for example, metal-containing substances such as indium tin oxide (ITO) or indium zinc oxide (IZO) can also be used. However, ITO or IZO containing the second metal is more preferable in terms of higher discharge stability in the sputtering step. By using these indium oxide-containing layers 11, a continuous film can be formed along the surface of the first substrate, and in this case, the metal layer laminated on the indium oxide-containing layer can be easily formed into, for example, islands The discontinuous structure of the shape is preferred. Furthermore, as described below, in this case, the metal layer tends to contain not only chromium (Cr) and indium (In) but also various metals such as aluminum which are generally difficult to have a discontinuous structure and are difficult to use for this application.

The mass ratio of tin oxide (SnО ₂ ) contained in ITO, that is, the content ratio (content ratio=(SnO ₂ /(In ₂ O ₃ +SnO ₂ ))×100) is not particularly limited, but is, for example, 2.5 wt % to 30 wt % %, more preferably 3 wt% to 10 wt%. The mass ratio of zinc oxide (ZnO) contained in IZO, that is, the content ratio (content ratio=(ZnO/(In ₂ O ₃ +ZnO))×100) is, for example, 2 wt % to 20 wt %. From the viewpoint of sheet resistance, electromagnetic wave transmittance, and productivity, the thickness of the indium oxide-containing layer 11 is usually preferably 1000 nm or less, more preferably 50 nm or less, and still more preferably 20 nm or less. On the other hand, the thickness of the indium oxide-containing layer 11 is preferably 1 nm or more in order to easily make the laminated metal layer 12 into a discontinuous state. The thickness of 11 is more preferably 2 nm or more, and more preferably 5 nm or more.

<4. Optical functional layer> The optical function layer is formed on the first base material 10 . The optical functional layer is a layer with optical characteristics, preferably a layer with metallic luster. The material for forming the optical functional layer is not particularly limited, and may include metals and resins. The optical functional layer can also be a metal layer. The case where the optical functional layer is a metal layer will be described. The metal layer 12 is preferably formed on the first substrate, and includes a plurality of parts in which at least one part is discontinuous with each other. When the metal layer 12 is in a discontinuous state on the first base material, sufficient brightness can be obtained, and the amount of radio wave transmission attenuation becomes small, so that the electromagnetic wave transmittance can be ensured.

Although the details of the mechanism of the case where the metal layer 12 is in a discontinuous state on the first base material is not necessarily clear, it is roughly estimated as follows. That is, in the thin film formation process of the metal layer 12, there is a correlation between the ease of forming the discontinuous structure and the surface diffusion on the first substrate for imparting the metal layer 12, that is, the higher the temperature of the first substrate, the more The lower the wettability of the layer to the first substrate and the lower the melting point of the material of the metal layer, the easier it is to form a discontinuous structure. Therefore, it is considered that metals other than aluminum (Al) especially used in the following examples, that is, metals with relatively low melting points such as zinc (Zn), lead (Pb), copper (Cu), and silver (Ag), can be Use the same method to form discontinuous structures.

Here, the average particle diameter of the plurality of parts 12a means the average value of the circle-equivalent diameters of the plurality of parts 12a. The circle-equivalent diameter of the portion 12a refers to the diameter of a true circle corresponding to the area of the portion 12a. The average particle diameter of the plurality of parts 12a can be obtained by using a scanning electron microscope (SEM) to obtain an SEM image of the laminate having the metal layer formed on the first substrate, and from the obtained values of the parts. For the area (V), the particle diameter R of each part was calculated from R=2×(V/π) ^0.5 , and the average value was obtained as the average particle diameter of a plurality of parts. The circle-equivalent diameter of the portion 12a of the metal layer 12 is not particularly limited, but is usually about 10 to 1000 nm. In addition, the distance between each part 12a is not specifically limited, Usually, it is about 10-1000 nm.

By setting the average particle diameter of the discontinuous portions 12a contained in the metal layer within the above-mentioned range, the brightness can be further improved while maintaining high electromagnetic wave transmittance.

It is desirable that the metal layer 12 not only exhibits sufficient brightness, but also has a relatively low melting point. The reason for this is that the metal layer 12 is preferably formed by thin film growth using sputtering. Therefore, the metal layer 12 is preferably a metal having a melting point of about 1000° C. or lower. For example, it is preferable to include a metal selected from the group consisting of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), and silver (Ag). at least one metal, and any alloy of the alloys containing the metal as the main component. In particular, for reasons such as brightness, stability, and price of the substance, Al and its alloys are preferred. Moreover, when using an aluminum alloy, it is preferable to make aluminum content 50 mass % or more.

The thickness of the metal layer 12 is usually preferably 20 nm or more in order to exhibit sufficient brightness, and is usually preferably 100 nm or less from the viewpoint of sheet resistance or electromagnetic wave transmittance. For example, it is preferably 20 nm to 100 nm, more preferably 30 nm to 70 nm. This thickness is also suitable for forming a uniform film with good productivity, and the appearance of the resin molded product as a final product is also good.

Furthermore, for the same reason, the ratio of the thickness of the metal layer to the thickness of the indium oxide-containing layer (thickness of the metal layer/thickness of the indium oxide-containing layer) is preferably in the range of 0.1 to 100, more preferably in the range of 0.3 to 35 .

The sheet resistance of the metal layer is preferably 100 Ω/□ or more. In this case, the electromagnetic wave transmittance is about 10 to 0.01 [-dB] at a wavelength of 1 GHz. More preferably, it is 1000 Ω/□ or more.

When the indium oxide-containing layer is further provided, the sheet resistance of the laminate of the metal layer and the indium oxide-containing layer is preferably 100 Ω/□ or more. In this case, the electromagnetic wave transmittance is about 10 to 0.01 [-dB] at a wavelength of 1 GHz. More preferably, it is 1000 Ω/□ or more. The sheet resistance is not only affected by the material or thickness of the metal layer, but also greatly affected by the material or thickness of the indium oxide-containing layer as the base layer. Therefore, when setting the indium oxide-containing layer, it is necessary to set based on consideration of the relationship with the indium oxide-containing layer.

<5. 1st adhesive layer> The first adhesive layer can be formed from the base adhesive composition. (1-1) Basic adhesive composition The base adhesive composition preferably contains the (meth)acrylic polymer (A) as a base polymer. The (meth)acrylic polymer (A) preferably contains the (meth)acrylic acid alkyl ester (a1) constituting the main skeleton of the (meth)acrylic polymer (A) as a monomer unit. In addition, (meth)acrylate means acrylate and/or methacrylate.

As said alkyl (meth)acrylate (a1), what has a linear or branched C1-C18 alkyl group is mentioned. For example, as said alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, 2-ethylhexyl group, isooctyl group can be illustrated. , nonyl, decyl, isodecyl, dodecyl, isomyristyl, lauryl, tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, etc. These can be used individually or in combination.

The mixing ratio of the above-mentioned alkyl (meth)acrylate (a1) is preferably 50% by mass or more, more preferably 50% by mass or more with respect to all the constituent monomers (100% by mass) constituting the (meth)acrylic polymer (A). It is 50-100 mass %, More preferably, it is 60-100 mass %, Especially preferably, it is 70-90 mass %.

The above-mentioned (meth)acrylic polymer (A) preferably contains a monomer selected from the group consisting of a carboxyl group-containing monomer (a2), a hydroxyl group-containing monomer (a3), and a nitrogen-containing monomer for the purpose of improving adhesion or heat resistance. One or more monomers in the group consisting of the body (a4) are used as monomer components.

As the carboxyl group-containing monomer (a2), those having an unsaturated double bond-containing polymerizable functional group such as a (meth)acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation. Examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itonic acid, maleic acid, and fumaric acid. Acid, crotonic acid, methacrylic acid, etc., which may be used alone or in combination. Acid anhydrides of itonic acid and maleic acid can be used. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is especially preferable.

The compounding ratio of the said carboxyl group-containing monomer (a2) is preferably 10 mass % or less, more preferably 0.05 to 10 mass %, more preferably 0.1 to 10 mass %, particularly preferably 0.5 to 5 mass %.

As a hydroxyl group-containing monomer (a3), what has a polymerizable functional group containing an unsaturated double bond, such as a (meth)acryloyl group or a vinyl group, and a hydroxyl group can be used without particular limitation. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and (meth)acrylic acid. 4-Hydroxybutyl, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, etc. Hydroxyalkyl (meth)acrylate; (meth)acrylate hydroxyalkylcycloalkane, such as (4-hydroxymethylcyclohexyl)methyl (meth)acrylate. Moreover, hydroxyethyl (meth)acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, etc. are mentioned. These can be used individually or in combination. Among these, hydroxyalkyl (meth)acrylate is preferable, and 2-hydroxyethyl (meth)acrylate is more preferable.

The mixing ratio of the above-mentioned hydroxyl group-containing monomer (a3) is preferably 20% by mass or less, more preferably 0.05 to 20 mass %, more preferably 0.1 to 15 mass %, particularly preferably 1 to 15 mass %.

As the nitrogen-containing monomer (a4), one having a polymerizable functional group containing an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and a functional group containing a nitrogen atom can be used without particular limitation.

The compounding ratio of the said nitrogen-containing monomer (a4) is preferably 20 mass % or less, more preferably 0.05 to 20 mass %, with respect to all the constituent monomers (100 mass %) constituting the (meth)acrylic polymer (A). The mass % is more preferably 0.1 to 15 mass %, and particularly preferably 1 to 15 mass %.

In the above-mentioned (meth)acrylic polymer (A), in addition to the above-mentioned alkyl (meth)acrylate (a1), carboxyl group-containing monomer (a2), hydroxyl group-containing monomer (a3), nitrogen-containing monomer In addition to (a4), for the purpose of improving adhesiveness or heat resistance, a copolymer having one or more types of polymerizable functional groups having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group may be introduced by copolymerization. polymerized monomers. Specific examples of such comonomers include caprolactone adducts of acrylic acid; styrene sulfonic acid or propylene sulfonic acid, sulfopropyl (meth)acrylate, and (meth)acryloyloxy sulfonic acid group-containing monomers such as naphthalenesulfonic acid; phosphate group-containing monomers such as 2-hydroxyethylacryloyl phosphate, etc.

The ratio of the above-mentioned carboxyl group-containing monomer (a2), hydroxyl group-containing monomer (a3), and co-polymerized monomers other than nitrogen-containing monomer (a4) is not particularly limited. In the total monomer of A), 10 mass % or less is preferable, 0.1-10 mass % is more preferable, 0.1-5 mass % is still more preferable.

The (meth)acrylic polymer (A) can be obtained by appropriately combining the above-mentioned monomers and polymerizing them according to the purpose or required properties. The obtained (meth)acrylic polymer (A) may be any of a random copolymer, a block copolymer, and a graft copolymer. The (meth)acrylic polymer (A) can be synthesized by any suitable method. For example, it can be synthesized with reference to "Chemistry and Application of Adhesion and Adhesion" published by Dainippon tosho and edited by Katsuhiko Nakamae.

For example, any appropriate method can be adopted as the polymerization method of the (meth)acrylic polymer (A). Specific examples include solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations.

The polymerization initiator, chain transfer agent, emulsifier, etc. used in the radical polymerization can be appropriately selected and used without particular limitation. In addition, the weight-average molecular weight of the (meth)acrylic polymer can be controlled according to the usage amount of the polymerization initiator, the chain transfer agent, the reaction conditions, etc., and the usage amount can be appropriately adjusted according to the type thereof.

For example, in solution polymerization or the like, as a polymerization solvent, for example, ethyl acetate, toluene, or the like is used. As a specific example of solution polymerization, the reaction is usually carried out under the reaction conditions of about 50 to 70° C. for about 5 to 30 hours after adding a polymerization initiator under an inert gas flow such as nitrogen gas.

As the thermal polymerization initiator used in solution polymerization or the like, for example, azo initiators such as 2,2'-azobisisobutyronitrile, peroxide initiators, peroxides and Redox-based initiators, etc., which are combined with reducing agents, are not limited thereto.

The above-mentioned polymerization initiator may be used alone or in combination of two or more, and is preferably about 1 part by mass or less with respect to 100 parts by mass of the total monomer components constituting the (meth)acrylic polymer (A). , more preferably about 0.005 to 1 part by mass, still more preferably about 0.02 to 0.5 part by mass.

Furthermore, when the (meth)acrylic polymer (A) is produced using, for example, 2,2'-azobisisobutyronitrile as a polymerization initiator, the amount of the polymerization initiator to be used is relative to the ratio of the monomer components. The total amount of 100 parts by mass is preferably about 0.2 parts by mass or less, and more preferably about 0.06 to 0.2 parts by mass.

In addition, in the case of producing the (meth)acrylic polymer (A) by radiation polymerization, the monomer components can be polymerized by irradiating the above-mentioned monomer components with radiation such as electron beam and UV (Ultraviolet). manufacture. In the case of carrying out the above-mentioned radiation polymerization by electron beams, it is not particularly necessary to contain a photopolymerization initiator in the above-mentioned monomer components, but in the case of carrying out the above-mentioned radiation polymerization by UV polymerization, in particular, the polymerization time can be shortened. In consideration of advantages and the like, a photopolymerization initiator may be contained in the monomer component. A photopolymerization initiator may be used individually by 1 type, or may be used in combination of 2 or more types.

The weight average molecular weight of the (meth)acrylic polymer (A) used in the present invention is preferably from 400,000 to 2.5 million, more preferably from 600,000 to 2.2 million. By making the weight average molecular weight larger than 400,000, the durability of the first adhesive layer can be satisfied, or the cohesive force of the first adhesive layer can be reduced to suppress the residual paste. In addition, the weight average molecular weight means the value computed by polystyrene conversion by measuring by gel permeation chromatography (GPC). Furthermore, for (meth)acrylic polymers obtained by radiation polymerization, the measurement of molecular weight is difficult to implement.

The base adhesive composition used in the present invention may also contain a crosslinking agent. As a crosslinking agent, an organic type crosslinking agent and a polyfunctional metal chelate compound are mentioned, for example. As an organic type crosslinking agent, an isocyanate type crosslinking agent, a peroxide type crosslinking agent, an epoxy type crosslinking agent, and an imine type crosslinking agent are mentioned, for example. Polyfunctional metal chelates are formed by covalent bonding or coordinate bonding of multivalent metals and organic compounds. Examples of polyvalent metals include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti. As an organic compound, an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound are mentioned, for example. As an atom in a covalently-bonded or coordinate-bonded organic compound, for example, an oxygen atom is exemplified. Among these, as a crosslinking agent, an isocyanate type crosslinking agent is preferable.

The isocyanate-based crosslinking agent typically refers to a compound having two or more isocyanate groups in one molecule. For example, isocyanate monomers such as tolylene diisocyanate, chlorobenzene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate, and the Isocyanate compounds, isocyanurate compounds, biuret compounds obtained by addition of trimethylolpropane, etc., and polyether polyols or polyester polyols, acrylic polyols, polybutadiene polyols Urethane prepolymer type isocyanates, etc. obtained by addition reaction of alcohols, polyisoprene polyols, etc. Particularly preferred is a polyisocyanate compound, that is, one selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate, or a polyisocyanate compound derived therefrom. Here, one kind selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate, or a polyisocyanate compound derived therefrom includes: hexamethylene Diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, polyol-modified hexamethylene diisocyanate, polyol-modified hydrogenated xylylene diisocyanate, trimer-type hydrogenated xylylene diisocyanate Diisocyanate, and polyol-modified isophorone diisocyanate, etc.

As the peroxide, any suitable compound capable of generating a radical reactive species by heating or light irradiation can be used to perform crosslinking of the base polymer. In consideration of workability and stability, a peroxide having a 1-minute half-life temperature of 80°C to 160°C is preferable, and a peroxide having a 1-minute half-life temperature of 90°C to 140°C is more preferable. Specific examples of peroxides include bis(2-ethylhexyl)peroxydicarbonate (1-minute half-life temperature: 90.6°C), bis(4-tert-butylcyclohexyl)peroxydicarbonate Esters (1-minute half-life temperature: 92.1°C), di-2-butyl peroxydicarbonate (1-minute half-life temperature: 92.4°C), 3-butyl peroxyneodecanoate (1-minute half-life temperature: 103.5°C), 3-hexyl pivalate oxide (1-minute half-life temperature: 109.1°C), 3-butyl peroxypivalate (1-minute half-life temperature: 110.3°C), dilaurin peroxide (1-minute half-life temperature: 116.4°C) ), di-n-octyl peroxide (1-minute half-life temperature: 117.4°C), 1,1,3,3-tetramethylbutyl peroxide 2-ethylhexanoate (1-minute half-life temperature: 124.3°C), Bis(4-methylbenzyl) oxide (1-minute half-life temperature: 128.2°C), Dibenzyl peroxide (1-minute half-life temperature: 130.0°C), tert-butyl peroxyisobutyrate (1 minute Half-life temperature: 136.1°C), 1,1-bis(third hexylperoxy)cyclohexane (1 minute half-life temperature: 149.2°C), and the like. In addition, the so-called half-life of peroxide is an index showing the decomposition rate of peroxide, and means the time until the residual amount of peroxide is reduced to half. Therefore, the 1-minute half-life temperature of peroxide refers to the temperature at which the residual amount of peroxide becomes half in 1 minute. The decomposition temperature at an arbitrary time for obtaining the half-life, or the half-life time at an arbitrary temperature, is described in the manufacturer's catalogue, etc., for example, in the "Organic Peroxide Catalogue 9th Edition" of NOF Co., Ltd. ( May 2003)” and so on.

The usage-amount of a crosslinking agent is preferably 0.01-20 mass parts with respect to 100 mass parts of (meth)acrylic-type polymers (A), More preferably, it is 0.03-10 mass parts. When the usage-amount of a crosslinking agent is less than 0.01 mass part, there exists a tendency for the cohesion force of an adhesive to become insufficient, and foaming may generate|occur|produce when heating. When the usage-amount of a crosslinking agent exceeds 20 mass parts, moisture resistance will become insufficient, and peeling etc. may arise easily.

The above-mentioned base adhesive composition may also contain any suitable additives. As an additive, a light-diffusing fine particle, an antistatic agent, an antioxidant, and a coupling agent are mentioned, for example. The kind, amount, combination, etc. of the additives can be appropriately set according to the purpose.

The content of the base adhesive composition in the first adhesive layer used in the present invention is preferably 50 to 99.7% by mass, more preferably 52 to 97% by mass, and still more preferably 70 to 97% by mass.

The total light transmittance of the first adhesive layer 13 as a whole is not particularly limited, and is preferably 10% or more, more preferably 30% or more, and more preferably 10% or more in terms of the value at any wavelength of visible light measured according to JIS K7361 more than 50%. The higher the total light transmittance of the first adhesive layer 13, the better.

From the viewpoint of suppressing extrusion deformation, the elastic modulus of the first adhesive layer 13 of the present embodiment is preferably 0.3 MPa or more, more preferably 0.5 MPa or more, and still more preferably 5 MPa or more.

Here, the modulus of elasticity of the first adhesive layer 13 can be calculated as follows: A rectangular sample having a width of 10 mm and a length of 150 mm is produced, and a tensile testing machine (manufactured by Minebea, Universal Tensile Compression Testing Machine, device name) is used. "Tensile Compression Tester, TCM-1kNB"), measured at a tensile speed of 50 mm/min, and calculated from the slope of the elastic deformation region of the obtained stress-displacement curve in the range where the displacement is less than 5% modulus of elasticity.

From the viewpoint of adhesive force, the thickness of the first adhesive layer 13 is preferably, for example, 5 μm or more, more preferably 15 μm or more, and from the viewpoint of suppressing extrusion deformation, for example, preferably 50 μm or more μm or less, more preferably 25 μm or less. The thickness of the first adhesive layer 13 can be measured using, for example, a film thickness gauge (dial gauge).

Moreover, the transparent adhesive which comprises the 1st adhesive layer 13 may be colored. In this case, since the metal layer 12 is visually recognized through the colored first adhesive layer 13, colored metallic luster can be expressed.

The method of coloring the transparent adhesive is not particularly limited, for example, it can be colored by adding a trace amount of pigment.

<6. Squeeze Relief Layer> In the electromagnetic wave transmissive laminated body 1 of one embodiment, as shown in FIG. 1 , the extrusion relaxation layer 14 is laminated on the surface of the first base material 10 opposite to the metal layer 12 . By providing the extrusion relaxation layer 14, the interface deformation on the visible side of the metal layer due to extrusion can be suppressed, and an electromagnetic wave transmissive laminate having an excellent metal appearance can be obtained. In the electromagnetic wave transmissive laminate 1 according to the embodiment of the present invention, the extrusion relief layer 14 includes the second base material 16 and the second adhesive layer 15 .

(2nd adhesive layer) The second adhesive layer 15 may be formed of a base adhesive composition.

The base adhesive composition for forming the second adhesive layer 15 is not particularly limited, and for example, the above-mentioned base adhesive composition for forming the first adhesive layer can be exemplified. As the base polymer contained in the base adhesive composition, from the viewpoints of processability and durability, for example, an acrylic adhesive is preferably used.

From the viewpoint of alleviating extrusion deformation, the elastic modulus of the second adhesive layer 15 of the present embodiment is preferably 5 MPa or less, more preferably 2 MPa or less, and still more preferably 1 MPa or more.

Here, the modulus of elasticity of the second adhesive layer 15 can be calculated as follows: a rectangular sample having a width of 10 mm and a length of 150 mm is produced, and a tensile testing machine (manufactured by Minebea, Universal Tensile Compression Testing Machine, device name) is used. "Tensile Compression Tester, TCM-1kNB"), measured at a tensile speed of 50 mm/min, and calculated from the slope of the elastic deformation region of the obtained stress-displacement curve in the range where the displacement is less than 5% modulus of elasticity.

From the viewpoint of suppressing extrusion deformation, the thickness of the second adhesive layer 15 is, for example, 5 μm or more, or preferably 25 μm or more. The thickness of the second adhesive layer 15 can be measured using, for example, a film thickness gauge (dial gauge).

(2nd base material) As a material of the 2nd base material 16, resin is mentioned preferably. Examples of resins include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; base) acrylic resins (acrylic resins and/or methacrylic resins); olefin resins such as polyethylene, polypropylene, and cycloolefin polymers; such as polycarbonate resins, polyether resins, polyarylate resins, Melamine resin, polyamide resin, polyimide resin, cellulose resin, polystyrene resin, nor alkene resin, etc. These resins may be used alone or in combination of two or more.

From the viewpoints of heat resistance, mechanical properties, etc., the resin is preferably a polyester resin, and more preferably PET.

These resins usually have light-transmitting properties, and for example, light-shielding properties can be adjusted by adding pigments or dyes to the resins.

The second substrate is preferably a light-shielding film, and the visible light transmittance of the second substrate 16 is preferably less than 50%.

Here, the modulus of elasticity of the second base material 16 can be calculated as follows: A rectangular sample having a width of 10 mm and a length of 150 mm is produced, and a tensile testing machine (manufactured by Minebea, Universal Tensile Compression Testing Machine, device name "" Tensile compression testing machine, TCM-1kNB”), measured under the condition of tensile speed of 50 mm/min, and calculated the elasticity according to the slope of the elastic deformation region of the obtained stress-displacement curve in the range where the displacement is less than 5% modulus.

From the viewpoint of suppressing extrusion deformation, the thickness of the second base material 16 is, for example, 23 μm or more, preferably 50 μm or more, and from the viewpoint of productivity, for example, 250 μm or less, preferably 150 μm or less μm or less. The thickness of the second base material 16 can be measured using, for example, a film thickness gauge (dial gauge).

As long as the effects of the present invention are exhibited, other layers may be provided in the electromagnetic wave transmissive laminate of the present embodiment in addition to the above-described metal layer 12 , first adhesive layer 13 , and extrusion relief layer 14 according to the application. Examples of other layers include: an optical adjustment layer (color adjustment layer) of a high-refractive material for adjusting the appearance such as color tone, and a protective layer (scratch resistance layer) for improving durability such as moisture resistance and scratch resistance. ), barrier layer (anti-corrosion layer), easy adhesion layer, hard coat layer, anti-reflection layer, light extraction layer, anti-glare layer, etc.

<7. Manufacture of electromagnetic wave transmissive laminates> An example of the manufacturing method of the electromagnetic wave transmissive laminated body 1 of this embodiment is demonstrated.

When forming the metal layer 12 on the first base material 10 , methods such as vacuum deposition and sputtering can be used, for example.

In addition, when forming the indium oxide-containing layer 11 on the first base material 10 , the indium oxide-containing layer 11 is formed by vacuum deposition, sputtering, ion plating, or the like before forming the metal layer 12 . However, sputtering is preferable because the thickness can be tightly controlled despite the large area.

Furthermore, when the indium oxide-containing layer 11 is disposed between the first substrate 10 and the metal layer 12 , the indium oxide-containing layer 11 and the metal layer 12 are preferably in direct contact without intervening other layers.

As a method of forming the first adhesive layer 13, for example, the above-described adhesive composition may be applied to a support, the solvent or the like may be dried and removed, and if necessary, a cross-linking treatment may be performed to form the first adhesive. layer, and transfer the first adhesive layer onto the optical functional layer; the above-mentioned adhesive composition can also be directly coated on the optical functional layer to form the first adhesive layer. The first adhesive layer 13 can be formed by, for example, applying the above-described base adhesive composition on the optical functional layer, and drying and removing the solvent or the like. When coating the adhesive composition, one or more solvents may be appropriately added. Furthermore, when the above-mentioned base adhesive composition is an active energy ray-curable type, a prepolymer obtained by partially polymerizing the above-mentioned base adhesive composition is prepared, and light diffusing fine particles are dispersed in the prepolymer, The obtained adhesive composition is coated on the optical functional layer, and the first coating layer is irradiated with active energy rays such as ultraviolet rays, whereby a first adhesive layer can be formed. Moreover, when the said transparent conductive layer is provided, the said adhesive composition may be apply|coated on the transparent conductive layer, and a 1st adhesive layer may be formed.

As the above-mentioned support, for example, a release-treated sheet can be used. As the release-treated sheet, a silicone release liner (release film) is suitably used.

Various methods can be used as a coating method of the adhesive composition. Specifically, for example, roll coating, touch roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, blade coating, air knife coating, Curtain coating, die lip coating, extrusion coating using die nozzle coating machine, etc.

The heating and drying temperature is preferably about 30°C to 200°C, more preferably 40°C to 180°C, and still more preferably 80°C to 160°C. By making heating temperature into the said range, the 1st adhesive bond layer which has the outstanding adhesive property can be obtained. As the drying time, a suitable time can be appropriately adopted. The above drying time is preferably about 5 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and still more preferably 1 minute to 8 minutes.

When the above-mentioned basic adhesive composition is an active energy ray curable adhesive, the first adhesive layer can be formed by irradiating active energy rays such as ultraviolet rays. For ultraviolet irradiation, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a chemical lamp, etc. can be used.

In the case where the extrusion relief layer 14 including the second base material 16 and the second adhesive layer 15 formed on the second base material is provided, the second adhesive layer 15 can be formed by The second adhesive layer on the separator is transferred to the surface of the first base material 10 opposite to the first adhesive layer 13 to be formed. In addition, the second adhesive layer 15 may be removed by directly applying the adhesive composition for an adhesive layer on the surface of the first base material 10 opposite to the first adhesive layer 13, and heating and drying the same. The solvent is used to form the second adhesive layer 15 on the first substrate 10 .

The second adhesive layer 15 can be formed by appropriately transferring the second adhesive layer formed on the release film subjected to the peeling treatment to the surface of the first base material 10 opposite to the metal layer 12 . In addition, the second adhesive layer 15 may be heated and dried to remove the solvent by directly applying the adhesive composition for the second adhesive layer on the surface of the first substrate 10 opposite to the metal layer 12 , and then heating and drying it. , thereby forming the second adhesive layer 15 on the first substrate 10 .

The above-mentioned description can be directly referred to the adhesive composition which can be used for forming the 2nd adhesive layer 15, and a separator.

＜8. Items＞ The article of the present embodiment is obtained by laminating the layered body or the electromagnetic wave-transmitting layered body 1 of the present embodiment to a transparent molded body. The article of this embodiment may also be a metallic luster article with metallic luster. 2 is a schematic cross-sectional view of a metallic glossy article according to an embodiment of the present invention. In the metallic glossy article 2, the electromagnetic wave transmissive laminate 1 having the configuration shown in FIG. 2 is attached to a transparent member 17 as a transparent molded body. In FIG. 2 , the electromagnetic wave-transmissive laminate 1 is attached to the surface on the opposite side (hereinafter, also referred to as the inner side) of the surface 17a on the visible side (hereinafter, also referred to as the outer side) of the transparent member 17 via the first adhesive layer 13 17 b , the metal layer 12 is visually recognized through the transparent member 17 and the first adhesive layer 13 . That is, the electromagnetic wave transmissive laminated body 1 of this embodiment can decorate the transparent member 17 from the inside. The metallic glossy article 2 of the present embodiment is obtained by attaching the electromagnetic wave transmissive layered body 1 to the inner side of the transparent member 17 , so it is not easily damaged. In addition, the transparent member 17 can be decorated directly using the texture of the transparent member 17 .

As the transparent member, from the viewpoint of transparency and electromagnetic wave transmittance, a member made of glass or plastic can be used.

The thickness of the transparent member is appropriately selected according to the application, and is preferably 100 μm to 2000 μm.

The method of attaching the electromagnetic wave transmissive layered body 1 to the transparent member 17 is not particularly limited, and for example, it can be attached by vacuum forming. Vacuum forming is a method of flattening the electromagnetic wave transmissive laminate 1 while heating and softening it, decompressing the space on the transparent member side of the electromagnetic wave transmissive laminate 1, and pressurizing the space on the opposite side as necessary , whereby the electromagnetic wave transmissive laminate 1 is formed, attached and laminated along the three-dimensional shape of the surface of the transparent member. As the electromagnetic wave transmissive laminate 1 , the above-mentioned description can be directly cited.

<9. Use of the item> The article provided with the electromagnetic wave transmissive laminate of the present embodiment is preferably a device (communication device) for transmitting and receiving electromagnetic waves, an article, its parts, and the like, since it has electromagnetic wave transmissivity. For example, housings for electronic equipment, structural parts for vehicles, automotive accessories, housings for home appliances, structural parts, mechanical parts, various automotive parts, electronic equipment parts, furniture, kitchen supplies, etc. Applications, medical equipment, parts of building materials, other structural parts or exterior parts, etc. As electronic equipment and home appliances, more specifically, home appliances such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting appliances, electric water heaters, televisions, clocks, ventilation fans, projectors, speakers, etc.; Electronic information devices such as telephones, smart phones, digital cameras, tablet PCs (Personal Computers), Walkmans, portable game consoles, chargers, batteries, etc. Vehicle-related aspects include: dashboards, console boxes, door handles, door trims, gear levers, pedals, glove boxes, bumpers, hoods, fenders, trunks, doors, sunroofs, and pillars , Seats, steering wheels, ECU (Electronic Control Unit, Electronic Control Unit) boxes, electrical parts, engine peripheral parts, drive system and gear peripheral parts, intake and exhaust system parts, cooling system parts, etc. [Example]

Hereinafter, an Example and a comparative example are given and this invention is demonstrated more concretely.

(1) Extrusion deformation force Fix the sample, use a small mechanical dynamometer UKK-20N with A-4 type attachment (IMADA company), press the attachment into the surface of the sample opposite to the glass surface, and judge by visual inspection. When the film in the sample is deformed, the pressing force [N] at this time is set as the pressing deformation force.

(2) Extrusion deformation parameter The extrusion deformation parameter was calculated according to the following formula (1). (E _O1 /T _O1 )×(E _S1 ×√T _S1 )×(T _O2 /E _O2 )×E _S2 Formula (1) E _O1 : elastic modulus of the first adhesive layer (MPa) T _O1 : the first 1 Thickness of the adhesive layer (μm) E _S1 : Modulus of elasticity of the first substrate (MPa) T _S1 : Thickness of the first substrate (μm) E _O2 : Modulus of elasticity of the second adhesive layer (MPa) T _O2 : Thickness of the second adhesive layer (μm) E _S2 : Elastic modulus of the second base material (MPa)

In addition, the elastic modulus at 25 degreeC of each layer which forms the electromagnetic wave transmissive laminated body was measured by the following method. A rectangular sample with a width of 10 mm and a length of 150 mm was produced, and a tensile testing machine (manufactured by Minebea, universal tensile and compressive testing machine, device name "tensile and compressive testing machine, TCM-1kNB") was used at a tensile speed of 50 The measurement is carried out under the condition of mm/min, and the elastic modulus is calculated according to the slope of the range where the displacement does not reach 5% in the elastic deformation region of the obtained stress-displacement curve.

(3) Film thickness of metal layer First, as shown in FIG. 4 , a square area 3 with a side of 5 cm is appropriately selected from the electromagnetic wave-transmitting laminate, and the center lines A and B of the vertical and horizontal sides of the square area 3 are divided into four equal parts to obtain a total of Five points "a" to "e" are selected, and points "a" to "e" are selected as measurement sites. Next, a cross-sectional image (transmission electron microscope (TEM image)) as shown in FIG. 5 at each selected measurement site was measured, and from the obtained TEM image, a section including five or more metal portions 12a was selected. field of view. The value obtained by dividing the total cross-sectional area of the metal layer in the viewing angle region selected by the 5 measurement sites by the lateral width of the viewing angle region is used as the film thickness of the metal layer in each viewing angle region. The average value of the film thickness of the metal layer in each viewing angle region is set as the thickness (nm) of the metal layer.

(4) Film thickness of the first adhesive layer, the second adhesive layer, and the first substrate The thicknesses of the first adhesive layer, the second adhesive layer, and the first base material were measured with a dial gauge.

(5) Sheet resistance The sheet resistance of the laminate was measured by the eddy current measurement method in accordance with JIS-Z2316 using a non-contact resistance measuring apparatus NC-80MAP manufactured by Napson Corporation. The sheet resistance is preferably 100 Ω/□ or more, more preferably 200 Ω/□ or more, and still more preferably 600 Ω/□ or more.

[Example 1] <Manufacture of a first base material with a metal layer> A film obtained by forming a UV-curable resin with a thickness of 2 μm on both sides of a PET film (thickness 50 μm) manufactured by Mitsubishi Plastics Co., Ltd. was used as a base material membrane. First, the ITO target was installed in a DC (Direct Current) magnetron sputtering device, and sputtering was performed while introducing argon gas, thereby forming an ITO layer with a thickness of 5 nm directly along the surface of the base film. When forming the ITO layer, the temperature of the base film was set to 130°C. The content ratio of tin oxide (SnО ₂ ) contained in ITO (content ratio=(SnO ₂ /(In ₂ O ₃ +SnO ₂ ))×100) was 10 wt %.

An aluminum (Al) target was installed in an AC sputtering apparatus (AC: 40 kHz), and sputtering was performed while introducing an argon gas, whereby an Al layer with a thickness of 35 nm was formed on the ITO layer, thereby obtaining a laminate 1. The obtained Al layer is a discontinuous layer. When forming the Al layer, the temperature of the base film was set to 130°C.

<Manufacture of the first adhesive layer with separator> An acrylic adhesive (SK Dyne 2563, manufactured by Soken Chemical Co., Ltd.) was applied to a polyester film with a thickness of 38 μm (trade name: DIAFOIL) with a final thickness of 5 μm, which had been peeled off with silicone on one side. MRF, the release-treated surface of Mitsubishi Plastics Co., Ltd.), thereby forming a coating layer. Next, the coating layer was dried at 85° C. for 5 minutes to form an acrylic adhesive layer, thereby producing a first adhesive layer with a release film. The polyester film covered with the first adhesive layer functions as a separator.

<Manufacture of an adhesive composition for forming a second adhesive layer> On the other hand, a monomer mixture containing 100 parts by mass of butyl acrylate, 0.01 part by mass of 2-hydroxyethyl acrylate, and 5 parts by mass of acrylic acid was placed in a reaction vessel equipped with a condenser tube, a nitrogen gas introduction tube, a thermometer, and a stirring device. Furthermore, 0.1 part by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator and 100 parts by mass of ethyl acetate were added together with respect to 100 parts by mass of the above-mentioned monomer mixture, and the mixture was slowly stirred. After nitrogen gas was introduced and replaced with nitrogen, the liquid temperature in the reaction vessel was maintained at around 55°C, and a polymerization reaction was performed for 8 hours to prepare a solution of an acrylic polymer having a weight average molecular weight (Mw) of 1.8 million and Mw/Mn=4.1 (Solid content concentration 30 mass %). With respect to 100 parts by mass of the solid content of the obtained acrylic polymer solution, 0.3 part by mass of benzyl peroxide (manufactured by NOF Corporation, Nyper BMT), and an isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, Coronate) were prepared. L) 1 part by mass to obtain an adhesive composition.

<Manufacture of electromagnetic wave transmissive laminates and metallic luster articles> The adhesive composition obtained above was applied to the surface opposite to the metal layer of the first base material in the laminated body 1 obtained above by applying the adhesive composition obtained above to a final thickness of 25 μm to form a second An adhesive layer, and a second base material with a thickness of 25 μm is attached to the second adhesive layer to form an extrusion relief layer. The 1st adhesive bond layer with the separator obtained above was transcribe|transferred to the surface of the metal layer side, and the separator was peeled off, and the electromagnetic wave transmissive laminated body was obtained. The 1st adhesive bond layer side of the electromagnetic wave transmissive laminated body obtained above was stuck to a transparent member, and the metallic glossy article was obtained. As the transparent member, glass with a thickness of 1.2 mm was used.

[Examples 2 to 4, Comparative Examples 1 to 8] The same procedure as in Example 1 was performed except that the thicknesses of the first adhesive layer, the first base material, the second adhesive layer, and the second base material in Example 1 were changed to the values described in Table 1. The electromagnetic wave-transmitting laminate was obtained in the same manner, and a metallic glossy article was obtained.

The evaluation results are shown in Table 1 below.

[Table 1] Table 1 1st adhesive layer 1st base material 2nd adhesive layer 2nd base material Extrusion parameters Extrusion force sheet resistance E _O1 T _O1 E _S1 T _S1 E _{O 2} T _{O 2} E _{S 2} T _{S 2} elastic modulus thickness elastic modulus thickness elastic modulus thickness elastic modulus thickness [MPa] [μm] [MPa] [μm] [MPa] [μm] [MPa] [μm] [N] [Ω/□] Example 1 0.5 5 4000 54 0.5 25 4000 25 587,877,538 5.7 ＞1,000 Example 2 0.5 5 4000 54 0.5 twenty three 4000 7 540,847,335 3.7 ＞1,000 Example 3 0.5 25 4000 54 0.5 100 4000 100 470,302,031 3.7 ＞1,000 Example 4 0.5 5 4000 54 0.5 20 4000 10 470,302,031 3.3 ＞1,000 Comparative Example 1 0.5 5 4000 54 0.5 10 4000 10 235,151,015 1.9 ＞1,000 Comparative Example 2 0.5 25 4000 150 0.5 25 4000 25 195,959,179 0.9 ＞1,000 Comparative Example 3 0.5 25 4000 100 0.5 25 4000 25 160,000,000 0.7 ＞1,000 Comparative Example 4 0.5 25 4000 54 0.5 25 4000 25 117,575,508 0.7 ＞1,000 Comparative Example 5 0.5 25 4000 twenty three 0.5 25 4000 25 76,733,304 0.2 ＞1,000 Comparative Example 6 0.5 50 4000 54 0.5 25 4000 25 58,787,754 0.2 ＞1,000 Comparative Example 7 0.5 100 4000 54 0.5 25 4000 25 29,393,877 0.2 ＞1,000 Comparative Example 8 0.5 5 4000 54 - - - - - 0.9 ＞1,000

As can be seen from Table 1, for the laminates of Examples 1 to 4 whose extrusion deformation parameters are 4×10 ⁸ or more, good metallic appearance can be obtained despite the extrusion of 3 N or more from the second base material side.

On the other hand, with respect to the laminated bodies of Comparative Examples 1 to 8, when a pressing force of about 3 N was applied from the second base material side, the metal appearance was defective as a result.

The present invention is not limited to the above-described embodiments, and can be appropriately modified and embodied within a range that does not deviate from the gist of the invention. [Industrial Availability]

The laminated body and the electromagnetic wave transmissive laminated body of the present invention have excellent appearance, and the metallic luster article provided with the laminated body or the electromagnetic wave transmissive laminated body of the present invention can be used as parts of devices for transmitting and receiving electromagnetic waves. For example, it can also be used in various applications requiring both designability and electromagnetic wave transmittance, such as housings for electronic devices such as mobile phones, smart phones, and computers, structural parts for vehicles, vehicle accessories, and housings for home appliances , Structural parts, mechanical parts, various automobile parts, electronic equipment parts, furniture, kitchen supplies, etc. for household purposes, medical equipment, parts of building materials, other structural parts or exterior parts, etc.

The present invention has been described in detail with reference to the specific embodiment, but it is clear to those skilled in the art that various changes and corrections can be added without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application (Japanese Patent Application No. 2020-063228) filed on March 31, 2020, the contents of which are incorporated herein by reference.

1: Electromagnetic wave transmissive laminate 2: Metallic glossy items 3: Square area 10: The first substrate 11: Indium oxide containing layer 12: Metal layer 12a: Section 12b: Gap 13: The first adhesive layer 14: Squeeze the easing layer 15: Second Adhesive Layer 16: 2nd substrate 17: Transparent Components 17a: face 17b: face A, B: center line a~e: point

FIG. 1 is a schematic cross-sectional view of an electromagnetic wave-transmissive laminate according to an embodiment of the present invention. 2 is a schematic cross-sectional view of a metallic glossy article according to an embodiment of the present invention. 3 is an electron microscope photograph of the surface of the metal layer of the electromagnetic wave-transmitting laminate according to one embodiment of the present invention. FIG. 4 is a diagram for explaining a method of measuring the film thickness of the metal layer of the electromagnetic wave-transmitting laminate according to one embodiment of the present invention. 5 is a diagram showing a transmission electron microscope photograph (TEM image) of a cross section of a metal layer in one embodiment of the present invention.

1: Electromagnetic wave transmissive laminate

10: The first substrate

11: Indium oxide containing layer

12: Metal layer

12a: Section

12b: Gap

13: The first adhesive layer

14: Squeeze the easing layer

15: Second Adhesive Layer

16: 2nd substrate

Claims (11)

A layered product comprising, in this order, a first substrate, an optical functional layer formed on the first substrate, and a first adhesive layer, and provided on the surface of the first substrate on the opposite side to the optical functional layer The extrusion relaxation layer includes a second base material and a second adhesive layer, and the extrusion deformation parameter is 4×10 ⁸ or more. The laminate according to claim 1, wherein the optical functional layer is a metal layer. The laminate according to claim 2, further comprising an indium oxide-containing layer between the first base material and the metal layer. The laminate of claim 3, wherein the indium oxide-containing layer is provided in a continuous state. The laminate according to claim 3 or 4, wherein the indium oxide-containing layer comprises any one of indium oxide (In ₂ O ₃ ), indium tin oxide (ITO), or indium zinc oxide (IZO). The laminate according to any one of claims 2 to 5, wherein the metal layer is comprised of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), silver (Ag), or an alloy thereof. either. The laminate according to any one of claims 2 to 6, wherein the first base material has light-shielding properties. An electromagnetic wave-transmitting laminate, which is the laminate according to any one of Claims 2 to 7, and The above-mentioned metal layer includes a plurality of parts in which at least a part is in a state of being discontinuous with each other. The electromagnetic wave transmissive laminate according to claim 8, wherein the plurality of parts are formed in an island shape. The electromagnetic wave-transmitting laminate of claim 8 or 9 has a sheet resistance of 100 Ω/□ or more. An article obtained by laminating the laminate according to any one of claims 1 to 7 or the electromagnetic wave-transmitting laminate according to any one of claims 8 to 10 to a transparent molded body.

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