JP2022129029A - Electromagnetic wave transmissive metallic sheen member and decorative member - Google Patents

Abstract

To improve an adhesive force which has been poor between an electromagnetic wave transmissive metallic sheen article and an adherend member, when the conventional electromagnetic wave transmissive metallic sheen article is adhered onto the adherend member interposing an adhesive agent to form a decorative member.SOLUTION: An electromagnetic wave transmissive metallic sheen member 1 includes a substrate 10, and on the substrate 10, a metallic sheen layer 12, a barrier layer 13 and an adhesive layer 14 arranged in this order. The metallic sheen layer 12 includes a plurality of portions in a state of discontinuity with each other at least in part. An average particle diameter at the plurality of portions is 15 to 90 nm. A ratio Sa/d is 0.05 or more, the ratio Sa/d being a ratio of arithmetic average roughness Sa (nm) on a surface of the barrier layer 13 to film thickness d (nm) of a total of the metallic sheen layer 12 and the barrier layer 13.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to an electromagnetic wave transmitting metallic glossy member and a decorative member.

BACKGROUND ART Conventionally, members having electromagnetic wave permeability and metallic luster have been suitably used for devices that transmit and receive electromagnetic waves because they have both a luxurious appearance derived from the metallic luster and electromagnetic wave permeability.
If metal is used for the member with metallic luster, the transmission and reception of electromagnetic waves are substantially impossible or obstructed. Therefore, there is a need for an electromagnetic wave-transmitting metallic luster member that has both metallic luster and electromagnetic wave transmittance so as not to interfere with the transmission and reception of electromagnetic waves and not to impair the design.

Such an electromagnetic wave permeable metallic luster member can be used as a device for transmitting and receiving electromagnetic waves in various devices that require communication, such as door handles of automobiles equipped with smart keys, in-vehicle communication devices, mobile phones, electronic devices such as personal computers. It is expected to be applied to equipment and the like. Furthermore, in recent years, with the development of IoT technology, it is expected to be applied in a wide range of fields, such as household appliances such as refrigerators and household appliances, where communication has not been performed in the past.

Regarding an electromagnetic wave transmitting metallic glossy member, Patent Document 1 discloses a substrate, a metal layer formed on the substrate, and a barrier layer formed on the surface of the metal layer opposite to the substrate. An electromagnetic wave transmitting metallic luster article is disclosed, wherein the metal layer includes a plurality of portions that are at least partially discontinuous with each other.

JP 2019-188805 A

However, when the electromagnetic wave transmitting metallic luster article disclosed in Patent Document 1 is attached to an adherend via an adhesive to form a decorative member, the electromagnetic wave transmitting metallic luster article and the adherend member There was a problem that the adhesive strength was poor between. If the adhesive strength is poor, for example, when the adherend member is removed from the commercialized decorative member for some reason, the adhesive may remain on the adherend member, resulting in poor reworkability. end up

The present invention has been made in view of the above, and an electromagnetic wave permeable metallic luster that can sufficiently increase the adhesive force to the decorating member when attached to a member to be adhered via an adhesive to form a decorating member. An object is to provide a member and a decorative member.

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have obtained a plurality of discontinuous metallic lustrous layers having a metallic lustrous layer, a barrier layer, and an adhesive layer in this order on a substrate. and setting the average particle size of the plurality of portions to a specific range, and the ratio of the arithmetic mean roughness Sa of the surface of the barrier layer and the total thickness d of the metallic luster layer and the barrier layer to The inventors have found that the above problems can be solved by adjusting the content to a specific range, and have completed the present invention.

That is, the present invention is as follows.
[1]
A substrate, and a metallic luster layer, a barrier layer, and an adhesive layer provided on the substrate in this order,
The metallic luster layer includes a plurality of portions that are discontinuous at least in part,
The average particle size of the plurality of portions is 15 to 90 nm,
Sa/d, which is a ratio of the arithmetic mean roughness Sa (nm) of the surface of the barrier layer to the total thickness d (nm) of the metallic luster layer and the barrier layer, is 0.05 or more. An electromagnetic wave transparent metallic luster member.
[2]
The electromagnetic wave transmitting metallic luster member according to [1], wherein the thickness of the barrier layer is 10 nm or more and 50 nm or less.
[3]
The barrier layer contains at least one selected from the group consisting of at least one oxide, nitride, carbide, oxynitride, oxycarbide, nitride carbide, and oxynitride carbide of at least one metal and semimetal. The electromagnetic wave transmitting metallic luster member according to [1] or [2].
[4]
The electromagnetic wave according to any one of [1] to [3], wherein the barrier layers each independently contain at least one selected from the group consisting of AZO, ITO, AlO _x and SiO ₂ . Permeable metallic luster member.
[5]
The electromagnetic wave transmitting metallic luster member according to any one of [1] to [4], wherein the metallic luster layer contains aluminum or an aluminum alloy.
[6]
The electromagnetic wave transmitting metallic luster member according to any one of [1] to [5], further comprising an indium oxide-containing layer between the substrate and the metallic luster layer.
[7]
The electromagnetic wave transmission according to [6], wherein the indium oxide-containing layer contains any one of indium oxide (In ₂ O ₃ ), indium tin oxide (ITO), or indium zinc oxide (IZO). material with metallic luster.
[8]
The electromagnetic wave transmitting metallic luster member according to any one of [1] to [7], wherein the metallic luster layer has a thickness of 3 nm to 50 nm.
[9]
The electromagnetic wave transmitting metallic luster member according to any one of [1] to [8], which has a sheet resistance of 100Ω/□ or more.
[10]
The electromagnetic wave transmitting metallic luster member according to any one of [1] to [9], wherein the plurality of portions are formed like islands.
[11]
The electromagnetic wave according to any one of [1] to [10], wherein the substrate is a substrate film, a resin molding substrate, a glass substrate, or an article to be imparted with metallic luster. Permeable metallic luster member.
[12]
An adherend and an electromagnetic wave transmitting metallic luster member according to any one of [1] to [11], wherein the electromagnetic wave transmitting metallic luster member is attached to the adherend via the adhesive layer. decorative material.

According to the present invention, there are provided an electromagnetic wave transmitting metallic luster member and a decorating member that can sufficiently increase the adhesive force to the decorating member when attached to an adherend via an adhesive to form a decorating member. be able to.

FIG. 1 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member according to one embodiment of the present invention. FIG. 2 is an electron micrograph (SEM image) of the surface of the metallic luster layer of the electromagnetic wave transmitting metallic luster member according to one embodiment of the present invention. FIG. 3 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member according to one embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of a decorative member according to one embodiment of the present invention. FIG. 5 is a diagram for explaining a method for measuring the thickness of the metallic luster layer of the electromagnetic wave transmitting metallic luster member according to one embodiment of the present invention. FIG. 6 is a diagram showing an electron microscope photograph (TEM image) of a cross section of the electromagnetic wave transmitting metallic luster member according to one embodiment of the present invention. FIG. 7 is a graph showing the results of Examples and Comparative Examples. "Actual" indicates an example, and "ratio" indicates a comparative example.

Preferred embodiments of the present invention will be described below with reference to the accompanying drawings. In the following, only preferred embodiments of the present invention are shown for convenience of explanation, but of course, this is not intended to limit the present invention.

<1. Basic configuration>
An electromagnetic wave transmitting metallic luster member according to an embodiment of the present invention comprises a substrate, and a metallic luster layer, a barrier layer, and an adhesive layer on the substrate in this order, and the metallic luster layer is at least partially mutually incompatible. It includes a plurality of portions in a continuous state, the average particle size of the plurality of portions is 15 to 90 nm, the arithmetic mean roughness Sa (nm) of the barrier layer surface, and the metallic luster layer and the barrier layer A ratio Sa/d to the total film thickness d (nm) is 0.05 or more.

FIG. 1 shows a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member 1 according to one embodiment of the present invention. Moreover, FIG. 2 shows an example of an electron microscope photograph (SEM image) of the surface of the metallic luster layer of the electromagnetic wave transmitting metallic luster member 1 according to one embodiment of the present invention.

As shown in FIG. 1, the electromagnetic wave transmitting metallic luster member 1 has a base 10, a metallic luster layer 12, a barrier layer 13, and an adhesive layer 14 formed on the base 10 in this order. . The electromagnetic wave transmitting metallic luster member 1 may further include an indium oxide-containing layer 11 between the substrate 10 and the metallic luster layer 12 . Metallic luster layer 12 is preferably formed on indium oxide-containing layer 11 . In the present invention, the layer optionally provided between the substrate 10 and the metallic luster layer 12 is not limited to the indium oxide-containing layer 11, and may be other inorganic oxide layers.

The indium oxide-containing layer 11 is preferably provided on the underlying surface in a continuous state, in other words, without gaps. By providing the indium oxide-containing layer 11 in a continuous state, the smoothness and corrosion resistance of the electromagnetic wave transmitting metallic luster member 1 can be improved, and the indium oxide-containing layer 11 can be formed uniformly in the plane. It also becomes easier.

In the form shown in FIG. 1 , the metallic luster layer 12 is laminated on the indium oxide-containing layer 11 . The metallic luster layer 12 includes a plurality of portions 12a. By stacking on the indium oxide-containing layer 11, these portions 12a are at least partially discontinuous, in other words, at least partially separated by gaps 12b. Since these portions 12a are separated by the gap 12b, the sheet resistance of these portions 12a is increased and the interaction with radio waves is reduced, so that the radio waves can be transmitted. Each of these portions 12a is an aggregate of sputtered particles formed by vapor deposition, sputtering, or the like of metal. When sputtered particles form a thin film on a substrate such as substrate 10, the surface diffusivity of the particles on the substrate affects the shape of the thin film.

The term "discontinuous state" as used in this specification means a state in which they are separated from each other by the gap 12b and, as a result, are electrically insulated from each other. By being electrically insulated, the sheet resistance is increased and the desired electromagnetic wave permeability can be obtained. The form of discontinuity is not particularly limited, and includes, for example, islands, cracks, and the like.

Here, the term "island-like" means that, as shown in the electron micrograph (SEM image) of the surface of the metallic luster layer of the electromagnetic wave transmitting metallic luster member shown in FIG. Each of them is independent, and means a structure in which those particles are laid out in a state that they are slightly spaced from each other or are partially in contact with each other.

A crack structure is a structure in which a metal thin film is divided by cracks.
The metal luster layer 12 having a crack structure can be formed, for example, by providing a metal thin film layer on the indium oxide-containing layer 11 formed on the substrate, and bending and stretching the metal thin film layer to cause cracks in the metal thin film layer. At this time, by providing a brittle layer made of a material having poor stretchability, that is, easily cracked by stretching, between the indium oxide-containing layer 11 and the metal thin film layer, the metallic luster layer 12 having a crack structure can be easily formed. be able to.

As described above, the mode in which the metallic luster layer 12 is discontinuous is not particularly limited, but from the viewpoint of productivity, it is preferably "island-shaped".

Further, the electromagnetic wave transmitting metallic luster member 1 according to the embodiment of the present invention preferably has a reflection Y value of 20% or more in the SCI method of the CIE-XYZ color system, more preferably 30% or more. , more preferably 40% or more.
The reflection Y value of the electromagnetic wave transmitting metallic luster member 1 according to the embodiment of the present invention can be measured according to JIS Z 8722 using a spectrophotometer.
By setting the reflection Y value of the electromagnetic wave transmitting metallic luster member 1 within a specific range, excellent electromagnetic wave transmitting properties can be obtained, metallic luster with suppressed coloring can be obtained, and good transparency can be obtained. As a result, when the electromagnetic wave transmitting metallic luster member 1 is adhered to an adherend to form a decorative member, the surface shape and color of the adherend can be visually recognized even through the electromagnetic wave transmitting metallic luster member 1 without impairing the surface shape and color of the adherend. can.
The reflection Y value of the electromagnetic wave transmitting metallic luster member 1 can be adjusted by the thickness of the metallic luster layer 12 .

The reflected Y value (luminous reflectance) is the average reflectance weighted by the luminosity and the light intensity of the light source in the range of the measurement wavelength measured by incident on the surface of the electromagnetic wave transmitting metallic luster member 1 on the metallic luster layer 12 side. is.
The reflection Y value is preferably 20% or more from the viewpoint of obtaining an appearance exhibiting metallic luster with suppressed coloring.

In the electromagnetic wave transmitting metallic luster member 1 according to the present embodiment, both the a* value and the b* value are close to 0 in the CIE-L*a*b* color system of the reflected light on the adherend member side. preferable.

The CIE-L*a*b* color system is a color system recommended by the CIE (International Commission on Illumination) in 1976. L* represents lightness, and the larger the value on a scale of 0 to 100, the brighter the color. Chromaticity is represented by a* and b*, where a* is an index indicating the degree of color tone from red to green, and when the value of a* is large in the positive direction, the color tone becomes red. Furthermore, b* is an index indicating the degree of color tone from yellow to blue, and when the value of b* is large in the positive direction, the color tone becomes yellow. When both a* and b* are 0, the color is achromatic.

Further, the electromagnetic wave permeability of the electromagnetic wave transparent metallic luster member 1 has a correlation with the sheet resistance.
The radio wave transmission attenuation in the microwave band (28 GHz) is preferably less than 10 [-dB], more preferably less than 5 [-dB], and even more preferably less than 2 [-dB]. . If the radio wave transmission attenuation in the microwave band (28 GHz) is 10 [-dB] or more, there is a problem that 90% or more of the radio waves are blocked.

The radio wave transmission attenuation and sheet resistance of the electromagnetic wave transparent metallic luster member 1 are affected by the material, thickness, etc. of the indium oxide-containing layer 11 and the metallic luster layer 12 .

<2. Substrate>
In the electromagnetic wave transmitting metallic luster member according to this embodiment, the substrate 10 includes resin, glass, ceramics, etc. from the viewpoint of electromagnetic wave transmitting properties.
The substrate 10 may be a substrate film, a resin molding substrate, a glass substrate, or an article to be imparted with metallic luster.
More specifically, the base film includes, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polyvinyl chloride, polycarbonate (PC), cycloolefin polymer (COP), polystyrene , polypropylene (PP), polyethylene, polycycloolefin, polyurethane, acrylic (PMMA), ABS, and other homopolymers or copolymers.

These members do not affect the brilliance and electromagnetic wave permeability. However, from the viewpoint of forming the indium oxide-containing layer 11 and the metallic luster layer 12 later, it is preferable that the material can withstand high temperatures such as vapor deposition and sputtering. Therefore, among the above materials, for example, polyethylene terephthalate, polyethylene naphthalate, acrylic, polycarbonate, cycloolefin polymer, ABS, polypropylene, and polyurethane are preferred. Among them, polyethylene terephthalate, cycloolefin polymer, polycarbonate, and acrylic are preferable because they have a good balance between heat resistance and cost.

The base film may be a single layer film or a laminated film. The thickness is preferably, for example, about 6 μm to 250 μm from the viewpoint of ease of processing. In order to strengthen the adhesion to the indium oxide-containing layer 11 and the metallic luster layer 12, plasma treatment, easy-adhesion treatment, or the like may be performed.
When the substrate 10 is a substrate film, the metallic luster layer 12 may be provided on at least a portion of the substrate film, and may be provided on only one side of the substrate film or may be provided on both sides.

The substrate film may have a smooth or antiglare hard coat layer formed thereon, if necessary. By providing the hard coat layer, the scratch resistance of the metal thin film can be improved. By providing the smooth hard coat layer, metallic luster is increased, and conversely, glare can be prevented by the anti-glare hard coat layer. The hard coat layer can be formed by applying a solution containing a curable resin.

Examples of the curable resin include thermosetting resin, ultraviolet curable resin, electron beam curable resin, and the like. Examples of curable resins include various resins such as polyester, acrylic, urethane, acrylic urethane, amide, silicone, silicate, epoxy, melamine, oxetane, and acrylic urethane. One or more of these curable resins can be appropriately selected and used. Among these resins, acrylic resins, acrylic urethane resins, and epoxy resins are preferable because they have high hardness, can be cured with ultraviolet rays, and are excellent in productivity.

It should be noted here that the base film is only one example of a target (substrate 10) on which the metallic luster layer 12 can be formed. The substrate 10 includes, in addition to the substrate film as described above, a resin molding substrate, a glass substrate, and the article itself to which metallic luster is to be imparted. Examples of resin molding substrates and articles to which metallic luster is to be imparted include structural parts for vehicles, articles mounted on vehicles, housings for electronic equipment, housings for home appliances, structural parts, machine parts, and various automobiles. electronic equipment, furniture, household goods such as kitchen utensils, medical equipment, building material parts, other structural parts and exterior parts.

The metallic luster layer 12 can be formed on all these substrates, and may be formed on a part of the surface of the substrate or on the entire surface of the substrate. In this case, the substrate 10 to which the metallic luster layer 12 is to be applied preferably satisfies the same materials and conditions as those of the substrate film described above.

<3. Indium oxide-containing layer>
Further, the electromagnetic wave transmitting metallic luster member 1 according to one embodiment may further include an indium oxide-containing layer 11 between the substrate 10 and the metallic luster layer 12, as shown in FIG. The indium oxide-containing layer 11 may be provided directly on the surface of the substrate 10 or may be provided indirectly via a protective film or the like provided on the surface of the substrate 10 . The indium oxide-containing layer 11 is preferably provided in a continuous state, in other words, without gaps. By being provided in a continuous state, it is possible to improve the smoothness and corrosion resistance of the indium oxide-containing layer 11, and thus the metallic luster layer 12 and the electromagnetic wave transmitting metallic luster member 1. It also becomes easy to form a film without variation in the thickness.

Thus, the indium oxide-containing layer 11 is further provided between the substrate 10 and the metallic luster layer 12, that is, the indium oxide-containing layer 11 is formed on the substrate 10, and the metallic luster layer 12 is formed thereon. This is preferable because it facilitates formation of the metallic luster layer 12 in a discontinuous state. Although the details of the mechanism are not necessarily clear, when sputtered particles from metal vapor deposition or sputtering form a thin film on a substrate, the surface diffusibility of the particles on the substrate affects the shape of the thin film. It is considered that a discontinuous structure is likely to be formed when the temperature is high, the wettability of the metallic luster layer to the substrate is small, and the melting point of the material of the metallic luster layer is low. By providing the indium oxide-containing layer 11 on the substrate, it is believed that the surface diffusibility of the metal particles on the surface is promoted, making it easier to grow the metallic lustrous layer 12 in a discontinuous state.

As the indium oxide-containing layer 11, indium oxide (In ₂ O ₃ ) itself can be used. For example, metal inclusions such as indium tin oxide (ITO) and indium zinc oxide (IZO) can be used. can also be used. However, ITO and IZO containing the second metal are more preferable in terms of high discharge stability in the sputtering process. By using these indium oxide-containing layers 11, a continuous film can be formed along the surface of the substrate, and in this case, a metallic luster layer laminated on the indium oxide-containing layer 11 12, for example, can be easily formed into an island-shaped discontinuous structure, which is preferable. Furthermore, as will be described later, in this case, in addition to chromium (Cr) or indium (In), the metallic luster layer 12 is usually difficult to form a discontinuous structure, and it is difficult to apply to this application. Or easier to include aluminum alloys.

The content ratio (content ratio = (SnO ₂ /(In ₂ O ₃ +SnO ₂ )) × 100), which is the mass ratio of tin oxide (SnO ₂ ) contained in ITO, is not particularly limited. .5% to 30% by weight, more preferably 3% to 10% by weight. Further, the content rate (content rate = (ZnO/(In ₂ O ₃ +ZnO)) x 100), which is the mass ratio of zinc oxide (ZnO) contained in IZO, is, for example, 2 mass% to 20 mass%.
The thickness of the indium oxide-containing layer 11 is usually preferably 1000 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less, from the viewpoints of sheet resistance, electromagnetic wave permeability, and productivity. On the other hand, the thickness is preferably 1 nm or more in order to facilitate the discontinuous state of the laminated metallic luster layer 12, and more preferably 3 nm or more in order to more reliably facilitate the discontinuous state. It is more preferably 5 nm or more.

<4. Metallic luster layer>
The metallic luster layer 12 is formed on the substrate and includes a plurality of portions that are at least partially discontinuous with each other. The metal contained in the metallic luster layer 12 is preferably aluminum or an aluminum alloy.
If the metallic lustrous layer 12 is in a continuous state on the substrate, sufficient luster can be obtained, but the amount of radio wave transmission attenuation becomes very large, and therefore the electromagnetic wave transmission cannot be ensured.

Although the details of the mechanism by which the metallic luster layer 12 becomes discontinuous on the substrate are not necessarily clear, it is presumed to be roughly as follows. That is, in the process of forming a thin film of the metallic luster layer 12, the ease of forming a discontinuous structure is related to the surface diffusion on the substrate to which the metallic luster layer 12 is applied. A discontinuous structure is easily formed when the wettability of the metallic luster layer is low and the melting point of the material of the metallic luster layer is low.

Here, the average particle size of the plurality of portions 12a means the average value of the equivalent circle diameters of the plurality of portions 12a. The equivalent circle diameter of the portion 12a is the diameter of a perfect circle corresponding to the area of the portion 12a.
The average grain size of the portion 12a of the metallic luster layer 12 should be 15 to 90 nm. Since the average grain size of the portion 12a is 15 to 90 nm, the arithmetic mean roughness Sa (nm) of the surface of the barrier layer 13 and the total thickness of the metallic luster layer 12 and the barrier layer 13 are reduced as described below. When Sa/d, which is the ratio to d (nm), is 0.05 or more, the unevenness based on the discontinuity of the metallic luster layer 12 exerts an anchor effect on the adhesive layer 14, and the metallic luster layer 12 and the barrier layer 13 and the pressure-sensitive adhesive layer 14 are increased, thereby improving the adhesion to the adherend.

The average particle size of the portion 12a of the metallic luster layer 12 is more preferably 10 nm or more and 90 nm or less, and particularly preferably 30 nm or more and 70 nm or less.
The average particle size of the plurality of portions 12a is measured by the method described in Examples.
Also, the average grain size can be adjusted by, for example, changing the metal sputtering conditions.
Also, the distance between the portions 12a is not particularly limited, but is usually about 10 to 1000 nm.

By setting the average grain size of the plurality of mutually discontinuous portions 12a included in the metallic luster layer within the above range, the luster can be further improved while maintaining high electromagnetic wave transmittance.

The metallic luster layer 12 preferably has a relatively low melting point, as well as being capable of exhibiting sufficient luster and good transparency. This is because the metallic luster layer 12 is preferably formed by thin film growth using sputtering.
For this reason, a metal with a melting point of about 1000° C. or less is suitable for the metallic luster layer 12, and it preferably contains aluminum or an aluminum alloy.
As the metallic luster layer 12, it is particularly preferable to use Al and their alloys for reasons such as brilliance, transparency, and price. Moreover, when using an aluminum alloy, it is preferable to make aluminum content into 50 mass % or more.

The thickness of the metallic luster layer 12 is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more in order to suppress coloration and exhibit sufficient luster and good transparency. preferable. From the viewpoint of electromagnetic wave permeability, the thickness is preferably 50 nm or less, more preferably 40 nm or less, and even more preferably 35 nm or less.
This thickness is also suitable for forming a uniform film with good productivity, and the appearance of decorative members and resin molded products, which are final products, is good.

The sheet resistance of the metallic luster layer is preferably 100Ω/□ or more. In this case, the electromagnetic wave transmittance is less than 10 [-dB] at a wavelength of 5 GHz. More preferably, it is 1000Ω/□ or more.

The sheet resistance of the electromagnetic wave transmitting metallic luster member 1 is also preferably 100Ω/□ or more.
From the viewpoint of electromagnetic wave permeability, the sheet resistance is more preferably 200Ω/square or more, still more preferably 600Ω/square or more, and even more preferably 1000Ω/square or more. The value of this sheet resistance is greatly affected by not only the material and thickness of the metallic luster layer 12 but also the material and thickness of the indium oxide-containing layer 11 .

<5. Barrier layer>
As described above, the electromagnetic wave transmitting metallic luster member 1 comprises a substrate 10, a metallic luster layer 12, a barrier layer 13, and an adhesive layer 14 in this order.

The barrier layer 13 will be explained.
The barrier layer 13 prevents entry of H ₂ O and O ₂ from the substrate 10 side and the opposite side (metallic luster layer side), suppresses oxidation of the metallic luster layer 12, and improves reliability over time, especially in a high temperature atmosphere. reliability can be improved.

Barrier layer 13 preferably contains at least one selected from the group consisting of at least one oxide, nitride, carbide, oxynitride, oxycarbide, nitride carbide, and oxynitride carbide of at least one metal and semimetal. Examples of metals that can be used include aluminum, titanium, indium, and magnesium, and examples of metalloids that can be used include silicon, bismuth, and germanium.

Specifically, for example, ZnO+Al ₂ O ₃ (AZO), indium zinc oxide (IZO), indium tin oxide (ITO), silicon oxycarbonitride film (SiOCN), silicon oxynitride film (SiON), silicon nitride film (SiN ), SiO _x , AlO _x , AlON, TiO _x and the like can be used. Among them, it is preferable to use at least one selected from the group consisting of AZO, ITO, AlO _X and SiO ₂ .
In order to improve the performance of the barrier layer 13 to suppress the oxidation (corrosion) of the metallic luster layer 12 (hereinafter also referred to as “barrier property”), the network structure (mesh-like structure) in the barrier layer should be made dense. It preferably contains carbon and nitrogen. In order to further improve transparency, it is preferable to contain oxygen. That is, the barrier layer preferably contains at least one carbide oxynitride of a metal and a metalloid.

Moreover, in order to improve the barrier property, it is preferable that the barrier layer 13 is difficult to permeate water vapor. The water vapor transmission rate of the barrier layer 13 is preferably 5 g/(m ² ·day) or less, more preferably 3 g/(m ² ·day) or less, and 2 g/(m ² ·day) or less. It is even more preferable to have

The thickness of the barrier layer 13 is preferably 10 nm or more and 50 nm or less, and preferably 20 nm or more and less than 40 nm, from the viewpoint of exhibiting the uneven anchor effect based on the discontinuous state of the metallic luster layer 12 with respect to the adhesive layer 14 described above. is more preferable.
The barrier layer 13 only needs to be laminated on the metallic luster layer 12, and does not necessarily have to completely fill the gap 12b. The thickness of the barrier layer 13 is measured by the method described in Examples.

<6. Adhesive layer>
The adhesive layer 14 is preferably a layer made of a transparent adhesive.
The adhesive that forms the adhesive layer 14 is, for example, any of an acrylic adhesive, a rubber adhesive, a silicone adhesive, a polyester adhesive, a urethane adhesive, an epoxy adhesive, and a polyether adhesive. can be used alone or in combination of two or more. From the viewpoint of transparency, processability, durability, etc., it is preferable to use an acrylic pressure-sensitive adhesive.

The thickness of the adhesive layer 14 is not particularly limited, but it is 100 μm or less because making it thinner contributes to the thinning of the final product structure and improves the visible light transmittance, film thickness accuracy, and flatness. is preferred, 75 µm or less is more preferred, and 50 µm or less is even more preferred.

A release liner may be provided on the pressure-sensitive adhesive layer in order to protect the pressure-sensitive adhesive layer until it is attached to an adherend.

In the electromagnetic wave transmitting metallic luster member 1 of the present invention, the ratio of the arithmetic mean roughness Sa (nm) of the surface of the barrier layer 13 to the total film thickness d (nm) of the metallic luster layer 12 and the barrier layer 13 is Sa /d must be 0.05 or more. If the Sa/d is less than 0.05, the uneven anchoring effect based on the discontinuous state of the metallic luster layer 12 with respect to the pressure-sensitive adhesive layer 14 is not exhibited.
Said Sa/d is preferably 0.07 or more. Moreover, Sa/d is preferably 0.30 or less, more preferably 0.20 or less.
By increasing the thickness of the metallic luster layer, the arithmetic mean roughness Sa of the surface of the barrier layer 13 can be adjusted to be large, and by increasing the thickness of the barrier layer, Sa can be reduced. d can be adjusted.
The arithmetic mean roughness Sa (nm) of the surface of the barrier layer 13 and the total film thickness d (nm) of the metallic luster layer 12 and the barrier layer 13 can be measured by the method described in Examples.

In the electromagnetic wave transmitting metallic luster member 1 of the present embodiment, in addition to the metallic luster layer 12, the indium oxide-containing layer 11, the barrier layer 13, and the adhesive layer 14 described above, as long as the effect of the present invention is exhibited, Other layers may be provided. Other layers include an optical adjustment layer (color adjustment layer) such as a high-refractive material for adjusting appearance such as color, and a protective layer (resistant layer) for improving durability such as moisture resistance and scratch resistance abrasion layer) and the like.

<7. Resin layer>
The electromagnetic wave transmitting metallic luster member 1 of the present embodiment may have a resin layer as long as the effects of the present invention are not impaired. The resin layer may be provided on the surface of the metallic luster layer 12 opposite to the substrate 10 side.

In the electromagnetic wave transmitting metallic luster member 1 of the present embodiment, the haze value of the resin layer is preferably less than 20%.
The haze value of the resin layer is preferably less than 20%, more preferably 10% or less, and even more preferably 5% or less, from the viewpoint of achieving an appearance with excellent transparency. Further, by adjusting the haze value of the resin layer, it is possible to control the L* value, the a* value, and the b* value of the obtained electromagnetic wave transmitting metallic luster member.
The haze value of the resin layer can be measured with a measuring instrument such as a haze meter HM-150N (manufactured by Murakami Color Science Laboratory Co., Ltd.), and can be measured by the method described in Examples.

The resin layer includes an optical adjustment layer (color adjustment layer) such as a high refractive material for adjusting appearance such as color, and a protective layer (scratch resistance) to improve durability such as moisture resistance and scratch resistance. layer), an easy adhesion layer, the hard coat layer described above, an antireflection layer, a light extraction layer, an antiglare layer, and the like.
A plurality of resin layers can be provided.

FIG. 3 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member according to one embodiment of the present invention. As shown in FIG. 3, the electromagnetic wave transmitting metallic luster member 1 includes a substrate 10, a hard coat layer 15, an indium oxide-containing layer 11, a metallic luster layer 12, a barrier layer 13, and an adhesive layer 14. may be

<7. Production of electromagnetic wave transparent metallic luster member>
An example of a method for manufacturing an electromagnetic wave transmitting metallic luster member will be described. Although not specifically described, the same method can be used for the case where a substrate other than the substrate film is used.

For forming the barrier layer 13, for example, a method such as vacuum deposition or sputtering can be used.

In forming the metallic luster layer 12, for example, a method such as vacuum deposition or sputtering can be used.

When the indium oxide-containing layer 11 is formed, the indium oxide-containing layer 11 is formed by vacuum deposition, sputtering, ion plating, or the like prior to the formation of the metallic luster layer 12 . However, sputtering is preferable because the thickness can be strictly controlled even in a large area.

The adhesive layer 14 can be formed by applying an adhesive composition or the like.
The adhesive composition can be applied using a conventional coater such as gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater and spray coater. Although the drying temperature can be appropriately employed, it is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 120°C. An appropriate drying time can be adopted as appropriate. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, particularly preferably 10 seconds to 5 minutes.

When the indium oxide-containing layer 11 is provided, it is preferable that the indium oxide-containing layer 11 and the metallic luster layer 12 are in direct contact with each other without intervening any other layer.

<8. Decorative material>
A decorative member according to the present embodiment includes an adherend member and the electromagnetic wave-transmitting metallic luster member described above, and the electromagnetic wave-transmitting metallic luster member (electromagnetic wave-transmitting metallic luster member 1) is attached via the pressure-sensitive adhesive layer. is affixed to the adherend member.

FIG. 4 shows a schematic cross-sectional view of the decorative member 2 according to one embodiment of the present invention. A decorative member 2 according to an embodiment of the present invention is a schematic cross-sectional view of a state in which the electromagnetic wave permeable metallic luster member 1 is adhered to an adherend member 20 . The decorative member 2 of the present embodiment comprises an electromagnetic wave transmitting metallic lustrous member 1 having a substrate 10 (base film), an indium oxide-containing layer 11, a metallic lustrous layer 12, and an adhesive layer 14 in this order, and an adherend member 20. are attached via the adhesive layer 14 .

The electromagnetic wave-transmitting metallic luster member 1 of the present embodiment has a metallic luster that suppresses coloring such as yellowishness and is excellent in visibility, so it is provided on the surface of the adherend member 20 It is possible to obtain the decorative member 2 in which the adherend 20 is decorated while keeping the design, color and texture as they are.

As the adherend member 20, for example, a transparent adherend member 20 can be used. Specifically, a member made of glass or plastic can be used, but the adherend member 20 is not limited to this.

Although the method for attaching the electromagnetic wave transmitting metallic luster member 1 to the adherend member 20 is not particularly limited, it can be attached by vacuum forming, for example. Vacuum forming is performed by stretching the electromagnetic wave transmitting metallic luster member 1 while heating and softening it, decompressing the space on the adherend side of the electromagnetic wave transmitting metallic luster member 1, and pressurizing the space on the opposite side if necessary. 1) is a method in which the electromagnetic wave permeable metallic luster member 1 is adhered and laminated while being shaped along the three-dimensional shape of the surface of the member to be adhered.
As for the electromagnetic wave transmitting metallic luster member 1, the above description can be used as it is.

<8. Applications of Electromagnetic Wave Transmitting Metallic Luster Member and Decorative Member>
Since the electromagnetic wave transmitting metallic luster member and the decorative member of the present embodiment have electromagnetic wave transmitting properties, they are preferably used for devices, articles, and parts thereof that transmit and receive electromagnetic waves. For example, structural parts for vehicles, articles mounted on vehicles, housings for electronic devices, housings for home appliances, structural parts, machine parts, various automobile parts, electronic device parts, furniture, household goods such as kitchen utensils , medical equipment, building material parts, other structural parts and exterior parts.

More specifically, for vehicles, instrument panels, console boxes, door knobs, door trims, shift levers, pedals, glove boxes, bumpers, bonnets, fenders, trunks, doors, roofs, pillars, seats, steering wheels , ECU boxes, electrical components, engine peripheral parts, drive system/gear peripheral parts, intake/exhaust system parts, cooling system parts, and the like.
More specifically, electronic devices and home appliances include household appliances such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, televisions, clocks, ventilation fans, projectors, speakers, personal computers, and mobile phones. , smart phones, digital cameras, tablet PCs, portable music players, portable game machines, battery chargers, electronic information devices such as batteries, and the like.

EXAMPLES The present invention will now be described more specifically with reference to examples and comparative examples. An electromagnetic wave transparent metallic luster member was produced and evaluated. A substrate film was used as the substrate 10 .

The details of the evaluation method are as follows.

<Film thickness of metallic luster layer>
A total of 5 points obtained by appropriately extracting a square area 3 with a side of 5 cm as shown in FIG. 'a' to 'e' were selected as measurement points.
Next, in the cross-sectional TEM image as shown in FIG. 6 at each of the selected measurement points, a viewing angle region including approximately five portions 12a was extracted. Obtain the maximum height (nm) of each of the approximately five portions 12a, that is, 25 (5 pieces x 5 locations) of the portions 12a at each of these five measurement locations, and average the maximum heights The value was taken as the "thickness of the metallic luster layer".

<Average particle size of multiple parts>
Using a scanning electron microscope (SEM), a 100,000-fold SEM image of a 1.92 μm×2.56 μm area of the metallic luster layer was obtained. From the obtained SEM image, the area V of the plurality of parts is obtained, the particle diameter R of the plurality of parts is obtained from R = 2 × (V / π) ^0.5 , and the average value is taken as the average particle diameter of the plurality of parts. did. In calculating the average value, those having R of 0.005 μm or less were ignored as noise.

<Film thickness of barrier layer>
The distance between the point indicating the maximum height of each of the 25 points used to determine the thickness of the metallic luster layer and the intersection of a straight line extending perpendicularly to the substrate 10 from that point and the upper surface of the barrier layer. The average value of a total of 25 values was used as the film thickness of the barrier layer.

<Arithmetic Surface Roughness Sa>
The arithmetic mean roughness Sa (nm) of the barrier layer surface was measured using an atomic force microscope (AFM) (observation field: 1 μm×1 μm).
Apparatus: Dimension 3100 + Nanoscope V manufactured by Bruker
Measurement mode: Tapping mode
Cantilever: Si single crystal Measurement field: 1 μm × 1 μm

<Adhesive strength to glass>
1000 g of acrylic adhesive SK Dyne 2094 (manufactured by Soken Chemical Co., Ltd.) and 2.7 g of curing agent E-5AX (manufactured by Soken Chemical Co., Ltd.) were mixed to obtain an adhesive coating liquid. An adhesive coating solution was applied onto the release-treated separator a and dried at 80° C. for 1 minute to form an adhesive layer with a thickness of 25 μm. The release-treated separator b was attached to the pressure-sensitive adhesive layer with a hand roller, and aged at 15° C. for 1 week to obtain a pressure-sensitive adhesive sheet (SK2094). The separator b was peeled off, and the pressure-sensitive adhesive layer surface and the AlO _x layer surface of laminate A described below were bonded together with a hand roller to obtain laminate B. The separator a of the laminate B was peeled off, and the surface of the adhesive layer and water-rimmed polished glass S200423 (manufactured by Matsunami Glass Industry Co., Ltd.) were bonded together to obtain a sample of adhesion to glass. Using a tensile tester Autograph AG-XD plus (manufactured by Shimadzu Corporation), the adhesion strength to glass sample was measured at 300 mm/min. A tensile test was performed on the laminate B at a peel speed of , and the adhesion to glass (N/25 mm) was measured.
Also, in the preparation of the adhesive sheet, the adhesive force to glass was similarly measured when a transparent adhesive CS9861UAS (manufactured by Nitto Denko Corporation) was used instead of SK Dyne 2094.

<Sheet resistance>
Using a non-contact resistance measuring device NC-80MAP manufactured by Napson, the sheet resistance of the electromagnetic wave transmitting metallic luster member was measured according to JIS-Z2316 by an eddy current measurement method.

[Example 1]
As a base film, an ultraviolet curable resin layer (hard coat layer) having a thickness of 1.5 μm was formed on a PET film 50-U483 (thickness of 50 μm) manufactured by Toray Industries, Inc. to obtain a base film with an ultraviolet curable resin layer.
First, an ITO target is attached to a magnetron sputtering apparatus, and sputtering is performed while introducing Ar gas, thereby forming an ITO layer as an indium oxide-containing layer along the surface of the substrate film with a thickness of 3.5 nm and forming an ultraviolet curable resin layer. formed directly on the The content of tin oxide (SnO ₂ ) contained in ITO (content=(SnO ₂ /(In ₂ O ₃ +SnO ₂ ))×100) is 10% by mass.
Next, an aluminum (Al) target was attached to a magnetron sputtering apparatus, and an Al layer with a thickness of 5 nm was formed as a metallic luster layer on the ITO layer by sputtering while introducing Ar gas. The resulting Al layer was a discontinuous layer as shown in FIG.
Subsequently, sputtering was performed while introducing a mixed gas of Ar gas and oxygen gas to form an AlO _x layer with a thickness of 20 nm as a barrier layer on the Al layer.
Using the obtained laminate A, the film thickness of the metallic luster layer, the average particle size of the plurality of portions, the film thickness of the barrier layer, the arithmetic surface roughness Sa, and the adhesion to glass were measured as described above. 1.
Table 1 also shows Sa/d, glass adhesive strength using SK2094, glass adhesive strength using CS9861UAS, and radio wave transmission. In Table 1, the standardized adhesive strength to glass is the relative adhesive strength to glass of each example when the adhesive strength to glass measured in Comparative Example 1 is taken as 100%. In addition, the radio wave transmittance is indicated by ◯ when the sheet resistance is 100 Ω/□ or more, and by X when it is less than 100 Ω/□.

[Examples 2-6, Comparative Examples 2-3, Comparative Examples 5-6]
Example 1 was repeated except that the thickness of the metallic luster layer, the average grain size of the plurality of portions, the thickness of the barrier layer or the arithmetic surface roughness Sa were changed as shown in Table 1. .

[Comparative Example 1]
Example 1 was repeated except that in Example 1 the metallic luster layer was not provided.

[Comparative Example 4]
In Example 1, a plurality of discontinuous portions were not provided as the metallic luster layer, but a continuous layer was formed, and the film thickness and arithmetic surface roughness Sa of the metallic luster layer were changed as shown in Table 1. , Example 1 was repeated.

Results are shown in Table 1 and FIG.

As is clear from Table 1 and FIG. 7, the electromagnetic wave-transmitting metallic luster members of Examples 1 to 6 were provided with a substrate, a metallic luster layer, a barrier layer, and an adhesive layer in this order on the substrate, and the metal The glossy layer includes a plurality of portions that are discontinuous at least in part, the average particle size of the plurality of portions is 15 to 90 nm, and the arithmetic mean roughness Sa (nm) of the barrier layer surface and , Sa/d, which is the ratio of the total film thickness d (nm) of the metallic luster layer and the barrier layer, is 0.05 or more, so that sufficiently high adhesive strength to the decorative member (glass) can be obtained. found to have.
On the other hand, in Comparative Example 1, no metallic luster layer was provided, and Sa/d was less than the lower limit specified in the present invention; In Comparative Example 3, the average particle size of the plurality of portions exceeds the upper limit specified in the present invention; and Sa / d is less than the lower limit specified in the present invention; in Comparative Examples 5 and 6, Sa / d is less than the lower limit specified in the present invention, so that the glass adhesive strength and radio wave transparency are satisfied at the same time. I couldn't.

The present invention is not limited to the above-described embodiments, and can be embodied with appropriate modifications without departing from the gist of the invention.

INDUSTRIAL APPLICABILITY The electromagnetic wave permeable metallic luster member according to the present invention can be used for devices, articles, and parts thereof that transmit and receive electromagnetic waves. For example, structural parts for vehicles, articles mounted on vehicles, housings for electronic devices, housings for home appliances, structural parts, machine parts, various automobile parts, electronic device parts, furniture, household goods such as kitchen utensils , medical equipment, building material parts, other structural parts and exterior parts, etc., where both good design and electromagnetic wave permeability are required.

REFERENCE SIGNS LIST 1 electromagnetic wave permeable metallic luster member 2 decorating member 10 substrate 11 indium oxide-containing layer 12 metallic luster layer 12a portion 12b gap 13 barrier layer 14 adhesive layer 15 hard coat layer 20 adherend member

Claims (12)

A substrate, and a metallic luster layer, a barrier layer, and an adhesive layer provided on the substrate in this order,
The metallic luster layer includes a plurality of portions that are discontinuous at least in part,
The average particle size of the plurality of portions is 15 to 90 nm,
Sa/d, which is a ratio of the arithmetic mean roughness Sa (nm) of the surface of the barrier layer to the total thickness d (nm) of the metallic luster layer and the barrier layer, is 0.05 or more. An electromagnetic wave transparent metallic luster member. 2. The electromagnetic wave transmitting metallic luster member according to claim 1, wherein the barrier layer has a film thickness of 10 nm or more and 50 nm or less. The barrier layer contains at least one selected from the group consisting of at least one oxide, nitride, carbide, oxynitride, oxycarbide, nitride carbide, and oxynitride carbide of at least one metal and semimetal. The electromagnetic wave transmitting metallic luster member according to claim 1 or 2. The electromagnetic wave according to any one of claims 1 to 3, wherein each of the barrier layers independently contains at least one selected from the group consisting of AZO, ITO, AlO _x and SiO ₂ . Permeable metallic luster member. The electromagnetic wave transmitting metallic luster member according to any one of claims 1 to 4, wherein the metallic luster layer contains aluminum or an aluminum alloy. 6. The electromagnetic wave transmitting metallic luster member according to claim 1, further comprising an indium oxide-containing layer between the substrate and the metallic luster layer. 7. The electromagnetic wave transmission of claim 6, wherein the indium oxide-containing layer comprises any one of indium oxide ₍ In2O3) _, indium tin oxide (ITO), or indium zinc oxide (IZO). material with metallic luster. The electromagnetic wave transmitting metallic luster member according to any one of claims 1 to 7, wherein the metallic luster layer has a thickness of 3 nm to 50 nm. The electromagnetic wave transmitting metallic luster member according to any one of claims 1 to 8, characterized in that the sheet resistance is 100Ω/□ or more. 10. The electromagnetic wave transmitting metallic luster member according to any one of claims 1 to 9, wherein the plurality of portions are formed like islands. The electromagnetic wave according to any one of claims 1 to 10, wherein the substrate is a substrate film, a resin molding substrate, a glass substrate, or an article to be imparted with metallic luster. Permeable metallic luster member. An adherend member and the electromagnetic wave transmitting metallic luster member according to any one of claims 1 to 11, wherein the electromagnetic wave transmitting metallic luster member is attached to the adherend member via the adhesive layer. decorative material.

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