WO2019208493A1 - Electromagnetic-wave-permeable metallic-luster article, and decorative member - Google Patents

Abstract

The present invention pertains to: an electromagnetic-wave-permeable metallic-luster article (1) provided with a substrate (10), a metal layer (12) formed on the substrate (10), and an optical adjustment layer (13), the metal layer (12) including in at least a part thereof a plurality of portions (12a) that are discontinuous with each other, and the optical adjustment layer (13) including at least one high-refractive-index layer that has a refractive index of 1.75 or higher; and a decorative member provided with an adherend member and a electromagnetic-wave-permeable metallic-luster article, the electromagnetic-wave-permeable metallic-luster article being affixed to the adherend member via an adhesive layer comprising a transparent adhesive.

Description

Electromagnetic wave permeable metallic luster article and decorative member

The present invention relates to an electromagnetic wave transmissive metallic luster article and a decorative member.

2. Description of the Related Art Conventionally, members having electromagnetic wave transparency and metallic luster have been suitably used for devices that transmit and receive electromagnetic waves because they have both a high-quality appearance derived from the metallic luster and electromagnetic wave transparency.
For example, there is a need for a metallic luster article that combines both luster and electromagnetic wave transmission, in which a cover member of a millimeter wave radar mounted on the front part of an automobile such as a front grill and an emblem is decorated.

Millimeter wave radar transmits millimeter wave electromagnetic waves (frequency: about 77 GHz, wavelength: about 4 mm) to the front of the car, receives reflected waves from the target, and measures and analyzes the reflected waves. The distance, target direction, and size can be measured.
The measurement result can be used for inter-vehicle measurement, automatic speed adjustment, automatic brake adjustment, and the like.
Since the front part of the automobile in which such a millimeter wave radar is arranged is a so-called automobile face and is a part that gives a large impact to the user, it is preferable to produce a high-class feeling with a metallic glossy front decoration. However, when metal is used for the front part of an automobile, transmission / reception of electromagnetic waves by the millimeter wave radar is substantially impossible or obstructed. Therefore, in order not to impair the design of the automobile without hindering the function of the millimeter wave radar, there is a need for a metallic luster article having both glitter and electromagnetic wave transparency.

This kind of metallic luster article is not only a millimeter wave radar but also various devices that require communication, for example, automobile door handles with smart keys, in-vehicle communication devices, mobile phones, electronic devices such as personal computers, etc. The application of is expected. Furthermore, in recent years, with the development of IoT technology, application in a wide range of fields such as household appliances such as refrigerators, daily life equipment, etc., which has not been conventionally performed, is expected.

Regarding a metallic luster member, Japanese Unexamined Patent Publication No. 2007-144988 (Patent Document 1) discloses a resin product including a metal coating made of chromium (Cr) or indium (In). This resin product includes a resin base material, an inorganic base film containing an inorganic compound formed on the resin base material, and glitter and discontinuity formed on the inorganic base film by physical vapor deposition. A metal film made of chromium (Cr) or indium (In) having a structure is included. As an inorganic base film, in Patent Document 1, (a) a thin film of a metal compound, for example, a titanium compound such as titanium oxide (TiO, TiO ₂ , Ti ₃ O ₅ etc.); silicon oxide (SiO, SiO ₂ etc.), nitriding Silicon compounds such as silicon (Si ₃ N ₄ etc.); aluminum compounds such as aluminum oxide (Al ₂ O ₃ ); iron compounds such as iron oxide (Fe ₂ O ₃ ); selenium compounds such as selenium oxide (CeO); oxidation Zircon compounds such as zircon (ZrO); zinc compounds such as zinc sulfide (ZnS), etc. (b) coating films of inorganic paints such as silicon and amorphous TiO _z (and other metal compounds exemplified above) as main components An inorganic coating film is used.

On the other hand, Japanese Unexamined Patent Publication No. 2009-298006 (Patent Document 2) describes not only chromium (Cr) or indium (In) but also aluminum (Al), silver (Ag), nickel (Ni) as a metal film. An electromagnetic wave transmissive bright resin product that can be formed as is disclosed.
Japanese Patent Application Laid-Open No. 2010-5999 (Patent Document 3) discloses an electromagnetic wave transmission property in which a metal film layer is formed on a base material sheet, and cracks are generated by performing heat treatment while applying tension to the base material sheet. A method for producing a metal film decorative sheet is described.
Japanese Patent No. 4601262 (Patent Document 4) describes a cover panel in which a decorative layer having a metal coloring portion by a metal thin film layer having a discontinuous film structure is laminated on a transparent resin molded product. ing.

Japanese Unexamined Patent Publication No. 2007-144988 Japanese Unexamined Patent Publication No. 2009-298006 Japanese Unexamined Patent Publication No. 2010-5999 Japanese Patent No. 4601262

In general, the metallic luster article in the prior art is one in which a metal layer is formed on a smooth surface. However, the needs for the design of metallic luster articles are diversified. For example, colored metallic luster articles are also desired.
The present invention has been made in view of the above, and is to provide a colored electromagnetic wave transmissive metallic luster article having both electromagnetic wave permeability and high glitter.

As a result of intensive studies to solve the above-mentioned problems, the present inventors usually have a discontinuous structure, for example, a metal layer made of other metals such as aluminum (Al) has a discontinuous structure, and It was found that by providing an optical adjustment layer including at least one high refractive index layer having a refractive index of 1.75 or more, both electromagnetic wave permeability and high glitter can be achieved, and a colored metal appearance can be obtained, and the present invention is completed. It came to do.

One embodiment of the present invention includes a base, a metal layer formed on the base, and at least one optical adjustment layer, wherein the metal layer is at least partially discontinuous with each other. And the optical adjustment layer relates to an electromagnetic wave transmissive metallic luster article including at least one high refractive index layer having a refractive index of 1.75 or more.

In one embodiment of the electromagnetic wave transmissive metallic luster article of the present invention, the thickness of the optical adjustment layer may be 10 nm to 1000 nm.

In one aspect of the electromagnetic wave transmissive metallic luster article of the present invention, the difference between the maximum value and the minimum value of the reflectance in the wavelength range of 380 nm to 780 nm on the side where the optical adjustment layer is provided may be 30% or more. .

In one aspect of the electromagnetic wave transmissive metallic luster article of the present invention, it is preferable that an indium oxide-containing layer is further provided between the base and the metal layer.

In one aspect of the electromagnetic wave transmissive metallic luster article of the present invention, the indium oxide-containing layer is preferably provided in a continuous state.

In one aspect of the electromagnetic wave transmissive metallic luster article of the present invention, the indium oxide-containing layer is made of either indium oxide (In ₂ O ₃ ), indium tin oxide (ITO), or indium zinc oxide (IZO). It is preferable to include.

In one aspect of the electromagnetic wave permeable metallic luster article of the present invention, the thickness of the indium oxide-containing layer is preferably 1 nm to 1000 nm.

In one aspect of the electromagnetic wave transmissive metallic luster article of the present invention, the thickness of the metal layer is preferably 20 nm to 100 nm.

In one aspect of the electromagnetic wave transmissive metallic luster article of the present invention, the ratio of the thickness of the metal layer to the thickness of the indium oxide-containing layer (the thickness of the metal layer / the thickness of the indium oxide-containing layer) is 0. .02 to 100 may be used.

In one aspect of the electromagnetic wave transmissive metallic luster article of the present invention, the plurality of portions may be formed in an island shape.

In one aspect of the electromagnetic wave transmissive metallic luster article of the present invention, the sheet resistance is preferably 100Ω / □ or more.

In one aspect of the electromagnetic wave transmissive metallic luster article of the present invention, the metal layer is made of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), silver (Ag), or an alloy thereof. It is preferable that

In one aspect of the electromagnetic wave transmissive metallic glossy article of the present invention, the substrate is preferably any one of a base film, a resin molded article base, a glass base, or an article to be provided with a metallic luster.

In one aspect of the electromagnetic wave transmissive metallic luster article of the present invention, it is preferable to further include an adhesive layer made of a transparent adhesive.

One aspect of the present invention is a decorative member comprising an adherent member and the electromagnetic wave transmissive metallic glossy article, wherein the electromagnetic wave transmissive metallic glossy article is attached to the adherend member via the adhesive layer. About.

In one aspect of the decorative member of the present invention, the square root of the square sum of the a ^* value and the b ^* value is preferably 5.0 or more in the CIE-Lab color system of reflected light on the adherent member side. .

In one aspect of the decorative member of the present invention, it is preferable that the difference between the maximum value and the minimum value of the reflectance in the wavelength range of 380 nm to 780 nm on the adherend side is 20% or more.

According to the present invention, it is possible to provide an electromagnetic wave-transmitting metallic glossy article and a metal thin film that have both electromagnetic wave transparency and high luster and have a colored metal appearance.

FIG. 1 is a schematic cross-sectional view of an electromagnetic wave transmissive metallic luster article according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of an electromagnetic wave transmissive metallic luster article according to an embodiment of the present invention. FIG. 3 is a view showing an electron micrograph of the surface of an electromagnetic wave transparent metallic glossy article according to an embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of a decorative member according to an embodiment of the present invention. FIG. 5 is a schematic cross-sectional view of a decorative member according to an embodiment of the present invention. FIG. 6 is a diagram showing the relationship between the wavelength of visible light and the reflectance (%) in the wavelength range of 380 nm to 780 nm of the decorative member of Example 5 and Comparative Example 1. FIG. 7 is a diagram showing the relationship between the a ^* value and the b ^* value of the decorative members of Examples 1 to 7 and Comparative Examples 1 and 2. FIG. 8 is a view for explaining a method for measuring the film thickness of the metal layer of the electromagnetic wave transmissive metallic luster article according to an embodiment of the present invention. FIG. 9 is a view showing a transmission electron micrograph (TEM image) of a cross section of a metal layer in one embodiment of the present invention.

Hereinafter, a preferred embodiment of the present invention will be described 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, the present invention is not intended to be limited thereto.

<1. Basic configuration>
FIG. 1 shows a schematic cross-sectional view of an electromagnetic wave transmissive metallic luster article (hereinafter referred to as “metallic luster article”) 1 according to an embodiment of the present invention, and FIG. 3 shows a metallic luster article according to an embodiment of the present invention. 1 shows an electron micrograph (SEM image) of the surface of No. 1; FIG. 9 shows a transmission electron micrograph (TEM image) of a cross-sectional view of the island-shaped metal layer 11 in one embodiment of the present invention.

The metallic luster article 1 includes a base 10, a metal layer 12 formed on the base 10, and an optical adjustment layer 13.

The metal layer 12 is formed on the substrate 10. The metal layer 12 includes a plurality of portions 12a. These portions 12a in the metal layer 12 are at least partially discontinuous from each other, in other words, at least partially separated by the gap 12b. Since the sheet is separated by the gap 12b, the sheet resistance of the metallic luster article is increased and the interaction with the radio wave is reduced, so that the radio wave can be transmitted. Each of these portions 12a may be an aggregate of sputtered particles formed by vapor deposition, sputtering or the like of metal.

In addition, the “discontinuous state” referred to in the present 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 increases, and the desired electromagnetic wave permeability can be obtained. That is, according to the metal layer 12 formed in a discontinuous state, sufficient glitter can be easily obtained, and electromagnetic wave permeability can be secured. A discontinuous form is not specifically limited, For example, an island-like structure, a crack structure, etc. are contained. Here, the “island-like structure” means that metal particles are independent from each other as shown in FIG. 3, and the particles are spread in a state of being slightly separated or partially in contact with each other. Means a structure.

The crack structure is a structure in which a metal thin film is divided by a crack.
The metal layer 12 having a crack structure can be formed, for example, by providing a metal thin film layer on a base film and bending and stretching it to cause a crack in the metal thin film layer. At this time, the metal layer 12 having a crack structure can be easily formed by providing a brittle layer made of a material having poor stretchability between the base film and the metal thin film layer. .

As described above, the aspect in which the metal layer 12 is discontinuous is not particularly limited, but an island structure is preferable from the viewpoint of productivity.

The electromagnetic wave permeability of the metallic luster article 1 can be evaluated by, for example, the amount of radio wave transmission attenuation.
Note that there is a correlation between the radio wave transmission attenuation in the microwave band (5 GHz) and the radio wave transmission attenuation in the millimeter wave radar frequency band (76 to 80 GHz). A metallic luster article excellent in electromagnetic wave transmission in the wave band is also excellent in electromagnetic wave transmission in the frequency band of the millimeter wave radar.
The radio wave transmission attenuation in the microwave band (5 GHz) is preferably 10 [−dB] or less, more preferably 5 [−dB] or less, and even more preferably 2 [−dB] or less. . If it is larger than 10 [-dB], there is a problem that 90% or more of radio waves are blocked.

The sheet resistance of the metallic luster article 1 also has a correlation with the electromagnetic wave permeability.
The sheet resistance of the metallic luster article 1 is preferably 100Ω / □ or more. In this case, the radio wave transmission attenuation in the microwave band (5 GHz) is about 10 to 0.01 [−dB].
The sheet resistance of the metallic luster article 1 is more preferably 200Ω / □ or more, and still more preferably 600Ω / □ or more.
Particularly preferably, it is 1000Ω / □ or more.
The sheet resistance of the metallic luster article 1 can be measured by an eddy current measurement method according to JIS-Z2316-1: 2014.

The radio wave transmission attenuation amount and sheet resistance of the metallic luster article are affected by the material and thickness of the metal layer 12.
In addition, when the metallic luster article 1 includes the indium oxide-containing layer 11, it is also affected by the material and thickness of the indium oxide-containing layer 11.

In the electromagnetic wave transparent metallic glossy article according to the present embodiment, the difference between the maximum value and the minimum value of the reflectance in the wavelength range of 380 nm to 780 nm on the side where the optical adjustment layer is provided is preferably 30% or more. When the difference between the maximum value and the minimum value of the reflectance is 30% or more, the coloring of the metal appearance can be deepened. From the viewpoint of coloring intensity, it is more preferably 35% or more, and further preferably 40% or more. The upper limit of the difference between the maximum value and the minimum value of the reflectance is not particularly limited. The reflectance can be measured by the method described in the examples.

<2. Base>
In the electromagnetic wave transmissive metallic glossy article according to this embodiment, examples of the substrate 10 include resin, glass, and ceramics from the viewpoint of electromagnetic wave transmission.
The substrate 10 may be any of a substrate film, a resin molded substrate, a glass substrate, or an article to which a metallic luster is to be imparted.
More specifically, as the base film, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polyvinyl chloride, polycarbonate (PC), cycloolefin polymer (COP), polystyrene A transparent film made of a homopolymer or copolymer such as polypropylene (PP), polyethylene, polycycloolefin, polyurethane, acrylic (PMMA), or ABS can be used.

These members do not affect the glitter and electromagnetic wave transmission. However, from the viewpoint of forming the indium oxide-containing layer 11 and the metal layer 12 later, it is preferably one that 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. Of these, polyethylene terephthalate, cycloolefin polymer, polycarbonate, and acrylic are preferable because of a good balance between heat resistance and cost.

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

The base film may be provided with a smooth or antiglare hard coat layer as 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, the metallic luster is increased, and on the contrary, glare can be prevented by the antiglare hard coat layer. The hard coat layer can be formed by applying a solution containing a curable resin.

Examples of the curable resin include a thermosetting resin, an ultraviolet curable resin, and an electron beam curable resin. Examples of the curable resin include various resins such as polyester, acrylic, urethane, acrylic urethane, amide, silicone, silicate, epoxy, melamine, oxetane, and acrylic urethane. One or two or more of these curable resins can be appropriately selected and used. Among these, acrylic resins, acrylic urethane resins, and epoxy resins are preferred because of their high hardness, UV curing, and excellent productivity.

Here, it should be noted that the base film is only an example of an object (substrate 10) on which the metal layer 12 can be formed. In addition to the base film as described above, the base 10 includes a resin molded product base, a glass base, and an article itself to which a metallic luster is to be imparted. Examples of articles that should be provided with a resin-molded base material and metallic luster include, for example, vehicle structural parts, vehicle-mounted products, electronic equipment casings, home appliance casings, structural parts, mechanical parts, and various automobiles. Parts, electronic equipment parts, furniture, household goods such as kitchenware, medical equipment, building material parts, other structural parts and exterior parts.

The metal layer 12 can be formed on all of 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 metal layer 12 is to be applied preferably satisfies the same materials and conditions as those of the base film.

<3. Indium oxide-containing layer>
Moreover, the metallic luster article 1 which concerns on one Embodiment may further be provided with the indium oxide containing layer 11 between the base | substrate 10 and the metal layer 12, as FIG. 2 shows. The indium oxide-containing layer 11 may be provided directly on the surface of the substrate 10 or indirectly through 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 on the surface of the substrate 10 to be provided with a metallic luster, in other words, without a gap. By providing in a continuous state, the smoothness and corrosion resistance of the indium oxide-containing layer 11, and thus the metal layer 12 and the metallic luster article 1 can be improved, and the indium oxide-containing layer 11 is formed without in-plane variation. It is also easy to do.

Thus, the indium oxide-containing layer 11 is further provided between the base 10 and the metal layer 12, that is, the indium oxide-containing layer 11 is formed on the base 10, and the metal layer 12 is formed thereon. Is preferable because the metal layer 12 can be easily formed in a discontinuous state. The details of the mechanism are not always clear, but when sputtered particles formed by metal deposition or sputtering form a thin film on the substrate, the surface diffusivity of the particles on the substrate affects the shape of the thin film. It is considered that the discontinuous structure is more easily formed when the temperature of the metal layer is higher, the wettability of the metal layer to the substrate is lower, and the melting point of the material of the metal layer is lower. By providing the indium oxide-containing layer on the substrate, it is considered that the surface diffusibility of the metal particles on the surface is promoted and the metal layer can be easily grown in a discontinuous state.

As the indium oxide-containing layer 11, indium oxide (In ₂ O ₃ ) itself can be used. For example, a metal-containing material such as indium tin oxide (ITO) or indium zinc oxide (IZO) is used. You can also However, ITO or IZO containing the second metal is more preferable in terms of high discharge stability in the sputtering process. By using these indium oxide-containing layers 11, a film in a continuous state can be formed along the surface of the substrate. In this case, a metal layer laminated on the indium oxide-containing layer is For example, it is preferable because an island-like discontinuous structure is easily obtained. Furthermore, as will be described later, in this case, not only chromium (Cr) or indium (In) but also a discontinuous structure is usually difficult to be applied to the metal layer. It becomes easy to include various metals.

The content ratio (content ratio = (SnO ₂ / (In ₂ O ₃ + SnO ₂ )) × 100) which is a mass ratio of tin oxide (SnO ₂ ) contained in ITO is not particularly limited. 0.5 wt% to 30 wt%, more preferably 3 wt% to 10 wt%. The content ratio (content ratio = (ZnO / (In ₂ O ₃ + ZnO)) × 100), which is a mass ratio of zinc oxide (ZnO) contained in IZO, is, for example, 2 wt% to 20 wt%.
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, from the viewpoints of sheet resistance, electromagnetic wave permeability, and productivity. On the other hand, in order to facilitate the discontinuous state of the metal layer 12 to be laminated, the thickness is preferably 1 nm or more, and in order to easily facilitate the discontinuous state, it is more preferably 2 nm or more, and 5 nm or more. More preferably.

<4. Metal layer>
The metal layer 12 is formed on the substrate and includes a plurality of portions that are discontinuous with each other at least partially.
When the metal layer 12 is in a continuous state on the substrate, sufficient radiance can be obtained, but the radio wave transmission attenuation amount becomes very large, and therefore electromagnetic wave transmission cannot be ensured.

The details of the mechanism by which the metal layer 12 becomes discontinuous on the substrate are not necessarily clear, but are estimated to be as follows. That is, in the thin film formation process of the metal layer 12, the ease of forming the discontinuous structure is related to the surface diffusion on the substrate to which the metal layer 12 is applied, the temperature of the substrate is high, and the metal layer with respect to the substrate The lower the melting point of the material of the metal layer, the easier it is to form a discontinuous structure. Therefore, for metals other than aluminum (Al) used in particular in the following examples, for metals with relatively low melting points such as zinc (Zn), lead (Pb), copper (Cu), and silver (Ag), It is considered that a discontinuous structure can be formed by a similar method.

Here, the average particle diameter 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 particle diameter of the plurality of portions 12a can be measured by the method described in the column of Examples.
The equivalent circle diameter of the portion 12a of the metal layer 12 is not particularly limited, but is usually about 10 to 1000 nm. The distance between the portions 12a is not particularly limited, but is usually about 10 to 1000 nm.

By setting the average particle size of the plurality of portions 12a in the discontinuous state included in the metal layer within the above range, the glitter can be further improved while maintaining high electromagnetic wave permeability.

It is desirable that the metal layer 12 has a relatively low melting point as well as sufficient glitter. This is because the metal layer 12 is preferably formed by thin film growth using sputtering. For this reason, a metal having a melting point of about 1000 ° C. or less is suitable as the metal layer 12. For example, aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), silver (Ag) It is preferable that at least one kind of metal selected from the above and an alloy containing the metal as a main component are included. In particular, Al and alloys thereof are preferable for the reasons such as the luster and stability of the substance and the price. Moreover, when using an aluminum alloy, it is preferable that aluminum content shall be 50 mass% or more.

The thickness of the metal layer 12 is usually preferably 20 nm or more so as to exhibit sufficient glitter, and is usually preferably 100 nm or less from the viewpoint of sheet resistance and electromagnetic wave transmission. For example, 20 nm to 100 nm is preferable, and 30 nm to 70 nm is more preferable. This thickness is also suitable for forming a uniform film with high productivity, and the appearance of the resin molded product as the final product is also good. In addition, the thickness of the metal layer 12 can be measured by the method as described in the column of an Example.

For the same reason, the ratio of the thickness of the metal layer to the thickness of the indium oxide-containing layer (the thickness of the metal layer / the thickness of the indium oxide-containing layer) is preferably in the range of 0.1 to 100. A range of 3 to 35 is more preferable.

The sheet resistance of the metal layer is preferably 100Ω / □ or more. In this case, the electromagnetic wave permeability is about 10 to 0.01 [-dB] at a wavelength of 5 GHz. More preferably, it is 1000Ω / □ or more.

When an indium oxide-containing layer is further provided, the sheet resistance as a laminate of the metal layer and the indium oxide-containing layer is preferably 100Ω / □ or more. In this case, the electromagnetic wave permeability is about 10 to 0.01 [-dB] at a wavelength of 5 GHz. More preferably, it is 1000Ω / □ or more. The value of the sheet resistance is greatly influenced not only by the material and thickness of the metal layer but also by the material and thickness of the indium oxide-containing layer that is the underlayer. Therefore, when providing an indium oxide content layer, it is necessary to set in consideration of a relation with an indium oxide content layer.

<5. Optical adjustment layer>
The optical adjustment layer includes at least one high refractive index layer having a refractive index of 1.75 or more.
The optical adjustment layer is preferably provided on the side where the metal layer 12 is visually recognized, and may be provided directly on the metal layer 12 or may be provided via another layer. For example, in the metallic luster article 1 according to one embodiment, as shown in FIG. 1, it may be provided on the surface of the metal layer 12 opposite to the base 10 side, and as shown in FIG. And the substrate 10 may be provided. In the case where the optical adjustment layer 13 is directly provided on the metal layer 12, the optical adjustment layer 13 may be laminated on the metal layer 12, and the gap 12b may not be completely filled.

When the refractive index of the high refractive index layer is 1.75 or more, a colored metallic appearance can be obtained and a metallic luster article excellent in design can be obtained. In order to obtain a darker metallic appearance, the refractive index of the high refractive index layer is preferably 1.8 or more, and more preferably 1.9 or more. Moreover, from a viewpoint of thickness controllability, 3.5 or less is preferable and 3.0 or less is more preferable.
The optical adjustment layer may be a laminate of at least one layer having a different refractive index.
Examples of the material for the high refractive index layer include CeO ₂ (2.30), Nd ₂ O ₃ (2.15), Nb ₂ O ₅ (2.20), SiN (2.03), and Sb ₂ O _3. (2.10), TiO ₂ (2.35), Ta ₂ O ₅ (2.10), ZrO ₂ (2.05), ZnO (2.10), ZnS (2.30) and other inorganic substances [above A numerical value in parentheses of each material is a refractive index] or a mixture thereof, and niobium oxide (Nb ₂ O ₅ ) or SiN (2.03) is preferable.

The thickness of the optical adjustment layer is preferably 10 nm to 1000 nm. From the viewpoint of cost, it is more preferably 800 nm or less, and further preferably 500 nm or less. Further, from the viewpoint of color, it is preferably 15 nm or more, more preferably 20 nm or more, and further preferably 30 nm or more.

<6. Adhesive layer>
The pressure-sensitive adhesive layer 14 is a layer made of a transparent pressure-sensitive adhesive. The metallic luster article 1 of the present embodiment may be used by being attached to the adherend member 15 via the pressure-sensitive adhesive layer 14. For example, when the substrate 10 is a substrate film or a glass substrate, the adherent member 15 can be decorated from the inside by being attached to the transparent adherent member 15 via the pressure-sensitive adhesive layer 14.

The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 14 is not particularly limited as long as it is a transparent pressure-sensitive adhesive. For example, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and an epoxy-based pressure-sensitive adhesive. Any of the agent and the polyether-based pressure-sensitive adhesive can be used alone or in combination of two or more. From the viewpoint of transparency, workability, durability, etc., it is preferable to use an acrylic pressure-sensitive adhesive.

Although the thickness of the pressure-sensitive adhesive layer 14 is not particularly limited, it is preferably 100 μm or less, more preferably 75 μm or less, because the visible light transmittance, film thickness accuracy, and flatness can be improved by reducing the thickness. Preferably, it is 50 μm or less.

The total light transmittance of the entire pressure-sensitive adhesive layer 14 is not particularly limited, but it is preferably 10% or more, more preferably 30% or more, as measured at any visible light wavelength measured according to JIS K7361. % Or more is more preferable. The total light transmittance of the pressure-sensitive adhesive layer 14 is preferably as high as possible.

Moreover, the transparent adhesive which comprises the adhesive layer 14 may be colored.
In this case, since the metal layer 12 is visually recognized through the colored adhesive layer 14, a colored metallic luster can be expressed.

Although the method for coloring the transparent adhesive is not particularly limited, for example, it can be colored by adding a small amount of a dye.

A release liner may be provided on the pressure-sensitive adhesive layer 14 in order to protect the pressure-sensitive adhesive layer 14 until it is attached to the adherend member 15.

In addition to the metal layer 12, the indium oxide-containing layer 11, the optical adjustment layer 13, and the pressure-sensitive adhesive layer 14 described above, the metallic luster article of the present embodiment has other layers depending on the application as long as the effects of the present invention are achieved. May be provided. Other layers include an optical adjustment layer (color adjustment layer) such as a highly refractive material for adjusting the appearance such as color, and a protective layer (abrasion resistance) for improving durability such as moisture resistance and scratch resistance. Property layer), barrier layer (corrosion prevention layer), easy adhesion layer, hard coat layer, antireflection layer, light extraction layer, antiglare layer and the like.

<7. Production of metallic luster articles>
An example of the manufacturing method of the metallic luster article 1 will be described. Although not specifically described, the same method can be used when a substrate other than the substrate film is used.

In forming the metal layer 12 on the substrate 10, for example, a method such as vacuum deposition or sputtering can be used.
Examples of the method of forming the optical adjustment layer 13 include a vacuum deposition method, a sputtering method, an ion plating method, a coating method, and the like, and an appropriate method is adopted depending on the type of material and the required film thickness. Can do.

Further, when the indium oxide-containing layer 11 is formed on the substrate 10, the indium oxide-containing layer 11 is formed by vacuum deposition, sputtering, ion plating or the like prior to the formation of the metal layer 12. However, sputtering is preferable because the thickness can be strictly controlled even in a large area.

When providing the adhesive layer 14, it can form by apply | coating an adhesive composition etc. to the surface in which the adhesive layer 14 is provided.
The pressure-sensitive adhesive composition can be applied using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater. The drying temperature can be appropriately employed, but is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and particularly preferably 70 ° C to 120 ° C. As the drying time, an appropriate time can be adopted as appropriate. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.

In addition, when providing the indium oxide containing layer 11 between the base | substrate 10 and the metal layer 12, it is preferable to contact directly between an indium oxide containing layer 11 and the metal layer 12 without interposing another layer.

<8. Decorating member>
The decorative member according to the present embodiment includes an adherent member and the above-described electromagnetic wave transmissive metallic glossy article, and the electromagnetic wave transmissive metallic glossy article (metallic glossy article 1) is interposed between the adhesive layer and the coated article. Affixed to the landing member.

The metallic luster article 1 may be attached to the inner surface of the transparent adherend member 2 for use. As the transparent adherent member 15, for example, a member made of glass or plastic can be used, but is not limited thereto.

FIG. 4 shows a schematic cross-sectional view of the decorative member 2 according to one embodiment of the present invention. The decorative member 2 according to one embodiment of the present invention is a schematic cross-sectional view of a state in which the metallic luster article 1 is attached to the adherend member 15. The decorative member 2 of the present embodiment includes a metallic glossy article 1 including a metal layer 12, an indium oxide-containing layer 11, an optical adjustment layer 13, a base 10 (base film), and an adhesive layer 14, and the adherend member 15 It is affixed to.

FIG. 5 is a schematic cross-sectional view of a decorative member according to an embodiment of the present invention. As for the decorating member 2, the metallic luster article 1 of the structure shown in FIG. In FIG. 5, the pressure-sensitive adhesive layer 14 with respect to the surface 2 b on the opposite side (hereinafter also referred to as the inner side) from the surface 2 a on the side (hereinafter also referred to as the outer side) where the metallic glossy article 1 is transparent. The optical adjustment layer 13 and the metal layer 12 are visually recognized through the adherend member 15 and the pressure-sensitive adhesive layer 14. That is, the metallic glossy article 1 of the present embodiment can decorate the transparent adherend member 15 from the inside.
Since the decorative member 2 of the present embodiment is obtained by pasting the metallic luster article 1 on the inside of the adherend member 15, a colored metal appearance that is hard to be damaged is obtained. Further, the adherent member 15 can be decorated while utilizing the texture of the adherent member 15 as it is.

Although the method of sticking the metallic luster article 1 to the adherend member 2 is not particularly limited, it can be attached by, for example, vacuum forming. With vacuum forming, the metallic glossy article 1 is stretched while being softened by heating, the space on the adherend member side of the metallic glossy article 1 is depressurized, and the space on the opposite side is pressurized as necessary. It is a method of sticking and laminating while forming along the three-dimensional shape of the surface of the adherend.
As the metallic luster article 1, the above description can be used as it is.

In the decorative member according to this embodiment, the square root of the sum of squares of the a ^* value and the b ^* value is 5.0 or more in the CIE-L ^* a ^* b ^* color system of the reflected light on the adherend member side. It is preferable. This is because coloring is sufficient when the square root of the square sum of the a ^* value and the b ^* value is 5.0 or more. The square root of the sum of squares of the a ^* value and b ^* value is more preferably 10 or more, and further preferably 15 or more. Although there is no restriction | limiting in particular in the upper limit of the square root of the square sum of a ^* value and b ^* value, It is preferable that it is 70 or less, It is more preferable that it is 65 or less, It is still more preferable that it is 60 or less.

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

In the decorative member 2 according to this embodiment, the difference between the maximum value and the minimum value of the reflectance in the wavelength range of 380 nm to 780 nm on the adherend member side is preferably 20% or more. From the viewpoint of coloring intensity, it is more preferably 35% or more, and further preferably 40% or more.
The upper limit of the difference between the maximum value and the minimum value of the reflectance is not particularly limited, but is preferably 90% or less, more preferably 85% or less, and still more preferably 80% or less.

<9. Use of metallic luster articles and decorative members>
Since the metallic luster article and the metal thin film of the present embodiment have electromagnetic wave permeability, it is preferable to use the metallic luster article and the metal thin film for an apparatus and an article that transmit and receive electromagnetic waves, and parts thereof. For example, use for household goods such as structural parts for vehicles, on-vehicle equipment, housing for electronic equipment, housing for home appliances, structural parts, mechanical parts, various automotive parts, electronic equipment parts, furniture, kitchenware, etc. , Medical equipment, building material parts, other structural parts and exterior parts.
More specifically, in the case of 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 components, drive system / gear peripheral components, intake / exhaust system components, cooling system components, and the like.
More specifically, electronic devices and home appliances include refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, TVs, clocks, ventilation fans, projectors, speakers, and other home appliances, personal computers, mobile phones Electronic information devices such as smartphones, digital cameras, tablet PCs, portable music players, portable game machines, chargers, and batteries.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. A metallic luster article was prepared, and the reflectance, the a ^* value and b ^* value in the CIE-L ^* a ^* b ^* display system, the radio wave transmission attenuation (-dB), and the sheet resistance were evaluated. Note that a base film was used as the substrate 10.
The radio wave transmission attenuation is an evaluation regarding electromagnetic wave transmission. A smaller radio wave transmission attenuation value is preferable.
Details of the evaluation method are as follows.

(1) Spectral reflectance Using a spectrophotometer U-4100 manufactured by Hitachi High-Tech, the reflected light irradiated on one surface of a metallic luster article at a 5 nm interval for visible light in the wavelength range of 380 nm to 780 nm. Spectral reflectance was measured.
In addition, when measuring, the said visible light was made to inject with respect to the to-be-adhered member surface, and it described in Table 1 as a reflectance (with paste). Table 1 shows the maximum value (max) and minimum value (min) of the spectral reflectance (%) in the wavelength range of 380 nm to 780 nm, and the difference between the maximum value (max) and the minimum value (min). It was.

(2) CIE-L ^* a ^* b ^* a ^* value and b ^* value in the display system Spectral reflectance of wavelength 380 to 780 nm measured with the above spectrophotometer U-4100 and relative spectral distribution of CIE standard illuminant D65 The a ^* value and b ^* value in the CIE-L ^* a ^* b ^* display system were calculated. Table 1 shows the a ^* value, the b ^* value, and the square root of the square sum of the a ^* value and the b ^* value.

(3) Radio wave transmission attenuation The radio wave transmission attenuation at 5 GHz was measured using a spectrum analyzer MS4644B manufactured by Anritsu Co., Ltd. with a sample sandwiched by a rectangular waveguide measurement evaluation jig WR-187.

(4) Sheet resistance A sheet resistance as a laminate of a metal layer and an indium oxide-containing layer was measured by an eddy current measurement method using a non-contact type resistance measuring device NC-80MAP manufactured by Napson, based on JIS-Z2316.
The sheet resistance is preferably 100Ω / □ or more, more preferably 200Ω / □ or more, and further preferably 600Ω / □ or more. If it is less than 100Ω / □, there is a problem that sufficient electromagnetic wave permeability cannot be obtained.

(5) Film thickness evaluation method First, as shown in FIG. 8, a square region 3 having a side of 5 cm is appropriately extracted from a metallic luster article, and the center lines A and B of the vertical and horizontal sides of the square region 3 are respectively extracted. A total of five points “a” to “e” obtained by dividing each of these into four equal parts were selected as measurement points.
Next, a cross-sectional image (transmission electron micrograph (TEM image)) as shown in FIG. 9 is measured at each selected measurement location, and five or more metal portions 12a are included from the obtained TEM image. The viewing angle region was extracted.
The total cross-sectional area of the metal layer in the viewing angle region extracted at each of the five measurement positions divided by the lateral width of the viewing angle region is defined as the thickness of the metal layer in each viewing angle region. The average value of the metal layer thickness in each viewing angle region was defined as the metallic luster layer thickness (nm).

[Example 1]
As the base film, a film in which a thermosetting resin having a thickness of 2000 μm was formed on one surface of a PET film (thickness 50 μm) manufactured by Mitsubishi Plastics, Inc. was used.
First, an ITO target was attached to a DC magnetron sputtering apparatus, and sputtering was performed while introducing Ar gas and O ₂ gas to directly form an ITO layer having a thickness of 5 nm along the surface of the base film. The temperature of the base film when forming the ITO layer was set to 130 ° C. The content of tin oxide (SnO ₂ ) contained in ITO (content rate = (SnO ₂ / (In ₂ O ₃ + SnO ₂ )) × 100) is 10 wt%.

An aluminum (Al) target was attached to an AC sputtering apparatus (AC: 40 kHz), and an Al layer (metal layer) having a thickness of 35 nm was formed on the ITO layer by sputtering while introducing Ar gas. The obtained Al layer was a discontinuous layer. The temperature of the base film when forming the Al layer was set to 130 ° C.

(Formation of optical adjustment layer)
Next, an Nb target (AC: 40 kHz) is attached to an AC sputtering apparatus, and sputtering is performed while introducing Ar gas and O ₂ gas, thereby forming a 110 nm Nb ₂ O ₅ layer as an optical adjustment layer on the Al layer. did.

As described above, a laminate (hereinafter referred to as a laminate) of a base film, an indium oxide-containing layer, a metal layer, and an optical adjustment layer was obtained. The reflectance of the obtained laminate (metallic glossy article) was measured by the above method, and listed in Table 1 as the reflectance (no glue).

<Manufacture of an adhesive composition>
On the other hand, a monomer mixture containing 100 parts by mass of butyl acrylate, 0.01 parts by mass of 2-hydroxyethyl acrylate, and 5 parts of acrylic acid in a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device. Prepared. Furthermore, with respect to 100 parts by mass of the monomer mixture, 0.1 part by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator was charged together with 100 parts by mass of ethyl acetate, and nitrogen gas was introduced while gently stirring. After purging with nitrogen, the temperature of the liquid in the reaction vessel was kept at around 55 ° C., and the polymerization reaction was carried out for 8 hours to obtain an acrylic polymer solution having a weight average molecular weight (Mw) of 1.8 million and Mw / Mn = 4.1. (Solid content concentration of 30% by mass) was prepared.
0.3 parts by mass of benzoyl peroxide (manufactured by NOF Corporation, Niper BMT) and 1 part of an isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, Coronate L) with respect to 100 parts by mass of the solid content of the obtained acrylic polymer solution An adhesive composition was obtained by blending parts by mass.

<Manufacture of metallic luster articles>
A metal having a colored metallic luster by forming the pressure-sensitive adhesive layer by applying the pressure-sensitive adhesive composition obtained above to the surface on the metal layer side of the laminate obtained above with a hand roller. A glossy article was obtained.

<Manufacture of decorative members>
Glass having a thickness of 1.2 mm was used as the adherent member.
The adhesive layer side of the metallic luster article obtained above was affixed to the adherend member to obtain a decorative member.

[Examples 2 to 5]
The thickness (nm) of the optical adjustment layer in Example 1 was changed as described in Table 1 to obtain a decorative member.

[Examples 6 and 7]
When forming the optical adjustment layer in Example 1, SiN (optical adjustment layer) is described in Table 1 on the Al layer by attaching the Si target to an AC sputtering apparatus and performing sputtering while introducing Ar gas and N ₂ gas. A decorative member was obtained in the same manner as in Example 1 except that the film was formed with a thickness of.

[Comparative Example 1]
A decorative member was obtained in the same manner as in Example 1 except that the optical adjustment layer in Example 1 was not provided.

[Comparative Example 2]
The optical adjustment layer in Example 1 is a mixture of niobium oxide (Nb ₂ O ₅ ), zinc oxide (ZnO), silicon oxide (SiOx), and aluminum oxide (Al ₂ O ₃ ) (by mass ratio, zinc oxide: silicon oxide). : Aluminum oxide = 77: 20: 3) A decorative member was obtained in the same manner as in Example 1 except that the sputtering apparatus was changed to a DC sputtering apparatus.

Table 1 below shows the evaluation results. In addition, the relationship between the wavelength of visible light and the reflectance (%) in the wavelength range of 380 nm to 780 nm of the decorative member of Example 5 and Comparative Example 1 is shown in FIG. FIG. 7 shows the relationship between the a ^* value and the b ^* value of the decorative members of Examples 1 to 7 and Comparative Examples 1 and 2.

As is clear from Table 1, Examples 1 to 7 include a high refractive index layer having a refractive index of 1.75 or more, and therefore the square sum of the a ^* value and b ^* value in the CIE-Lab color system The square root was 13 to 30, and a colored metallic luster article and decorative member were obtained. In addition, since the aluminum layer includes a plurality of portions 12a formed in a discontinuous state, good results with respect to electromagnetic wave transmission were obtained.
On the other hand, the metallic luster articles and decorative members of Comparative Examples 1 and 2 had a small difference in reflectance. Further, the square root of the sum of squares of the a ^* value and b ^* value was small, and coloring was insufficient.

In addition, for metals other than aluminum (Al) used in particular in the above examples, for metals with relatively low melting points such as zinc (Zn), lead (Pb), copper (Cu), silver (Ag), It is considered that a discontinuous structure can be formed by a similar method.

The present invention is not limited to the above-described embodiments, and can be modified and embodied as appropriate without departing from the spirit of the invention.

The preferred embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments, and various modifications may be made to the above-described embodiments without departing from the scope of the present invention. And substitutions can be added.
This application is based on a Japanese patent application filed on April 23, 2018 (Japanese Patent Application No. 2018-082656) and a Japanese patent application filed on April 22, 2019 (Japanese Patent Application No. 2019-080625). The contents are incorporated by reference into this application.

The metallic luster article according to the present invention can be used for devices and articles for transmitting and receiving electromagnetic waves, and parts thereof. For example, applications for household goods such as structural parts for vehicles, vehicle-mounted products, housings for electronic devices, housings for home appliances, structural components, mechanical parts, various automotive parts, electronic device parts, furniture, kitchenware, etc. It can also be used for various applications that require both design and electromagnetic wave transmission properties, such as medical equipment, building material parts, other structural parts and exterior parts.

DESCRIPTION OF SYMBOLS 1 Metal luster article 2 Decorating member 10 Base | substrate 11 Indium oxide content layer 12 Metal layer 12a Part 12b Gap 13 Optical adjustment layer 14 Adhesive layer 15 Adhering member

Claims (17)

1. A base, a metal layer formed on the base, and at least one optical adjustment layer;
   The metal layer includes a plurality of portions at least partially discontinuous with each other,
   The optical adjustment layer is an electromagnetic wave transmissive metallic luster article including a high refractive index layer having a refractive index of 1.75 or more.
2. The electromagnetically transparent metallic glossy article according to claim 1, wherein the thickness of the optical adjustment layer is 10 nm to 1000 nm.
3. 3. The electromagnetically transparent metallic glossy article according to claim 1, wherein a difference between the maximum value and the minimum value of the reflectance in the wavelength range of 380 nm to 780 nm on the side where the optical adjustment layer is provided is 30% or more.
4. The electromagnetically transparent metallic glossy article according to any one of claims 1 to 3, further comprising an indium oxide-containing layer between the substrate and the metal layer.
5. The electromagnetically transparent metal glossy article according to claim 4, wherein the indium oxide-containing layer is provided in a continuous state.
6. The electromagnetic wave-transmitting metallic luster according to claim 4 or 5, wherein the indium oxide-containing layer includes any one of indium oxide (In ₂ O ₃ ), indium tin oxide (ITO), or indium zinc oxide (IZO). Goods.
7. The electromagnetically transparent metallic glossy article according to any one of claims 4 to 6, wherein the indium oxide-containing layer has a thickness of 1 nm to 1000 nm.
8. The electromagnetically transparent metallic glossy article according to any one of claims 1 to 7, wherein the metal layer has a thickness of 20 nm to 100 nm.
9. The ratio of the thickness of the metal layer to the thickness of the indium oxide-containing layer (the thickness of the metal layer / the thickness of the indium oxide-containing layer) is 0.02 to 100. 2. An electromagnetic wave transparent metallic luster article according to item 1.
10. The electromagnetically transparent metallic glossy article according to any one of claims 1 to 9, wherein the sheet resistance is 100Ω / □ or more.
11. The electromagnetically transparent metal glossy article according to any one of claims 1 to 10, wherein the plurality of portions are formed in an island shape.
12. The metal layer is any one of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), silver (Ag), or an alloy thereof. The electromagnetically transparent metallic luster article described.
13. The electromagnetic wave transmissive metallic glossy article according to any one of claims 1 to 12, wherein the substrate is any one of a base film, a resin molded article base, a glass base, or an article to be provided with metallic luster. .
14. The electromagnetically transparent metallic glossy article according to any one of claims 1 to 13, further comprising an adhesive layer made of a transparent adhesive.
15. A decorative member comprising: an adherent member; and the electromagnetic wave transmissive metallic glossy article according to claim 14, wherein the electromagnetic wave transmissive metallic glossy article is affixed to the adherend member via the adhesive layer.
16. The decorative member according to claim 15, wherein a square root of a square sum of a ^* value and b ^* value is 5.0 or more in the CIE-Lab color system of reflected light on the adherend side.
17. The decorative member according to claim 16, wherein the difference between the maximum value and the minimum value of the reflectance in the wavelength range of 380 nm to 780 nm on the adherent member side is 20% or more.

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