TW201945176A - Electromagnetic-wave-permeable metallic-luster article, and decorative member - Google Patents

Abstract

The present invention pertains to: an electromagnetic-wave-permeable metallic-luster article provided with a substrate, a metal layer formed on the substrate, and an optical adjustment layer, the metal layer including in at least a part thereof a plurality of portions that are discontinuous with each other, and the optical adjustment layer 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-transmitting metallic luster articles and decorative members

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

Conventionally, a member having electromagnetic wave permeability and metallic luster has both high-grade appearance and electromagnetic wave permeability from the appearance of metallic luster, and is therefore suitable for a device for transmitting and receiving electromagnetic waves.
For example, a cover member of a millimeter-wave radar mounted on a front part of a car such as a front grille or an emblem is required to provide both decoration with both brilliance and electromagnetic wave permeability. Metallic shiny items.

The millimeter-wave radar sends millimeter-wave electromagnetic waves (frequency of about 77 GHz and wavelength of about 4 mm) to the front of the car, receives reflected waves from the target, and measures and analyzes the reflected waves to measure the distance to the target or the direction of the target. ,size.
The measurement results can be used for workshop measurement, automatic speed adjustment, and automatic brake adjustment.
The front part of a car equipped with such a millimeter-wave radar is a so-called face of a car that gives a user a great influence. Therefore, it is ideal to perform a high-end look with a metallic gloss-tone front decoration. However, in the case of using metal in the front part of the car, it is practically impossible or obstructed to transmit and receive electromagnetic waves by the millimeter wave radar. Therefore, in order not to hinder the function of the millimeter-wave radar and not to destroy the design of the car, it is necessary to have a metallic luster that has both brightness and electromagnetic wave permeability.

Such metallic luster items are used for various devices that not only communicate with millimeter-wave radar, but also door handles of automobiles equipped with smart keys, on-board communication devices, mobile phones, personal computers, and other electronic devices. look forward to. In addition, with the development of IoT technology in recent years, applications in a wide range of fields, such as home appliances and living appliances, which have not conventionally been used for communication, are also expected.

Regarding metallic luster members, Japanese Patent Application Laid-Open No. 2007-144988 (Patent Document 1) discloses a resin product including a metal film made of chromium (Cr) or indium (In). The resin product includes an inorganic underlayer film including a resin substrate and an inorganic compound formed on the resin substrate, and the brightness and discontinuity of the film formed by the physical evaporation method on the inorganic underlayer film. Structured metal film made of chromium (Cr) or indium (In). As the inorganic underlayer film, Patent Document 1 is a thin film using (a) 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.), nitrogen Silicon compounds such as silicon oxide (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); Zirconium compounds such as zirconium oxide (ZrO); zinc compounds such as zinc sulfide (ZnS); (b) coating films of inorganic coatings; for example, silicon, amorphous TiO _z, etc. (other metal compounds as exemplified above) ) A coating film of an inorganic paint as a main component.

On the other hand, Japanese Patent Application Laid-Open No. 2009-298006 (Patent Document 2) discloses that not only chromium (Cr) or indium (In), but also aluminum (Al), silver (Ag), and nickel (Ni) can be used as the metal. Film-formed electromagnetic wave transmissive bright resin product.
In Japanese Patent Application Laid-Open No. 2010-5999 (Patent Document 3), it is described that a metal film layer is formed on a base material sheet, and heat treatment is performed while facing the base material sheet load tension, thereby producing cracked electromagnetic wave permeability. Method of decorating thin metal film.
Japanese Patent No. 4601262 (Patent Document 4) describes a cover panel in which a decorative layer having a metal colored portion generated by a metal thin film layer having a discontinuous film structure is laminated on a transparent resin molded article.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-144988
[Patent Document 2] Japanese Patent Laid-Open No. 2009-298006
[Patent Document 3] Japanese Patent Laid-Open No. 2010-5999
[Patent Document 4] Japanese Patent No. 4601262

(Problems to be solved by the invention)

Conventionally, metallic luster articles are generally those in which a metal layer is formed on a smooth surface. However, the demand for the design of metallic shiny articles is diversified, and for example, colored metallic shiny articles are also desired.
The present invention has been developed in view of the above-mentioned circumstances, and provides a colored electromagnetic wave-transmitting metallic luster article that is compatible with electromagnetic wave permeability and high brightness.

(Means for solving problems)

In order to solve the above-mentioned problems, the inventors have conducted an in-depth review and found that it is difficult to form a discontinuous structure, for example, a metal layer made of other metals such as aluminum (Al) has a discontinuous structure and has at least The optical adjustment layer including one high refractive index layer having a refractive index of 1.75 or more can achieve both the electromagnetic wave transmission and high brightness, and obtain a colored metallic appearance, and completed the present invention.

One aspect of the present invention relates to an electromagnetic wave-transmitting metallic luster article including a substrate, a metal layer formed on the substrate, and at least one optical adjustment layer.
The aforementioned metal layer includes a plurality of portions in which at least a portion is in a state of being discontinuous from each other,
The optical adjustment layer includes at least one high refractive index layer having a refractive index of 1.75 or more.

In one form 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 form of the electromagnetic-wave-transmitting metallic luster article of the present invention, the difference between the maximum value and the minimum value of the reflectance in a range of wavelengths from 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-transmitting metallic luster article of the present invention, it is preferable to further include an indium oxide-containing layer between the substrate and the metal layer.

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

In one aspect of the electromagnetic wave-transmitting metallic luster article of the present invention, the indium oxide-containing layer includes any one of indium oxide (In ₂ O ₃ ), indium tin oxide (ITO), or indium zinc oxide (IZO). One is ideal.

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

In one form 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) may be 0.02 to 100.

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

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

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

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

In one aspect of the electromagnetic wave-transmitting 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 relates to a decorative member comprising: an adhered member and the aforementioned electromagnetic wave-transmitting metallic luster article,
The electromagnetic wave-transmitting metallic luster article is adhered to the adherend member via the adhesive layer.

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

In one form of the decorative member 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 of the adhered member is preferably 20% or more.

[Effect of the invention]

According to the present invention, it is possible to provide an electromagnetic wave transmissive metallic luster and a metal film that have both the electromagnetic wave permeability and high brightness and have a metallic appearance that is colored.

Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. In the following, for convenience of explanation, only suitable embodiments of the present invention will be shown, but the present invention is not limited thereto.

＜ 1. Basic structure ＞
FIG. 1 shows a schematic cross-sectional view of an electromagnetic wave-transmitting metallic luster article (hereinafter referred to as a “metal luster article”) 1 according to an embodiment of the present invention, and FIG. 3 illustrates a surface of the metallic luster article 1 according to an embodiment of the present invention. Electron micrograph (SEM image). In addition, FIG. 9 shows a transmission electron microscope photograph (TEM image) of a cross section of the metal layer 11 of the island structure according to the embodiment of the present invention.

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

The metal layer 12 is formed on the base body 10. The metal layer 12 includes a plurality of portions 12a. Such portions 12a of the metal layer 12 are at least partially discontinuous from each other, in other words, at least a portion is separated by a gap 12b. Since they are 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 easily transmitted. Each of these portions 12a is an aggregate of sputtered particles that may be formed by metal deposition, sputtering, or the like.

In addition, the "discontinuous state" referred to in this specification means a state separated from each other by the gap 12b. As a result, the states are electrically insulated from each other. By being electrically insulated, the sheet resistance is increased, and desired electromagnetic wave permeability can be obtained. That is, when the metal layer 12 is formed in a discontinuous state, sufficient brightness is easily obtained, and electromagnetic wave permeability is also ensured. The discontinuous form is not particularly limited, and includes, for example, an island structure and a cracked structure. The "island-like structure" here is a structure in which metal particles are independent from each other as shown in FIG. 3, and such particles are in a state of being slightly apart or partially in contact with each other.

The crack structure is a structure in which a metal thin film is broken by cracks.
The metal layer 12 with a cracked structure can be formed, for example, by providing a metal thin film layer on a base film, and bending and extending to cause cracks in the metal thin film layer. At this time, there is a lack of elasticity between the base film and the metal thin film layer, that is, a metal layer 12 having a cracked structure can be easily formed by providing a brittle layer made of a material that is easily cracked by extension.

As described above, it is not particularly limited that the metal layer 12 has a discontinuous form, but an island structure is preferable from the viewpoint of productivity.

The electromagnetic wave permeability of the metallic glossy article 1 can be evaluated, for example, by the amount of attenuation of radio wave transmission.
In addition, there is a correlation between the radio wave transmission attenuation of the microwave band (5GHz) and the radio wave transmission attenuation of the millimeter-wave radar band (76 to 80GHz). Since the values are shown to be relatively close, the electromagnetic wave transmission of the microwave band Good metallic luster items have good electromagnetic wave permeability in the millimeter wave radar frequency band.
The microwave wave (5GHz) radio wave transmission attenuation is preferably 10 [-dB] or less, more preferably 5 [-dB] or less, and 2 [-dB] or less. If it is larger than 10 [-dB], more than 90% of the radio waves are blocked.

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

The amount of radio wave transmission attenuation and sheet resistance of the metallic glossy article 1 are affected depending on the material or thickness of the metal layer 12.
In addition, the case where the metallic luster article 1 includes the indium oxide-containing layer 11 is affected depending on the material, thickness, and the like of the indium oxide-containing layer 11.

In the electromagnetic-wave-transmitting metallic luster article of 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 side where the optical adjustment layer is provided is preferably 30% or more. If the difference between the maximum value and the minimum value of the reflectance is 30% or more, the tint of the appearance of the metal can be made thicker. From the viewpoint of the coloring density, 35% or more is more preferable, and 40% or more is more preferable. 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 Examples.

＜ 2. Matrix ＞
In the electromagnetic wave-transmitting metallic luster article of this embodiment, the base 10 may be resin, glass, ceramic, or the like from the viewpoint of electromagnetic wave permeability.
The base body 10 may be any of a base film, a resin molded base, a glass base, or an article to be provided with a metallic luster.
More specifically, the base film can be made of, for example, polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polybutylene terephthalate, polyamide, Individual polymers of polyvinyl chloride, polycarbonate (PC), cycloolefin polymer (COP), polystyrene, polypropylene (PP), polyethylene, polycycloolefin, polyurethane, acrylic (PMMA), ABS, etc. or Copolymer is a transparent film.

According to these components, there is no case that the brightness or electromagnetic wave transmission is affected. However, from the viewpoint of forming the indium oxide-containing layer 11 or the metal layer 12 later, those which can withstand high temperatures such as evaporation and sputtering are desirable. Therefore, among the above materials, for example, polyethylene terephthalate, poly Ethylene terephthalate, acrylic acid, polycarbonate, cycloolefin polymer, ABS, polypropylene, and polyurethane are ideal. Among them, polyethylene terephthalate, a cycloolefin polymer, polycarbonate, and acrylic acid are preferable from the viewpoint of a good balance between heat resistance and cost.

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

The base film can be formed into a smooth or anti-glare hard coat layer as required. By providing a hard coat layer, the abrasion resistance of the metal thin film can be improved. By providing a smooth hard coat layer, the metallic luster is increased. Conversely, with an anti-glare hard coat layer, glare can be prevented. The hard coat layer can be formed by applying a solution containing a curable resin.

Examples of the curable resin include thermosetting resin, ultraviolet curing resin, and electron beam curing resin. Types of the curable resin are polyester, acrylic, urethane, acrylic polyurethane, amine, silicone, silicate, epoxy, melamine, and oxetane. And acrylic resins. These curable resins can be used by selecting one or two or more of them as appropriate. Among these, acrylic resins, acrylic urethane resins, and epoxy resins are preferable, because they have high hardness, are likely to be cured by ultraviolet rays, and have good productivity.

Here, it should be noted that the base film is only one example of an object (substrate 10) on which the metal layer 12 can be formed on the surface. As described above, the base body 10 includes, in addition to the base material film, a resin molded article base material, a glass base material, and an article itself that should be provided with a metallic luster. Resin-molded article substrates and articles that should be provided with metallic luster are, for example, structural parts for vehicles, vehicle-mounted articles, housings of electronic devices, housings of home appliances, structural parts, mechanical parts, and various automotive parts , Electronic equipment parts, furniture, kitchen appliances and other household applications, medical equipment, construction materials parts, other structural parts or exterior parts.

The metal layer 12 may be formed on all the substrates, may be formed on a part of the surface of the substrate, or may be formed on the entire surface of the substrate. In this case, the base body 10 to be provided to the metal layer 12 is preferably made of the same material and conditions as those of the above-mentioned base film.

＜ 3. Indium oxide-containing layer ＞
In addition, as shown in FIG. 2, the electromagnetic-wave-transmitting metallic luster article 1 according to an embodiment may further include an indium oxide-containing layer 11 between the substrate 10 and the metal layer 12. The indium oxide-containing layer 11 may be directly provided on the surface of the substrate 10, or may be provided 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, that is, without gaps, on the surface of the substrate 10 that should be provided with metallic gloss. By setting in a continuous state, the smoothness or corrosion resistance of the indium oxide-containing layer 11, the further metal layer 12, or the metallic luster article 1 can be improved, and the indium oxide-containing layer 11 can be easily formed without deviation in the plane.

If the indium oxide-containing layer 11 is further provided between the substrate 10 and the metal layer 12 in this way, that is, the indium oxide-containing layer 11 is formed on the substrate 10 and the metal layer 12 is formed thereon, it is easy to form it in a discontinuous state. The metal layer 12 is therefore preferable. The details of the mechanism may not be clear, but it can be considered that when a thin film is formed on a substrate by sputtering particles of metal evaporation or sputtering, the surface diffusivity of the particles on the substrate will affect the shape of the film, and the temperature of the substrate is high. The wettability of the metal layer to the substrate is small, and the melting point of the material of the metal layer is low, and it is easy to form a discontinuous structure. Moreover, by providing an indium oxide-containing layer on the substrate, the surface diffusivity of the metal particles on the surface is promoted, and the metal layer is easily grown in a discontinuous state.

As the indium oxide-containing layer 11, indium oxide (In ₂ O ₃ ) itself may be used, or for example, a metal-containing substance such as indium tin oxide (ITO) or indium zinc oxide (IZO) may be used. However, ITO or IZO containing a second metal is more desirable at the point of higher discharge stability of the sputtering process. By using such an indium oxide-containing layer 11, it is also easy to form a continuous film along the surface of the substrate, and in this case, it is easy to make the metal layer laminated on the indium oxide-containing layer into an island-like layer. Continuous structure is ideal. In addition, as will be described later, in this case, not only chromium (Cr) or indium (In), but also various metals such as aluminum, which are generally difficult to form a discontinuous structure and difficult to apply to the present application, are easily contained in the metal layer.

The content ratio (content ratio = (SnO ₂ / (In ₂ O ₃ + SnO ₂ )) × 100) of the mass ratio of tin oxide (SnО ₂ ) contained in ITO is not particularly limited, for example, 2.5 wt% to 30 wt %, More preferably 3wt% ~ 10wt%. The content ratio (content ratio = (ZnO / (In ₂ O ₃ + ZnO)) × 100) of the mass ratio of zinc oxide (ZnO) contained in the IZO is, for example, 2 wt% to 20 wt%.
The thickness of the indium oxide-containing layer 11 is preferably 1,000 nm or less, more preferably 50 nm or less, and more preferably 20 nm or less from the viewpoints of sheet resistance, electromagnetic wave permeability, and productivity. On the other hand, in order to make the laminated metal layer 12 into a discontinuous state easily, 1 nm or more is preferable, and in order to easily and reliably form the discontinuous state, 2 nm or more is more preferable, and 5 nm or more is more preferable.

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

The details of the mechanism in which the metal layer 12 becomes discontinuous on the substrate are not necessarily clear, but it can be presumed to be the second most. 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 given, the temperature of the substrate is high, and the wettability of the metal layer to the substrate The small, low melting point of the material of the metal layer makes it easier to form a discontinuous structure. Therefore, regarding metals other than aluminum (Al), which are specifically used in the following examples, metals with relatively low melting points such as zinc (Zn), lead (Pb), copper (Cu), and silver (Ag) can also be considered. The same technique is used to form discontinuous structures.

Here, the average particle diameter of the plural portion 12a means an average value of the diameters of the circles corresponding to the plural portion 12a. The circle-equivalent diameter of the portion 12a is the diameter of the complete 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 the examples.
The diameter corresponding to a circle 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 diameter of the plurality of portions 12a contained in the metal layer in a state of being discontinuous to each other within the above-mentioned range, it is possible to further enhance the brightness while maintaining high electromagnetic wave permeability.

Of course, the metal layer 12 can exhibit sufficient brightness, and preferably has a relatively low melting point. This is because the metal layer 12 is preferably formed by growing a thin film by sputtering. For this reason, it is suitable that the metal layer 12 is a metal having a melting point of about 1000 ° C. or lower, and is selected from, for example, aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), and silver (Ag). Any one of at least one metal and an alloy containing the metal as a main component is preferable. In particular, Al and these alloys are preferable for reasons such as the brightness, stability, and price of the substance. When an aluminum alloy is used, the aluminum content is preferably 50% by mass or more.

The thickness of the metal layer 12 is sufficient to exhibit sufficient brightness, and is usually preferably 20 nm or more. On the other hand, from the viewpoint of sheet resistance or electromagnetic wave permeability, it is usually 100 nm or less. For example, 20 nm to 100 nm is ideal, and 30 nm to 70 nm is more ideal. This thickness is also suitable for forming a uniform film with high productivity, and the appearance of the resin molded product of the final product is also good. The thickness of the metal layer 12 can be measured by the method described in the column of the examples.

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

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

When an indium oxide-containing layer is further provided, the sheet resistance of the laminate of the metal layer and the indium oxide-containing layer is preferably 100 Ω / □ or more. In this case, the electromagnetic wave transmittance is at a wavelength of 5 GHz, and becomes approximately 10 to 0.01 [-dB]. More preferably, it is 1000Ω / □ or more. The value of this sheet resistance is, of course, affected by the material or thickness of the metal layer, and the material or thickness of the underlying indium oxide-containing layer is also greatly affected. Therefore, when the indium oxide-containing layer is provided, the relationship with the indium oxide-containing layer must be set after taking into consideration.

<5. Optical adjustment layer>
The optical adjustment layer is a high refractive index layer including at least one layer and having a refractive index of 1.75 or more.
The optical adjustment layer is preferably provided on the side where the metal layer 12 will be recognized, and may be directly provided on the metal layer 12 or may be provided through another layer. For example, as shown in FIG. 1, the metallic luster article 1 in one embodiment may be provided on the surface opposite to the base 10 side of the metal layer 12, as shown in FIG. 2, or may be provided on the metal layer. 12 and the base body 10. When 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 12 b may not necessarily 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 it can be set as a metallic glossy article with good design. In order to obtain a metallic appearance with a stronger color, the refractive index of the high refractive index layer is preferably 1.8 or more, and more preferably 1.9 or more. Further, from the 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 different refractive indexes.
Examples of the material of 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), Sb ₂ O ₃ (2.10), TiO ₂ (2.35), Inorganic substances such as Ta ₂ O ₅ (2.10), ZrO ₂ (2.05), ZnO (2.10), ZnS (2.30) (the values in parentheses of the above materials are refractive indices) or a mixture thereof is preferred. 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 a cost standpoint, 800 nm or less is more desirable, and 500 nm or less is more desirable. From a color standpoint, 15 nm or more is preferable, 20 nm or more is more preferable, and 30 nm or more is more preferable.

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

The adhesive forming the adhesive layer 14 is not particularly limited as long as it is a transparent adhesive, such as an acrylic adhesive, a rubber adhesive, a silicone adhesive, a polyester adhesive, and a urethane. Any one of a system-based adhesive, an epoxy-based adhesive, and a polyether-based adhesive may be used in combination of two or more types. From the viewpoints of transparency, processability, and durability, it is desirable to use an acrylic adhesive.

The thickness of the adhesive layer 14 is not particularly limited, but by forming thin, it is possible to improve visible light transmittance, film thickness accuracy, and flatness. Therefore, the thickness is preferably 100 μm or less, 75 μm or less, and 50 μm or less.

The total light transmittance of the entire adhesive layer 14 is not particularly limited, but an arbitrary visible light wavelength value measured in accordance with JIS K7361 is preferably 10% or more, more preferably 30% or more, and more preferably 50% or more. The higher the total light transmittance of the adhesive layer 14 is, the more desirable it is.

The transparent adhesive constituting the adhesive layer 14 may be colored.
In this case, since the metal layer 12 is visually recognized by the colored adhesive layer 14, the colored metallic luster can be found.

The method of coloring a transparent adhesive is not specifically limited, For example, it can color by adding a small amount of pigment.

A release liner may be provided on the adhesive layer 14 to protect the adhesive layer 14 until it is attached to the member 15 to be adhered.

In the metallic luster article of this embodiment, as long as the effect of the present invention can be obtained, in addition to the above-mentioned metal layer 12, the indium oxide-containing layer 11, the optical adjustment layer 13, and the adhesive layer 14, other layers may be provided according to the application. . The 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 (scratch resistance) for improving durability such as moisture resistance and abrasion resistance. Layer), barrier layer (corrosion prevention layer), easy adhesion layer, hard coating layer, anti-reflection layer, light extraction layer, anti-glare layer, etc.

<7. Manufacturing of metallic shiny articles>
An example of the manufacturing method of the metallic luster article 1 is demonstrated. Although not specifically described, when a substrate other than a base film is used, it can be produced in the same manner.

When forming the metal layer 12 on the substrate 10, a method such as vacuum deposition, sputtering, or the like can be used.
Examples of the method for forming the optical adjustment layer 13 include a vacuum evaporation method, a sputtering method, an ion plating method, and a coating method. An appropriate method may be adopted according to the type of the material and the required film thickness.

When the indium oxide-containing layer 11 is formed on the substrate 10, the indium oxide-containing layer 11 is formed by vacuum evaporation, sputtering, ion plating, or the like before the formation of the metal layer 12. However, from the point that the thickness can be strictly controlled from a large area, sputtering is preferable.

When the adhesive layer 14 is provided, it can be formed by applying an adhesive composition or the like to the surface on which the adhesive layer 14 is provided.
The adhesive composition can be applied by a conventional coater such as a gravure roll coater, an inverse roll coater, a touch roll coater, a dip roll coater, a rod coater, It is performed by a knife coater, a spray coater, or the like. The drying temperature can be appropriately adopted, and is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and particularly preferably 70 ° C to 120 ° C. The drying time is an appropriate and appropriate time. 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 the indium oxide-containing layer 11 is provided between the base body 10 and the metal layer 12, it is preferable that no other layers be interposed between the indium oxide-containing layer 11 and the metal layer 12 and direct contact is made.

＜ 8. Decoration member ＞
The decorative member according to this embodiment includes an adhered member and the electromagnetic wave-transmitting metallic luster article described above, and the electromagnetic wave-transmitting metallic luster article (metallic luster article 1) is attached to the adherend member through the adhesive layer.

The metallic luster article 1 can also be used by sticking to the inner surface of the transparent adherend 2. The transparent adhered member 15 is, for example, a member made of glass or plastic, but is not limited thereto.

FIG. 4 is a schematic cross-sectional view of a decorative member 2 according to an embodiment of the present invention. The decorative member 2 according to an embodiment of the present invention is a schematic cross-sectional view of a state where the metallic luster article 1 is attached to the adhered member 15. The decorative member 2 of this embodiment is a metallic luster article 1 including a metal layer 12, an indium oxide-containing layer 11, an optical adjustment layer 13, a substrate 10 (base film), and an adhesive layer 14. 15.

5 is a schematic cross-sectional view of a decorative member according to an embodiment of the present invention. The decorative member 2 is a metallic luster article 1 having a structure shown in FIG. 5, and is adhered to the adhered member 15. In FIG. 5, the metallic lustrous article 1 passes through the adhesive layer 14 to face on the opposite side (hereinafter also referred to as the inside) of the surface 2 a of the side (hereinafter also referred to as the outside) viewed from the transparent adhered member 15. 2b is attached, and the optical adjustment layer 13 and the metal layer 12 are visually recognized through the adhered member 15 and the adhesive layer 14. That is, the metallic luster article 1 of this embodiment is a transparent adherend 15 which can be decorated from the inside.
The decorative member 2 of the present embodiment is obtained by attaching the metallic luster article 1 to the inner side of the adhered member 15, and thus it is possible to obtain a metallic appearance that is not easily damaged and colored. In addition, the texture of the adhered member 15 can be displayed as it is, and the adhered member 15 can be decorated.

The method for attaching the metallic luster article 1 to the adhered member 2 is not particularly limited, and for example, it can be attached by vacuum forming. The so-called vacuum forming is to expand the metal luster article 1 while heating and softening it, and decompress the space on the side of the adhered member of the metal luster article 1 as needed. A three-dimensional three-dimensional shape is a method of attaching and laminating the metallic luster article 1 while forming it.
The metallic luster article 1 can apply the above description.

In the decorative member of this embodiment, in the CIE-L ^* a ^* b ^* color system of the reflected light on the adhered member side, the square root of the square sum of the a ^* value and the b ^* value is preferably 5.0 or more. This is because if the square root of the sum of the squares of the a ^* value and the b ^* value is 5.0 or more, the coloring becomes sufficient. The square root of the squared sum of a ^* value and b ^* value is more preferably 10 or more, and more preferably 15 or more. The upper limit of the square root of the sum of the squares of the a ^* value and the b ^* value is not particularly limited, but is preferably below 70, more preferably below 65, and even more preferably below 60.

CIE-L ^* a ^* b ^* The color system is the color system recommended by CIE (International Commission for Illumination) in 1976. L ^* is the brightness, from 0 to 100, the larger the value, the brighter it is. Chroma is represented by a ^* and b ^* , a ^* is an index indicating the degree from red to green of the hue, and if the value of a ^* is large in the positive direction, a red hue is formed. In addition, b ^* is an index indicating the degree from yellow to blue of a hue. When a ^* and b ^{* are both} 0, it becomes achromatic.

The decorative member 2 according to the present embodiment preferably has a difference between the maximum value and the minimum value of the reflectance in the range of 380 nm to 780 nm in the side of the adhered member, which is preferably 20% or more. From the viewpoint of the coloring density, 35% or more is more preferable, and 40% or more is more preferable.
The upper limit of the difference between the maximum value and the minimum value of the reflectance is not particularly limited, but it is preferably below 90%, more preferably below 85%, and even below 80%.

<9. Use of metallic luster articles and decorative members>
Since the metallic luster article 1 and the metal thin film of this embodiment are electromagnetic wave transmissive, they are preferably used in a device or article for transmitting and receiving electromagnetic waves, and parts thereof. For example, it is possible to use household parts such as vehicle structural parts, vehicle-mounted supplies, housings of electronic devices, housings of home appliances, structural parts, mechanical parts, various automotive parts, electronic device parts, furniture, and kitchen supplies. Intended use, medical equipment, parts of building materials, other structural parts, exterior parts, etc.
More specifically, in terms of vehicle relationship, the dashboard, central storage box, door handle, door trim, shift lever, pedals, glove box, bumper, hood, fender, rear luggage Cases, doors, roofs, pillars, seats, steering wheels, ECU boxes, electrical parts, engine peripheral parts, drive system / gear peripheral parts, air intake / exhaust system parts, cooling system parts, etc.
As electronic devices and home appliances, more specifically, refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, televisions, clocks, ventilators, projectors, speakers, and other household appliances, personal computers, mobile phones Telephones, smart phones, digital cameras, tablet PCs, portable music players, portable game consoles, chargers, batteries and other electronic information equipment.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. A metallic shiny article was prepared, and the reflectance, CIE-L ^* a ^* b ^* , a ^* values and b ^* values of the system, radio wave transmission attenuation (-dB), and sheet resistance were evaluated. In addition, as the base 10, a base film is used.
The radio wave transmission attenuation is an evaluation of electromagnetic wave transmission. It is desirable that the value of radio wave transmission attenuation is small.
The details of the evaluation method are as follows.

(1) Spectral reflectance Using a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation, the visible light in a wavelength range of 380 nm to 780 nm was measured at 5 nm intervals, and the reflected light was irradiated to one side of a metallic shiny article. Spectral reflectance.
In the measurement, the visible light was incident on the surface of the member to be adhered, and Table 1 describes the reflectance (with a paste). Table 1 shows the maximum value (max), the minimum value (min), and the difference between the maximum value (max) and the minimum value (min) of the spectral reflectance (%) in the wavelength range of 380 nm to 780 nm.

(2) CIE-L ^* a ^* b ^* indicates the a ^* value and b ^* value of the system. The spectral reflectance at a wavelength of 380 to 780 nm measured with the above-mentioned spectrophotometer U-4100 and the relative spectrophotometry of the CIE standard light source D65 are used. Distribution to calculate CIE-L ^* a ^* b ^* represents the a ^* value and b ^* value of the system. Table 1 shows the square roots of the a ^* value, b ^* value, a ^* value, and the second power of the b ^* value.

(3) Radio wave transmission attenuation amount A rectangular waveguide measurement and evaluation fixture WR-187 was used to clamp the sample, and a spectrum analyzer MS4644B manufactured by Anritsu Company was used to measure the radio wave transmission attenuation amount at 5 GHz.

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

(5) Evaluation method of film thickness First, as shown in FIG. 8, a square area 3 with a side of 5 cm is appropriately extracted from a metallic luster, so that the centerline of each of the vertical and horizontal sides of the square area 3 is drawn. The points "a" to "e" at five points obtained by dividing A and B into four equal parts are taken as measurement points.
Next, a cross-sectional image (a transmission electron microscope photograph (TEM image)) of each of the selected measurement locations is shown in FIG. 9, and a viewing angle region containing five or more metal portions 12 a is extracted from the obtained TEM image.
The total cross-sectional area of the metal layer in each of the viewing angle regions that were cut out at the five measurement points by the horizontal width of the viewing angle region was defined as the thickness of the metal layer in each viewing angle region. The average value of the thickness of the metal layer in each viewing angle region is defined as the thickness (nm) of the metal layer.

[Example 1]
A film having a thermosetting resin having a thickness of 2000 μm formed on one side of a PET film (thickness: 50 μm) made by Mitsubishi Resin Co., Ltd. was used as a base film.
First, an ITO target is installed in a DC magnetron sputtering apparatus, and an Ar gas and an O ₂ gas are introduced, and sputtering is performed, thereby directly forming an ITO layer with a thickness of 5 nm along the surface of the substrate film. The temperature of the base film when the ITO layer was formed was set to 130 ° C. The content rate of tin oxide (SnО ₂ ) contained in ITO (content rate = (SnO ₂ / (In ₂ O ₃ + SnO ₂ )) × 100) was 10% by weight.

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

(Formation of optical adjustment layer)
Next, an Nb target (AC: 40 kHz) was installed in the AC sputtering device, and Ar gas and O ₂ gas were introduced while sputtering, thereby forming a 110 nm Nb ₂ O ₅ layer as an optical adjustment layer on the Al layer.

In this way, 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 is obtained. The reflectance of the obtained laminate (metallic luster article) was measured by the method described above, and is shown in Table 1 as the reflectance (no paste).

＜ Production of 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 was discharged to a reaction vessel including a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device. In addition, with respect to 100 parts by mass of the monomer mixture, 0.1 part by mass of 2,2′-azobisisobutyronitrile and 100 parts by mass of ethyl acetate were cut off, and as a polymerization initiator, nitrogen gas was introduced while gently stirring. After nitrogen substitution, the temperature of the liquid in the reaction container was maintained at about 55 ° C for 8 hours to perform a polymerization reaction to prepare a solution of an acrylic polymer having a weight average molecular weight (Mw) of 1.8 million and Mw / Mn = 4.1 (solid concentration: 30). quality%).
With respect to 100 parts by mass of the solid portion of the obtained acrylic polymer solution, 0.3 parts by mass of over-gasified benzamidine (manufactured by Japan Oil Corporation, NYPER® BMT) was prepared, and an isocyanate-based crosslinking agent (manufactured by TOSOH CORPORATION, Coronate®) L) 1 part by mass was prepared to obtain an adhesive composition.

＜ Manufacture of metallic shiny articles ＞
With respect to the surface of the metal layer side of the obtained laminated body, a hand roller was used to apply the obtained adhesive composition to form an adhesive layer, thereby obtaining a metallic luster having a metallic luster that was colored. .

＜ Manufacture of decorative members ＞
As the adhered member, a glass having a thickness of 1.2 mm was used.
The adhesive layer side of the obtained metallic luster article was attached to a member to be adhered to obtain a decorative member.

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

[Examples 6 and 7]
Except for the formation of the optical adjustment layer in Example 1, the Si target was mounted on an AC sputtering device, and the Ar gas and N ₂ gas were introduced and sputtered to thereby form the film thicknesses in Table 1 on the Al layer. A decorated member was obtained in the same manner as in Example 1 except that SiN (optical adjustment layer) was formed.

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

[Comparative Example 2]
In addition to changing the optical adjustment layer of Example 1 from niobium oxide (Nb ₂ O ₅ ) to a mixture of zinc oxide (ZnO), silicon oxide (SiOx), and aluminum oxide (Al ₂ O ₃ ) (mass ratio, zinc oxide: oxidation A sintered body of silicon: alumina = 77: 20: 3) was obtained in the same manner as in Example 1 except that the sputtering device was changed to a DC sputtering device.

The evaluation results are shown in Table 1 below. The relationship between the wavelength of visible light and the reflectance (%) in the range of 380 nm to 780 nm of the decorative member of Example 5 and Comparative Example 1 is shown in FIG. 6. 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 is shown in FIG. 7.

As clearly shown in Table 1, since Examples 1 to 7 include high refractive index layers having a refractive index of 1.75 or more, the square root of the square sum of the a ^* value and b ^* value of the CIE-Lab color system is 13 ~ 30, can obtain colored metallic luster items and decorative members. In addition, since the aluminum layer includes a plurality of portions 12a formed in a discontinuous state, good results can be obtained regarding the electromagnetic wave permeability.
On the other hand, the metallic luster articles and decorative members of Comparative Examples 1 and 2 have small differences in reflectance. In addition, the square root of the quadratic sum of the a ^* value and the b ^* value is also small, and the coloring becomes insufficient.

In addition, regarding metals other than aluminum (Al), which are particularly used in the above examples, metals with relatively low melting points such as zinc (Zn), lead (Pb), copper (Cu), and silver (Ag) can also be considered. A discontinuous structure is formed in the same way.

The present invention is not limited to the foregoing embodiments, and may be appropriately modified and embodied without departing from the spirit of the invention.

As mentioned above, although the preferred embodiment of this invention was described, this invention is not limited to the said embodiment, Various deformation | transformation and substitution can be added to the said embodiment within the range which does not deviate from the scope of this invention.
In addition, this case is based on the Japanese patent application (Japanese Patent Application No. 2018-082656) filed on April 23, 2018 and the Japanese Patent Application (Japanese Patent Application No. 2019-080625) filed on April 22, 2019. Reference is made in this case.

[Industrial availability]

The metallic luster article of the present invention is a device or article and its parts that can be used for transmitting and receiving electromagnetic waves. For example, it can also be used in structural parts for vehicles, vehicle-mounted supplies, housings of electronic devices, housings of home appliances, structural parts, mechanical parts, various automotive parts, electronic device parts, furniture, kitchen supplies, etc. For home use, medical equipment, parts for building materials, other structural parts, exterior parts, etc., there are various applications that require both design and electromagnetic wave permeability.

1‧‧‧ metallic shiny items

2‧‧‧ Decoration

10‧‧‧ Matrix

11‧‧‧ Indium oxide layer

12‧‧‧ metal layer

12a‧‧‧part

12b‧‧‧Gap

13‧‧‧Optical adjustment layer

14‧‧‧ Adhesive layer

15‧‧‧ Adhesive member

FIG. 1 is a schematic cross-sectional view of an electromagnetic wave-transmitting metallic luster article according to an embodiment of the present invention.

FIG. 2 is a schematic cross-sectional view of an electromagnetic wave-transmitting metallic luster article according to an embodiment of the present invention.

3 is a view showing an electron microscope photograph of a surface of an electromagnetic wave-transmitting metallic luster 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.

5 is a schematic cross-sectional view of a decorative member according to an embodiment of the present invention.

FIG. 6 is a graph showing the relationship between the wavelength of visible light and the reflectance (%) of the decorative member of Example 5 and Comparative Example 1 in a wavelength range of 380 nm to 780 nm.

FIG. 7 is a graph showing the relationship between a ^* value and b ^* value of the decorative members of Examples 1 to 7 and Comparative Examples 1 and 2. FIG.

FIG. 8 is a diagram illustrating a method for measuring a film thickness of a metal layer of an electromagnetic wave-transmitting metallic luster article according to an embodiment of the present invention.

9 is a view showing a transmission electron microscope photograph (TEM image) of a cross section of a metal layer according to an embodiment of the present invention.

Claims (17)

An electromagnetic wave-transmitting metallic luster article, comprising: a base body; a metal layer formed on the base body; and at least one optical adjustment layer. The aforementioned metal layer includes a plurality of portions in which at least a portion is in a state of being discontinuous from each other, The optical adjustment layer includes a high refractive index layer having a refractive index of 1.75 or more. For example, the electromagnetic wave-transmitting metallic luster article of the first patent application range, wherein the thickness of the optical adjustment layer is 10 nm to 1000 nm. For example, in the electromagnetic wave-transmitting metallic luster article of the scope of claims 1 or 2, 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 provided with the optical adjustment layer is 30% or more. The electromagnetic wave-transmitting metallic luster article according to any one of claims 1 to 3, further comprising an indium oxide-containing layer between the substrate and the metal layer. For example, the electromagnetic wave-transmitting metallic luster article of the scope of application for patent No. 4, wherein the aforementioned indium oxide-containing layer is provided in a continuous state. For example, the electromagnetic wave-transmitting metallic luster article of the scope of application for the patent item 4 or 5, wherein the aforementioned indium oxide-containing layer contains indium oxide (In ₂ O ₃ ), indium tin oxide (ITO), or indium zinc oxide ( IZO). The electromagnetic wave-transmitting metallic luster article according to any one of claims 4 to 6, in which the thickness of the indium oxide-containing layer is 1 nm to 1000 nm. The electromagnetic wave-transmitting metallic luster article according to any one of claims 1 to 7, wherein the thickness of the metal layer is 20 nm to 100 nm. The electromagnetic wave-transmitting metallic luster article according to any one of claims 4 to 7, wherein 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 metal layer) The thickness of the indium oxide layer is 0.02 to 100. The electromagnetic wave-transmitting metallic luster article according to any one of claims 1 to 9 of the scope of patent application, wherein the sheet resistance is 100 Ω / □ or more. The electromagnetic wave-transmitting metallic luster article according to any one of claims 1 to 10, wherein the plurality of portions are formed in an island shape. The electromagnetic wave-transmitting metallic luster article according to any one of claims 1 to 11, wherein the metal layer is made of aluminum (Al), zinc (Zn), lead (Pb), or copper (Cu). , Silver (Ag), or any of these alloys. The electromagnetic wave-transmitting metallic luster article according to any one of claims 1 to 12, in which the aforementioned substrate is a substrate film, a resin molded article substrate, a glass substrate, or a metal luster Any of the items. The electromagnetic wave-transmitting metallic luster article according to any one of claims 1 to 13 of the scope of application for a patent, further including an adhesive layer made of a transparent adhesive. A decorative member, comprising: an adhered member, and an electromagnetic wave-transmitting metallic luster article as described in item 14 of the scope of patent application, The electromagnetic wave-transmitting metallic luster article is adhered to the adherend member via the adhesive layer. For example, in the decorative member of the scope of application for patent No. 15, in the CIE-Lab color system of the reflected light on the adhered member side, the square root of the square sum of the a ^* value and the b ^* value is 5.0 or more. For example, the decorative member according to the 16th aspect of the application for a patent, wherein the difference between the maximum value and the minimum value of the reflectance in the range of 380nm to 780nm of the adhered member side is 20% or more.