JP2022082052A - Metallic decorative film, metallic molded body, and metallic interior and exterior members for vehicles - Google Patents

Abstract

To provide a metallic decorative film that can give a metallic design that allows the passage of millimeter waves, can cover and conceal devices such as a radar so that they are difficult to be seen or cannot be seen from outside, and have high designability, and provide a metallic molded body, and metallic interior and exterior members for vehicles.SOLUTION: This metallic decorative film has a base material, an anchor layer provided on the base material, and a metal deposition layer provided on the anchor layer. The metal deposition layer has: a first metal deposition layer that forms a prescribed pattern on the anchor layer; and a second metal deposition layer that is formed from a first portion for covering the first metal deposition layer, and a second portion other than the first portion. The first metal deposition layer contains indium. The second metal deposition layer contains indium.SELECTED DRAWING: Figure 2

Description

The present invention relates to a metal-like decorative film, a metal-like molded body, and a metal-like vehicle interior / exterior member. More specifically, the present invention allows millimeter waves to be transmitted while being able to form various metallic patterns and covering a device such as a millimeter wave radar from the outside so that it is difficult to see or cannot be seen from the outside. The present invention relates to a metal-like decorative film, a metal-like molded body, and a metal-like vehicle interior / exterior member.

Conventionally, a technique for forming a pattern of a metal vapor deposition layer on a base material has been developed. Patent Document 1 discloses a method for producing a partially vapor-deposited foil used in a transfer decoration method on the surface of a molded product such as a housing of a home electric appliance or a communication device and a simultaneous molding decoration method. Patent Document 2 discloses a method for producing a film in which a metal-deposited layer is laminated and a metal-deposited film.

Japanese Unexamined Patent Publication No. 2006-239962 Japanese Unexamined Patent Publication No. 2006-123295

By the way, an electric vehicle does not require a grill at the front portion of the vehicle. Therefore, various studies have been made on how to design the front part of the automobile. By law, soft, reversible plastic is used for parts that may collide with people, such as the front part of an electric vehicle (the grill part of an engine vehicle). Therefore, by using the same material as the bonnet part (metal) for the front part of the automobile, it is not possible to create a sense of unity.

Further, in recent automobiles, a millimeter-wave radar may be provided on the front part of the automobile due to ADAS (advanced driver assistance system) and automatic driving technology. In the case of an engine vehicle, equipment such as a millimeter-wave radar may be placed behind the grille, and the equipment is difficult to see from the outside. Further, since the millimeter wave can pass through the gap of the grill, the grill portion of the engine vehicle does not need to consider the transparency of the millimeter wave. On the other hand, when a design without a grill is adopted in an electric vehicle, it is possible to transmit millimeter waves, and it is difficult to see or hide equipment such as millimeter wave radar from the outside, and further, it is possible to hide it so that it cannot be seen. There is a demand for a technique capable of providing a metal-like design with excellent design. The invention that solves such a problem is not disclosed in the above-mentioned Patent Documents 1 and 2.

The present invention has been made in view of such a conventional invention, and is capable of transmitting millimeter waves and making it difficult or invisible to see a device such as a radar from the outside. Further, it is an object of the present invention to provide a metal-like decorative film, a metal-like molded body, and a metal-like vehicle interior / exterior member capable of providing a metal-like design having excellent design.

As a result of diligent studies, the present inventor can form various designs by providing a plurality of metal vapor deposition layers containing indium in a metallic decorative film, can transmit millimeter waves, and further, can be used for radar and the like. We have found that the device is difficult to see from the outside or can be covered so that it cannot be seen, and completed the present invention. That is, the metal-like decorative film, the metal-like vehicle interior / exterior member, and the metal-like molded body of the present invention that solve the above problems mainly include the following configurations.

(1) It has a base material, an anchor layer provided on the base material, and a metal vapor deposition layer provided on the anchor layer, and the metal vapor deposition layer has a predetermined pattern on the anchor layer. It has a first metal vapor deposition layer to be formed, a first portion covering the first metal vapor deposition layer, and a second metal vapor deposition layer composed of a second portion other than the first portion, and the first metal vapor deposition layer. The metal vapor deposition layer of the above is a metal-like decorative film containing indium, and the second metal vapor deposition layer contains indium.

According to such a configuration, a predetermined pattern can be formed by the first metal vapor deposition layer. Thereby, for example, the metallic decorative film of the present invention can give various designs to an object (for example, an exterior member of an automobile). Further, the metal vapor deposition layer contains indium. Therefore, the metallic decorative film can transmit millimeter waves, and it is difficult to see the device such as a radar from the outside, or it can cover it so that it cannot be seen.

(2) The metal-like decorative film according to (1), wherein the average thickness of the first metal-deposited layer is 90 nm or less, and the average thickness of the second metal-deposited layer is 90 nm or less.

According to such a configuration, the metallic decorative film can have high millimeter wave transparency in both the first portion and the second portion.

(3) The metallic decorative film according to (1) or (2), wherein the total light reflectance at an incident angle of 5 ° at a wavelength of 550 nm in the second portion is 35% or more.

According to such a configuration, the metallic decorative film is more likely to express a metallic appearance. In addition, the metallic decorative film is easy to cover up devices such as radar so that they cannot be seen from the outside.

(4) The metal-like decorative film according to any one of (1) to (3), wherein the first metal-deposited layer has a sea-island structure, and the second metal-deposited layer has a sea-island structure. ..

According to such a configuration, the metallic decorative film is more likely to transmit millimeter waves.

(5) Any of (1) to (4), wherein the radio wave attenuation rate at a frequency of 77 GHz in the first part is 1 dB or less, and the radio wave attenuation rate at a frequency of 77 GHz in the second part is 1 dB or less. Metallic decorative film described in Crab.

According to such a configuration, the metallic decorative film is more likely to transmit millimeter waves, which are preferably used in a forward-looking radar for detecting a long distance, for example.

(6) Any of (1) to (5), the radio wave attenuation rate at a frequency of 24 GHz in the first part is 1 dB or less, and the radio wave attenuation rate at a frequency of 24 GHz in the second part is 1 dB or less. Metallic decorative film described in Crab.

According to such a configuration, the metallic decorative film is more likely to transmit millimeter waves (quasi-millimeter waves) preferably used in, for example, a peripheral monitoring radar.

(7) A metallic molded product using the metallic decorative film according to any one of (1) to (6).

According to such a configuration, the metallic molded body is easily manufactured by molding. As the molded metal-like molded body, the above-mentioned metal-like decorative film is used. Therefore, various designs can be given to the metallic molded body. Further, the metal-like molded body can transmit millimeter waves and can cover a device such as a radar so that it cannot be visually recognized from the outside.

(8) A metal-like vehicle interior / exterior member using the metal-like molded body according to (7).

According to such a configuration, the metal-like molded body is used as the metal-like vehicle interior / exterior member. Therefore, various designs can be applied to the metal-like vehicle interior / exterior members. Further, the metal-like vehicle interior / exterior member can transmit millimeter waves, and can make it difficult to see the device such as a radar from the outside, or can cover it so that it cannot be seen.

According to the present invention, a metal-like design capable of transmitting millimeter waves, making it difficult to see a device such as a radar from the outside, or covering it so that it cannot be seen, and further providing an excellent design. It is possible to provide a metal-like decorative film, a metal-like molded body, and a metal-like vehicle interior / exterior member.

FIG. 1 is a schematic cross-sectional view of a metallic decorative film according to an embodiment of the present invention. FIG. 2 is an external photograph of a metallic molded product produced by using the metallic decorative film of the embodiment of the present invention. FIG. 3A is a schematic cross-sectional view illustrating a patterning process for producing a metallic decorative film according to an embodiment of the present invention. FIG. 3B is a schematic cross-sectional view illustrating a patterning process for producing a metallic decorative film according to an embodiment of the present invention. FIG. 3C is a schematic cross-sectional view illustrating a patterning process for producing a metallic decorative film according to an embodiment of the present invention. FIG. 3D is a schematic cross-sectional view illustrating a patterning process for producing a metallic decorative film according to an embodiment of the present invention. FIG. 3E is a schematic cross-sectional view illustrating a patterning process for producing a metallic decorative film according to an embodiment of the present invention. FIG. 3F is a schematic cross-sectional view illustrating a patterning process for producing a metallic decorative film according to an embodiment of the present invention. FIG. 4 is a schematic diagram illustrating a state in which a gravure coater is used in a patterning step when producing a metallic decorative film according to an embodiment of the present invention. FIG. 5 is a schematic view illustrating a roll of a gravure coater used in a patterning step when producing a metallic decorative film according to an embodiment of the present invention.

<Metallic decorative film>
In one embodiment of the present invention, the metallic decorative film (hereinafter, also referred to as a film) has a base material, an anchor layer provided on the base material, and a metal vapor deposition layer provided on the anchor layer. The metal vapor deposition layer is a second portion composed of a first metal vapor deposition layer forming a predetermined pattern on the anchor layer, a first portion covering the first metal vapor deposition layer, and a second portion other than the first portion. It has a metal vapor deposition layer. The first metal vapor deposition layer contains indium. The second metal vapor deposition layer contains indium. According to such a film, a predetermined pattern can be formed by the first metal vapor deposition layer. Thereby, for example, the film can give various designs to an object (for example, an exterior member of an automobile). Further, the metal vapor deposition layer contains indium. Therefore, the metallic decorative film can transmit millimeter waves, and it is difficult to see the device such as a radar from the outside, or it can cover it so that it cannot be seen. That is, according to the film of the present embodiment, various designs can be applied to an object (for example, an exterior member of an automobile). At this time, as a design, in addition to a design in which a device such as a radar is hidden so that it cannot be seen from the outside, a design in which the device such as a radar can be seen from the outside can be adopted. Each will be described below.

(Base material)
The base material is not particularly limited. As an example, the substrate is a poly (meth) acrylic acid ester such as polymethyl methacrylate (PMMA), polycarbonate, polyethylene terephthalate, polyethylene-2,6-naphthalate, polyvinyl fluoride (PVF), polyvinylidene fluoride (polyfluoride). PVDF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene-per It is composed of a fluoroalkyl vinyl ether copolymer (PFA), a tetrafluoroethylene-hexafluoropropylene copolymer (FEP) and the like.

The thickness of the base material is not particularly limited. As an example, the thickness of the base material is preferably 1.0 to 300 μm. When the thickness of the base material is within the above range, the film is excellent in scratch resistance and wear resistance.

As the base material, one having a desired surface treatment may be used. The surface treatment is not particularly limited. As an example, the surface processing includes matte processing, satin processing, embossing processing, hairline processing and the like. Further, various coatings (fluorine processing, hard coat processing, etc.), surface treatment such as transfer may be applied to the surface of the base material (the surface opposite to the surface on which the anchor layer is formed). As a result, various designs and functionality can be imparted to the surface of the base material.

(Anchor layer)
The anchor layer is provided on the substrate. The anchor layer is provided to improve the adhesion between the base material and the metal vapor deposition layer.

The anchor layer is not particularly limited. As an example, the anchor layer may be a raw material having good adhesion to the base material and good acceptance of indium contained in the metal vapor deposition layer, and may be an acrylic resin, a nitrocellulose resin, or a polyurethane resin. , Polyester-based resin, styrene-maleine-based acid resin, chlorinated PP-based resin, etc.

The thickness of the anchor layer is not particularly limited. As an example, the thickness of the anchor layer is preferably 0.1 to 3 μm. When the thickness of the anchor layer is within the above range, the film has excellent adhesion between the base material and the metal vapor deposition layer.

The anchor layer may be imparted with design by applying a colorant or a metal pigment. For example, by blending a yellow pigment as a colorant, the laminated film can express a golden appearance. The type and content of the colorant can be appropriately adjusted according to the desired metallic appearance. Further, the anchor layer may be provided with functionality such as an antistatic effect by blending an antistatic agent or the like.

The method of forming the anchor layer is not particularly limited. As an example, for the anchor layer, a resin solution constituting the anchor layer appropriately dissolved in a solvent (for example, methyl ethyl ketone, toluene, ethyl acetate, etc.) is applied onto the substrate using a roll coater or the like, and then 80 to 80 to It can be formed by drying at about 100 ° C. for 30 seconds to 1 minute.

The resin solution of the anchor layer is applied to the substrate and then dried. As a result, the solvent of the resin solution is immersed in the surface of the base material, and the resin constituting the anchor layer and the base material are compatible with each other. As a result, the anchor layer and the base material can be firmly adhered to each other.

(Metal vapor deposition layer)
The metal vapor deposition layer is provided on the anchor layer. The metal vapor deposition layer is a second metal vapor deposition layer composed of a first metal vapor deposition layer forming a predetermined pattern on the anchor layer, a first portion covering the first metal vapor deposition layer, and a second portion other than the first portion. Has a layer.

-First metal vapor deposition layer The first metal vapor deposition layer is provided on the anchor layer. The first metal vapor deposition layer contains indium. Indium may be contained as an oxide or a nitride. The inclusion of indium in the first metal vapor deposition layer allows the resulting film to transmit millimeter waves from a millimeter wave radar. In addition, the first metal-deposited layer containing indium is less likely to cause poor appearance and has excellent molding processability. As a result, the film is easily processed into various three-dimensional shapes.

Further, the first metal vapor deposition layer may contain various non-metals, metals, metal oxides and metal nitrides in addition to indium. Non-metals, metals and the like are not particularly limited. For example, non-metals are amorphous carbon (DLC) and its composites, and metals and the like are metals such as gold, silver, platinum, tin, chromium, silicon, titanium, zinc, aluminum and magnesium, and their oxidation. A thing, its nitride.

The content of indium in the first metal vapor deposition layer is not particularly limited. As an example, the content of indium in the first metal vapor deposition layer is preferably 95% by mass or more, and more preferably 98% by mass or more. The content of indium may be 100% by mass.

The thickness (average thickness) of the first metal vapor deposition layer is not particularly limited. As an example, the thickness of the first metal vapor deposition layer is preferably 9 nm or more. The thickness of the first metal vapor deposition layer is preferably 90 nm or less, more preferably 80 nm or less. When the thickness of the first metal vapor deposition layer is within the above range, millimeter waves are easily transmitted. Further, the first metal vapor deposition layer has a difference in reflectance and color of reflected light between the first portion formed in combination with the second metal vapor deposition layer described later and the second portion described later. Easy to adjust. Therefore, the obtained film can realize various metallic patterns, and is more excellent in design and design. Further, since the thickness of the first metal-deposited layer is within the above range, the first metal-deposited layer is likely to be provided so as to have a sea-island structure described later. In this embodiment, the metal vapor deposition layer may have a sea-island structure. In such a case, the thickness of the metal-deposited layer is the height when assuming a rectangle having the same width and the same area as the cross-sectional area (substantially fan-shaped cross-sectional area) of the metal-deposited layer having an island structure. be.

In the present embodiment, the method for measuring the thickness of the first metal-deposited layer and the second metal-deposited layer described later is not particularly limited. As an example, the thickness can be measured by scanning electron microscope (SEM) observation, fluorescent X-ray analysis (XRF), ultraviolet-visible spectroscopy, and the like. When the thickness of the metal vapor deposition layer is determined by observation with a scanning electron microscope (SEM), the cross section of the vapor deposition film containing indium is observed using a scanning electron microscope (SEM), and the metal layer containing indium at 5 to 10 places is observed. Measure the thickness of and calculate the average. When the thickness of the metal vapor deposition layer is determined by fluorescent X-ray analysis (XRF), the thickness of the vapor deposition film containing indium at 5 to 10 points is measured by quantitative analysis, and the average is calculated. Further, when the thickness of the metal vapor deposition layer is determined by ultraviolet-visible spectroscopy, the reflectance of the vapor deposition film containing indium at 5 to 10 points is measured by an ultraviolet-visible spectrophotometer, and the metal vapor deposition layer is obtained from the obtained reflectance spectrum. Calculate the average thickness of. In this embodiment, the thickness (nm) of the metal vapor deposition layer is calculated by the fluorescent X-ray analysis method (XRF).

The first metal vapor deposition layer preferably has a sea-island structure (so-called discontinuous structure). Thereby, the first metal vapor deposition layer containing indium can obtain an excellent metallic luster as compared with other general metal vapor deposition layers such as an aluminum vapor deposition layer. Further, by having the sea-island structure, the obtained film is more likely to transmit millimeter waves.

The method of providing the first metal vapor deposition layer so as to have a sea-island structure is not particularly limited. As an example, the first metal vapor deposition layer uses a vapor deposition source containing indium and has a sea-island structure by a physical vapor deposition (PVD) method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method. Can be formed.

-Second metal-deposited layer The second metal-deposited layer is composed of a first portion that covers the first metal-deposited layer and a second portion other than the first portion. The second metal vapor deposition layer contains indium. Indium may be contained as an oxide or a nitride. The inclusion of indium in the second metal vapor deposition layer allows the resulting film to transmit millimeter waves from the millimeter wave radar. In addition, the second metal-deposited layer containing indium is less likely to cause poor appearance and has excellent molding processability. As a result, the film is easily processed into various three-dimensional shapes.

Further, the second metal vapor deposition layer may contain various non-metals, metals, metal oxides and metal nitrides in addition to indium. Non-metals, metals and the like are not particularly limited. For example, non-metals include amorphous carbon (DLC) and its composites, and metals and the like include metals such as gold, silver, platinum, tin, chromium, silicon, titanium, zinc, aluminum and magnesium, and their oxides. It is the nitride.

The content of indium in the second metal vapor deposition layer is not particularly limited. As an example, the content of indium in the second metal vapor deposition layer is preferably 95% by mass or more, and more preferably 98% by mass or more. The content of indium may be 100% by mass.

The thickness (average thickness) of the second metal vapor deposition layer is not particularly limited. As an example, the thickness of the second metal vapor deposition layer is preferably 20 nm or more. The thickness of the second metal vapor deposition layer is preferably 90 nm or less, more preferably 80 nm or less. When the thickness of the second metal vapor deposition layer is within the above range, millimeter waves are easily transmitted. Further, as will be described later, in the second metal vapor deposition layer, the value of the total light reflectance is higher than the value of the total light transmittance, making it difficult to see the back of the film, and a device such as a radar is used. It becomes difficult to see from the outside. Further, since the thickness of the second metal-deposited layer is within the above range, the second metal-deposited layer is likely to be provided so as to have a sea-island structure described later.

The second metal vapor deposition layer preferably has a sea-island structure (so-called discontinuous structure). As a result, the second metal vapor deposition layer containing indium can obtain an excellent metallic luster as compared with other general metal vapor deposition layers such as an aluminum vapor deposition layer. Further, by having the sea-island structure, the obtained film is more likely to transmit millimeter waves.

The method of providing the second metal vapor deposition layer so as to have a sea-island structure is not particularly limited. As an example, the second metal vapor deposition layer uses a vapor deposition source containing indium and has a sea-island structure by a physical vapor deposition (PVD) method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method. Can be formed.

In the present embodiment, the first portion of the second metal vapor deposition layer is a portion that covers the first metal vapor deposition layer. On the other hand, the second portion of the second metal vapor deposition layer is a portion other than the first portion. Therefore, the second portion is provided on the anchor layer.

The film of the present embodiment is capable of transmitting millimeter waves in both the first portion and the second portion. That is, the radio wave attenuation rate at a frequency of 77 GHz in the first portion is preferably 1 dB or less, and more preferably 0.5 dB or less. Further, the radio wave attenuation rate at a frequency of 77 GHz in the second portion is preferably 1 dB or less, and more preferably 0.5 dB or less. The radio attenuation at a frequency of 77 GHz in the first and second parts is within the above range, so that the film is more transparent to millimeter waves, which are preferably used in forward surveillance radars for detecting long distances, for example. It's easy to do.

In this embodiment, the radio wave attenuation rate and the radio wave transmittance can be calculated based on the following equations.
Radio wave attenuation rate (dB) = (Attenuation rate without metal-like decorative film)-(Attenuation rate when metal-like decorative film is installed)
Radio wave transmittance (%) = 10 ^a x 100
Here, the index a is "-((radio wave attenuation rate) / 20)".
The radio wave attenuation rate is determined by using a "waveguide type transmission attenuation / shield effect measurement system Model No. SEM02" manufactured by Keycom Co., Ltd. and a vector network analyzer (ME7838A) manufactured by Anritsu Co., Ltd. Can be measured.

In addition, the film of the present embodiment can transmit millimeter waves in both the first portion and the second portion. That is, the radio wave attenuation rate at a frequency of 24 GHz in the first portion is preferably 1 dB or less, and more preferably 0.5 dB or less. Further, the radio wave attenuation rate at a frequency of 24 GHz in the second portion is preferably 1 dB or less, and more preferably 0.5 dB or less. Since the radio wave attenuation rate at the frequency of 24 GHz in the first part and the second part is within the above range, the film more transmits millimeter waves (quasi-millimeter waves) preferably adopted in, for example, peripheral monitoring radar. It's easy to do.

The total light reflectance at an incident angle of 5 ° at a wavelength of 550 nm in the second portion is preferably 35% or more, and more preferably 37% or more. Further, the total light reflectance at an incident angle of 5 ° at a wavelength of 550 nm in the second portion is preferably 75% or less, and more preferably 70% or less. When the total light reflectance is within the above range, the film can easily express a metallic appearance. Further, when the film is provided on the front portion of an automobile or the like equipped with a millimeter-wave radar, it is difficult to see the device such as the radar from the outside, or it is easy to cover up the film so that it cannot be seen. In this embodiment, the total light reflectance was measured using an ultraviolet-visible near-infrared spectrophotometer (UV-3600) manufactured by Shimadzu Corporation. Specifically, when the incident light is incident from a direction inclined by 5 ° from the film normal direction, the total light reflected light (mirror surface reflected light (normally reflected light)) when the aluminum mirror as the reference plate is installed. + The amount of diffused reflected light (excluding mirror-reflected light) is set to 100%, whereas the total light reflected light (mirror-reflected light (normally reflected light)) when the film of the present embodiment is installed is + diffused reflected light. The amount of (excluding mirror-reflected light)) was defined as the total light reflectance (%).

Returning to the description of the entire metal-deposited layer, the method for forming the metal-deposited layer (deposited method) is not particularly limited. As an example, as the vapor deposition method, a conventionally known vacuum vapor deposition method, a sputtering method, a physical vapor deposition method such as an ion plating method, a chemical vapor deposition method, or the like can be appropriately adopted. Among these, it is preferable to provide a metal vapor deposition layer by a vacuum vapor deposition method because of its high productivity. As the vapor deposition conditions, conventionally known conditions can be appropriately adopted based on the desired thickness of the metal vapor deposition layer. The metal material preferably has few impurities and a purity of 99% by weight or more, and more preferably 99.5% by weight or more. Further, the metal material is preferably processed into a granular shape, a rod shape, a tablet shape, a wire shape, or a crucible shape to be used. The heating method for evaporating the metal material is a method of putting the metal material in the rutsubo and performing resistance heating or high frequency heating, a method of performing electron beam heating, and putting the metal material directly on a ceramic board such as boron nitride. A well-known method such as a method of performing resistance heating can be used. The crucible used for vacuum deposition is preferably made of carbon, and may be made of alumina, magnesia, titania, or beryllia.

In the present embodiment, the first metal vapor deposition layer is formed so as to have a predetermined pattern with respect to the anchor layer. Next, a second metal vapor deposition layer is formed so as to cover the anchor layer and the first metal vapor deposition layer.

(Other layers)
In addition to the above-mentioned structure, the film of the present embodiment may be provided with other layers as appropriate. As an example, the film may be provided with an adhesive layer. The adhesive layer is provided to bond the film to the adherend.

The adhesive layer is not particularly limited. For example, the adhesive layer is composed of various adhesives, adhesives, pressure-sensitive adhesives (PSA: Pressure Sensitive Adhesive) and the like. The adhesive is not particularly limited. As an example, the adhesives are acrylic resin-based, urethane resin-based, urethane-modified polyester resin-based, polyester resin-based, epoxy resin-based, ethylene-vinyl acetate copolymer resin (EVA) -based, and vinyl resin-based (vinyl chloride, vinegar). Bi, vinyl chloride-vinegar bi-polymer resin), styrene-ethylene-butylene copolymer resin system, polyvinyl alcohol resin system, polyacrylamide resin system, polyacrylamide resin system, isobutylene rubber, isoprene rubber, natural rubber, SBR, NBR, It is made of resin such as silicone rubber. These resins may be appropriately dissolved in a solvent and used, or may be used without a solvent.

The thickness of the adhesive layer is not particularly limited. As an example, the thickness of the adhesive layer is preferably 10 μm or more, and more preferably 15 μm or more. The thickness of the adhesive layer is preferably 60 μm or less, more preferably 55 μm or less. When the thickness of the adhesive layer is within the above range, the obtained film is further excellent in appearance and adhesiveness at the time of adhesion.

The adhesive layer may be imparted with design by applying a metal pigment. Further, the adhesive layer may be imparted with functionality such as an antistatic effect by blending an antistatic agent or the like. Thereby, the adhesive layer can improve the bonding suitability.

The method of forming the adhesive layer is not particularly limited. As an example, for the adhesive layer, a resin solution constituting the adhesive layer appropriately dissolved in a solvent is applied to a separator described later using a roll coater or the like, and then the separator on which the adhesive layer is formed is metal-deposited. It may be bonded to the layer, or the above resin solution may be applied directly onto the metal vapor deposition layer to form an adhesive layer. Further, as the adhesive layer, an off-the-shelf product in which the adhesive layer is provided on the separator may be used. The method for forming the adhesive layer can be appropriately selected depending on the characteristics of the adhesive and the adhesive to be used.

Returning to the description of the entire film, the OD (Optical Density) value of the film is preferably 1.5 or less, and more preferably 1.3 or less. The OD value is preferably 0.4 or more, and more preferably 0.5 or more. The OD value is a parameter indicating the transparency of light, and can be measured using, for example, a transmission densitometer (X-Rite 361T, manufactured by X-Rite). Since the OD value of the film of the present embodiment is within the above range, it is possible to make it difficult to see the back of the film and to make it difficult for a device such as a radar to be seen from the outside while maintaining millimeter wave transparency. Will be.

As described above, the film of the present embodiment has a first metal vapor deposition layer containing indium and a second metal vapor deposition layer containing indium. The second metal vapor deposition layer includes a first portion that covers the first metal vapor deposition layer and a second portion other than the first portion. Both the first metal-deposited layer and the second metal-deposited layer have radio wave transmission and transmit millimeter waves. Therefore, for example, a predetermined pattern can be formed by the first metal vapor deposition layer, and a film having excellent design can be obtained. Further, since the metal vapor deposition layer has a metallic luster, the millimeter wave radar can be obscured so that it is difficult to see from the outside or cannot be seen from the outside.

FIG. 1 is a schematic cross-sectional view of the film 1 of the present embodiment. In FIG. 1, the anchor layer is omitted. As shown in FIG. 1, the first metal vapor deposition layer 3 is provided so as to form a predetermined pattern on the base material 2 provided with the anchor layer. The first metal vapor deposition layer 3 has a sea-island structure. In other words, the island part is the area where indium exists, and the sea part is the area where indium does not exist. Further, the second metal vapor deposition layer 4 is provided so as to cover the base material 2 provided with the anchor layer and the first metal vapor deposition layer 3. In FIG. 1, the portion P1 is the first portion of the second metal vapor deposition layer 4 that covers the first metal vapor deposition layer 3. The portion P2 is a second portion other than the first portion. In FIG. 1, the second metal vapor deposition layer 4 is drawn in the shape of scattered islands. This is because the suitable second metal vapor deposition layer 4 has a sea-island structure.

Further, the obtained film may be provided with a separator. As the film, a separator provided with an adhesive layer in advance may be used, or an adhesive layer may be formed on the separator and the adhesive layer may be bonded so as to be in contact with the metal vapor deposition layer.

The separator is not particularly limited. As an example, the separator is a plastic film or paper surface-coated with a release agent such as polyethylene terephthalate (PET), polyethylene, polypropylene, a fluorine-based release agent, or a long-chain alkyl acrylate-based release agent.

When the separator is peeled off, the adhesive layer is exposed. The exposed adhesive layer is attached to an adherend (described later) before molding.

(Applied body)
In the film of the present embodiment, an adherend (backing sheet, backer) may be provided on the adhesive layer. The adherend is preferably provided when the film insert method is adopted when manufacturing the metallic molded body described later. The adherend is not particularly limited. As an example, the adherend may be a polymer sheet capable of thermoforming, and may be an ABS sheet, a polyvinyl acrylic sheet, a polypropylene sheet, a polyethylene sheet, a polycarbonate sheet, an A-PET sheet, or a PET-G sheet. , Vinyl chloride (PVC) -based sheet, polyamide-based sheet and the like are preferable.

The thickness of the adherend is not particularly limited. As an example, the thickness of the adherend is preferably 0.05 to 5 mm, more preferably 0.3 to 3 mm from the viewpoint of formability in compression molding and the like.

As the adherend, one having a desired surface treatment may be used. The surface treatment is not particularly limited. As an example, the surface processing includes matte processing, satin processing, embossing processing, hairline processing, various patterns and the like.

As the adherend, an adherend provided with an adhesive layer in advance may be used, or an adhesive layer may be formed on the adherend and bonded so that the adhesive layer is in contact with the metal vapor deposition layer.

After that, the adherend to which the film of the present embodiment is attached is appropriately processed into a three-dimensional shape to produce a molded product (metal-like molded product). The molding method of the metallic molded body is not particularly limited. As an example, the molding method is formed by vacuum forming, TOM (Three dimension Overlay Method) forming or the like. In TOM molding, the film is applied to a pre-prepared adherend and softened by heat to be integrally molded to follow the adherend. On the other hand, in vacuum forming, the film is heated and softened by a heater. Next, the heated film is pressed against a mold having a desired three-dimensional shape while being vacuum-sucked, and is deformed to follow the shape of the three-dimensional molded product.

As described above, the metallic molded body is easily manufactured by the molding process. The above-mentioned film is used as the metal-like molded body that has been molded. Therefore, various designs can be given to the metallic molded body. Further, the metallic molded body can transmit millimeter waves.

The metallic molded body is not particularly limited. As an example, the metal-like molded body is a metal-like vehicle interior / exterior member, a metal-like signboard, a metal-like home appliance, a metal-like amusement product, a metal-like building material, and the like. Among these, the metal-like molded body is preferably used as a metal-like vehicle interior / exterior member. The metal-like vehicle interior / exterior members are not particularly limited. For example, metallic vehicle interior and exterior parts include instrument panel garnishes and ornaments, audio panels, auto air conditioner panels, steering ornaments, door trim ornaments, power window switch bezels, operation knobs, switches and caps or covers, and radiators. Grills, pillar garnishes, back door ornaments, side mirror covers, outer panels, rear spoilers, inside or outside door handles, side visors, wheel covers, motorcycle cowlings, etc. Among these, the metallic vehicle interior / exterior member of the present embodiment is preferably used for the front portion (grill portion in the engine vehicle) of the electric vehicle. That is, the electric vehicle does not require a grill at the front portion of the vehicle. Further, for ADAS (advanced driver assistance system) and automatic driving technology, a millimeter-wave radar is provided on the front part of the automobile. In such a case, since the metallic molded body of the present embodiment can transmit millimeter waves, it is possible to cover up equipment such as a millimeter wave radar while transmitting millimeter waves. As a result, the metallic molded body can adopt various designs for the front part of the electric vehicle instead of the grill part without impairing the function of the millimeter wave radar.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass" and "part" means "part by mass".

<Example 1>
A substrate (thickness 75 μm) made of PMMA was prepared. Using a gravure coater, apply an anchor coating agent solution containing an acrylic polyol and an isocyanate-based coating material to the substrate so that the thickness becomes 1.3 μm after drying, and then dry it at 100 ° C. for 1 minute. And formed an anchor layer. Next, a metal vapor deposition layer (first metal vapor deposition layer) made of indium was formed on the anchor layer by a vacuum vapor deposition method so as to have a predetermined pattern and a thickness of 9 nm (patterning step, details of which will be described later). do.). Next, a metal vapor deposition layer (second metal vapor deposition layer) having a thickness of 9 nm was formed so as to cover the anchor layer and the first metal vapor deposition layer by a vacuum vapor deposition method. Separately from this, a separator (PET film) with an adhesive layer (thickness 25 μm) made of an acrylic adhesive was prepared. The metal vapor deposition layer and the adhesive layer (adhesive layer) are bonded so as to be in contact with each other, the adhesive layer (adhesive layer) is transferred to the metal vapor deposition layer, and then the separator is peeled off to prepare the metal-like decorative film of Example 1. did.

<Examples 2 to 6>
A metal-like decorative film was produced by the same method as in Example 1 except that the thickness, OD value, etc. of the metal-deposited layer were adjusted according to the formulations shown in Table 1.

<Comparative Example 1>
A substrate made of PET (thickness 12 μm) was prepared. A solution containing 5% cellulose acetate butyrate (CAB) was applied to the substrate by a gravure coating method at a coating rate of 0.06 g / m ² ± 0.01 g / m ² , and the temperature was 110 ° C. or higher and 120. It was dried below ° C to form a 50 nm anchor layer. Next, a metal vapor deposition layer made of aluminum was formed on the anchor layer by a vacuum vapor deposition method so as to have a predetermined pattern and a thickness of 20 nm. Separately from this, a separator (PET film) with an adhesive layer (thickness 25 μm) made of an acrylic adhesive was prepared. The metal vapor deposition layer and the adhesive layer (adhesive layer) are bonded so as to be in contact with each other, the adhesive layer (adhesive layer) is transferred to the metal vapor deposition layer, and then the separator is peeled off to prepare the metal-like decorative film of Comparative Example 1. did.

In Table 1, O.D. L. Is an abbreviation for Over Load, which means that the resistance value exceeds the range of the measuring instrument and cannot be measured (the same applies to Table 3). In terms of resistance value, it is a value of ¹⁰⁷ Ω / □ or more. That is, although the films of Examples 1 to 6 are indium films which are metal films, they have high resistance, low conductivity, and indium has a sea-island structure. That is, it can be said that the indium film is a discontinuous film.

For the films obtained in Examples 1 to 6 and Comparative Example 1, the OD value, the thickness, the resistance value, the total light transmittance and the total light transmittance at a wavelength of 550 nm, the radio wave attenuation rate and the radio wave at a frequency of 77 GHz, are according to the following methods. The transmittance, the radio wave attenuation rate and the radio wave transmission rate at a frequency of 24 GHz were evaluated. The results are shown in Tables 1 and 2.

<OD value>
The OD value was measured using a transmission densitometer (X-Rite361T, manufactured by X-Rite).

<Thickness>
The thickness was measured by X-ray fluorescence analysis (XRF). Specifically, the thickness is quantitatively analyzed using a fluorescent X-ray measuring device (ZSX Primus IV, Rigaku Denki Kogyo Co., Ltd.), and the thickness (nm) of the metal vapor deposition film at 5 to 10 points is measured and averaged. Was calculated.

<Resistance value>
The resistance value was measured using a surface resistance measuring device (Lorester GP MCP-T360, Dia Instruments).

<Total light reflectance and total light transmittance at a wavelength of 550 nm>
The total light reflectance and the total light transmittance were measured using an ultraviolet-visible near-infrared spectrophotometer (UV-3600, Shimadzu Corporation). Regarding the total light reflectance, when the incident light is incident from a direction inclined by 5 ° from the film normal direction, the total light reflected light (mirror surface reflected light (normally reflected light)) when the aluminum mirror as the reference plate is installed. ) + Diffused reflected light (excluding mirror reflected light)) is set to 100%, whereas the total light reflected light (mirror reflected light (normal reflected light) + diffused reflected light) when the film of the present invention is installed is set to 100%. The amount of (excluding mirror-reflected light)) was defined as the total light reflectance (%). Regarding the total light transmittance, the amount of incident light in the state where the film is not installed (air; Air only) is set to 100%, and when the film of the present invention is installed, the diffusion component transmitted through the film is used. The amount of emitted light included was defined as the total light transmittance (%).

<Radio wave attenuation and transmittance at frequency 77 GHz and frequency 24 GHz>
The radio wave attenuation rate and the radio wave transmittance were calculated based on the following formulas.
Radio wave attenuation rate (dB) = (Attenuation rate without metal-like decorative film)-(Attenuation rate when metal-like decorative film is installed)
Radio wave transmittance (%) = 10 ^a x 100
Here, the index a is "-((radio wave attenuation rate) / 20)".
The radio wave attenuation rate is determined by using a "waveguide type transmission attenuation / shield effect measurement system Model No. SEM02" manufactured by Keycom Co., Ltd. and a vector network analyzer (ME7838A) manufactured by Anritsu Co., Ltd. It was measured.

As shown in Table 1, in the metallic decorative films of Examples 1 to 6, the radio wave attenuation rate at frequencies 77 GHz and 24 GHz in the first portion and the second portion was almost unchanged, and the radio wave transmittance was high. Therefore, it was found that all of these films can transmit millimeter waves well. Here, in the film of Example 1, in the second part, the value of the total light transmittance is higher than the value of the total light reflectance, and the back of the film is easily visible, so that a device such as a radar can be used. It is easy to see from the outside, and it is suitable for a skeleton-like design that makes it easy to see devices such as radar from the outside. On the other hand, in each of the films of Examples 2 to 6, in the second part, the value of the total light reflectance is higher than the value of the total light transmittance, making it difficult to see the back of the film, such as a radar. It is suitable when a design that makes it difficult for the device to be visually recognized from the outside is required. Since the first portion is a portion where the indium layer is vapor-deposited twice, it is considered that the reflectance is higher than that of the second portion, which is the portion where the indium layer is vapor-deposited once. Therefore, if it is difficult to see the back of the film in the second part, it is considered that it is difficult to see the back of the film in the first part as well. Further, since there is almost no difference in the radio wave attenuation rate between the first portion and the second portion in any of the films of Examples 1 to 6, the films of Examples 1 to 6 are the first metal vapor deposition layer. It was found that the pattern shape formed by the film is not easily restricted and the design is excellent.

FIG. 2 is an external photograph of a molded product obtained by molding the metallic decorative film of Examples 1, 2 and 5. In FIG. 2, from the left, molded bodies (molded bodies F1 to F3) obtained by molding the films of Examples 5, 2 and 1 are shown. In FIG. 2, the inside of the rhombus pattern is the first portion (the portion where the indium layer is vapor-deposited twice), and the outside of the rhombus pattern is the second portion (the portion where the indium layer is vapor-deposited once). As shown in FIG. 2, the molded bodies F1 and F2 of Examples 5 and 2 have a metallic tone not only in the first portion but also in the second portion, making it difficult to visually recognize the back of the film. , It is preferable because it is difficult for devices such as radars to be visually recognized from the outside. In the molded product F3 of the first embodiment, the back of the film is hard to be visually recognized in the first portion, but the back of the film is easily visible in the second portion, and the device such as a radar is easily visible from the outside. It is suitable when a skeleton-like design is required. In the molded bodies F1 and F2 of Examples 5 and 2, not only the reflectance in the first portion in the diamond pattern but also the color of the reflected light is changed by changing the thickness of the second metal vapor deposition layer. You can see that. By changing the thicknesses of the first metal-deposited layer and the second metal-deposited layer in this way, it is possible to freely realize a design pattern having various metallic-like designs. Further, the portion shown by the diamond shape indicates the first portion of the second metal vapor deposition layer, which is a portion covering the first metal vapor deposition layer (first portion P1a, P1b, P1c). On the other hand, the other portion indicates a second portion in which the anchor layer is provided with the second metal vapor deposition layer (second portion P2a, P2b, P2c). As shown in FIG. 2, according to the present invention, a predetermined design (diamond pattern in FIG. 2) can be freely expressed, and its color can be adjusted.

On the other hand, the metal-like decorative film of Comparative Example 1 in which the metal-deposited layer was formed by using aluminum had low radio wave transmission. Therefore, it was found that the film of Comparative Example 1 could not transmit millimeter waves well. It is presumed that the film of Comparative Example 1 has an aluminum-deposited film that is close to a continuous film and cannot transmit millimeter waves satisfactorily.

<Reference example 1>
A substrate (thickness 75 μm) made of PMMA was prepared. Using a gravure coater, apply an anchor coating agent solution containing an acrylic polyol and an isocyanate-based coating material to the substrate so that the thickness becomes 1.3 μm after drying, and then dry it at 100 ° C. for 1 minute. And formed an anchor layer. Next, a solid film of the metal vapor deposition layer made of indium was formed on the anchor layer by a vacuum vapor deposition method so as to have a thickness of 9 nm. As a result, the metallic decorative film of Reference Example 1 was produced.

<Reference Examples 2 to 7>
A metal-like decorative film was produced by the same method as in Reference Example 1 except that the thickness, OD value, etc. of the metal-deposited layer were adjusted according to the formulations shown in Table 3. Here, the films of Reference Examples 1 to 7 correspond to the second portion (the portion where the indium layer is vapor-deposited once) in Examples 1 to 6.

As can be seen from Table 3, the films of Reference Examples 1 to 4 had a low radio wave attenuation rate at frequencies of 77 GHz and 24 GHz with almost no change, and a high radio wave transmittance. Therefore, it was found that all of these films can transmit millimeter waves well.

On the other hand, the films of Reference Examples 5 to 7 had high radio wave attenuation at frequencies of 77 GHz and 24 GHz and low radio wave transmittance. Therefore, it was found that none of these films could transmit millimeter waves well. In the films of Reference Examples 5 to 7, the indium-deposited film no longer exhibits a sea-island structure, and is a film close to a continuous film, and it is presumed that millimeter waves cannot be transmitted well. Therefore, it is considered that the upper limit of the thickness of the metal vapor-deposited film in the second portion, which enables the millimeter wave to be transmitted satisfactorily, is 90 nm. That is, if the thickness of the indium-deposited film is 90 nm or less, it is considered that millimeter waves can be satisfactorily transmitted. The same can be said for the first metal vapor deposition layer.

<Patterning process>
Hereinafter, the patterning steps of Examples 1 to 6 will be described in detail with reference to FIGS. 3 to 5.

First, as shown in FIG. 3A, a base material 2 (thickness 75 μm) made of PMMA was prepared. Next, as shown in FIG. 3B, a gravure coater was used on the base material 2 to apply an anchor coating agent solution in which an acrylic polyol and an isocyanate-based coating material were mixed so as to be 1.3 μm after drying. Then, it was dried at 100 ° C. for 1 minute to form an anchor layer 2a. Using the gravure coater GC shown in FIG. 4, the intermediate film A having the anchor layer 2a formed on the base material 2 is oriented so that the anchor layer 2a side of the intermediate film A faces the roll R side, and the water-soluble primer layer Wp. Was partially formed (see FIG. 3C). As the water-soluble primer, polyvinyl butyral resin was used, and the heat was dried at 100 ° C. for 1 minute to form a water-soluble primer layer Wp. As shown in FIG. 5, the roll R is composed of a convex portion D protruding in a rhombus shape and a concave portion E other than that protruding. In the gravure coater GC, the concave portion E can be filled with the water-soluble primer layer Wp by rotating the roll R while immersing the roll R in the tray WB in which the water-soluble primer layer Wp is stored. At this time, the convex portion D is not filled with the water-soluble primer layer Wp. Then, as shown in FIG. 4, the roll R is rotated by using the gravure coater GC, and the intermediate film A is brought into contact with the roll R and passed while being wound up on the anchor layer 2a. In addition, an intermediate film A'in which the water-soluble primer layer Wp was formed only outside the diamond-shaped portion could be obtained (see FIG. 3C). Then, as shown in FIG. 3D, the first metal (indium) vapor deposition layer 3 was formed on the entire surface of the intermediate film A'. The first metal (indium) vapor-deposited layer 3 actually exhibits a sea-island structure as shown in FIG. 1 instead of a continuous film as shown in FIG. 3D. Then, the entire film was immersed in a vat containing pure water to remove the first metal (indium) vapor-deposited layer 3 on the portion where the water-soluble primer layer Wp was present (water washing step) (see FIG. 3E). .. Then, the second metal (indium) vapor deposition layer 4 was vapor-deposited on the entire surface. The second metal (indium) vapor-deposited layer 4 actually exhibits a sea-island structure as shown in FIG. 1 instead of a continuous film as shown in FIG. 3F. As described above, the metallic decorative film 1 in which the first portion P1 and the second portion P2 are patterned can be produced (see FIG. 3F).

1 Metallic decorative film 2 Base material 2a Anchor layer 3 First metal vapor deposition layer 4 Second metal vapor deposition layer A, A'Intermediate film D Convex part E Concave part F1 to F3 Molded body GC gravure coater P1, P1a, P1b , P1c 1st part P2, P2a, P2b, P2c 2nd part R roll WB tray Wp water-soluble primer layer

Claims (8)

It has a base material, an anchor layer provided on the base material, and a metal vapor deposition layer provided on the anchor layer.
The metal vapor deposition layer is
A first metal vapor deposition layer that forms a predetermined pattern on the anchor layer,
It has a first portion covering the first metal vapor deposition layer and a second metal vapor deposition layer composed of a second portion other than the first portion.
The first metal vapor deposition layer contains indium and contains indium.
The second metal vapor deposition layer is a metal-like decorative film containing indium. The average thickness of the first metal vapor deposition layer is 90 nm or less, and the average thickness is 90 nm or less.
The metal-like decorative film according to claim 1, wherein the average thickness of the second metal-deposited layer is 90 nm or less. The metallic decorative film according to claim 1 or 2, wherein the total light reflectance at an incident angle of 5 ° at a wavelength of 550 nm in the second portion is 35% or more. The first metal vapor deposition layer has a sea-island structure and has a sea-island structure.
The metal-like decorative film according to any one of claims 1 to 3, wherein the second metal-deposited layer has a sea-island structure. The radio wave attenuation rate at a frequency of 77 GHz in the first portion is 1 dB or less.
The metallic decorative film according to any one of claims 1 to 4, wherein the radio wave attenuation rate at a frequency of 77 GHz in the second portion is 1 dB or less. The radio wave attenuation rate at a frequency of 24 GHz in the first portion is 1 dB or less.
The metallic decorative film according to any one of claims 1 to 5, wherein the radio wave attenuation rate at a frequency of 24 GHz in the second portion is 1 dB or less. A metallic molded product using the metallic decorative film according to any one of claims 1 to 6. A metal-like vehicle interior / exterior member using the metal-like molded body according to claim 7.

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