JP2022102747A - Laminate and decorative member - Google Patents

Abstract

To provide a laminate and a decorative member, having good metallic sheen, excellent in transparency, preventing incident light from being absorbed inside a film and reducing an optical loss.SOLUTION: A laminate includes a substrate, a metallic sheen layer formed on the substrate, and an optical regulation layer. The optical regulation layer includes a high refractive index layer having a refractive index of 1.75 or higher. When light of a wavelength 380 to 780 nm is incident on a surface at a side on which the metallic sheen layer of the substrate in the laminate is formed, a transmission Y value being a Y value of transmitted light in a CIE-XYZ colorimetric system is 20% or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminated body and a decorative member.

Conventionally, as a decorative member having electromagnetic wave permeability and metallic luster, a member having a metal layer having an island-like structure, which is obtained by vacuum-depositing a metal such as indium on a base material, is known.

Since such a member has both a high-class appearance derived from its metallic luster and electromagnetic wave transmission, it is suitably used for decoration of a device for transmitting and receiving electromagnetic waves. For example, it is used for housings of mobile phones, smartphones, computers, etc., and decoration of the front part of automobiles. Furthermore, in recent years, with the development of IoT technology, home appliances and household appliances are also equipped with communication functions, and are expected to be applied in a wider range of fields.

Regarding the laminated body, Patent Document 1 includes a transparent base film and a metal layer formed on one side of the transparent base film, and the metal layer is a discontinuous layer made of aluminum or an aluminum alloy. A layer that transmits visible light, the light source is arranged on the side opposite to the metal layer side of the transparent base film, and an electromagnetic wave transmissive half mirror-like film used together with the light source is disclosed.

JP-A-2019-123224

However, it has been found that the electromagnetic wave transmissive half mirror-like film disclosed in Patent Document 1 has a problem that incident light is absorbed in the film and optical loss occurs.
The present invention has been made in view of the above, and an object of the present invention is to provide a laminate and a decorative member having good metallic luster, excellent transparency, and reduced optical loss. ..

As a result of diligent studies to solve the above problems, the present inventors have a substrate, a metallic luster layer formed on the substrate, and an optical adjustment layer, and the optical adjustment layer has a refractive index of 1. By setting the transmission Y value when light having a wavelength of 380 nm to 780 nm is incident on the surface of the laminated body on the side where the metallic luster layer of the substrate is formed, which includes a high refractive index layer of 75 or more, the above-mentioned We have found that the problem can be solved and have completed the present invention.

That is, the present invention is as follows.
[1]
A laminate provided with a substrate, a metallic luster layer formed on the substrate, and an optical adjustment layer.
The optical adjustment layer includes a high refractive index layer having a refractive index of 1.75 or more.
When light having a wavelength of 380 nm to 780 nm is incident on the surface of the laminate on the side where the metallic luster layer of the substrate is formed, the transmitted Y value, which is the Y value in the CIE-XYZ color system of the transmitted light, is 20%. The above-mentioned laminated body.
[2]
When the Y value of the reflected light in the CIE-XYZ color system when light having a wavelength of 380 nm to 780 nm is incident on the surface of the laminate on the side where the metallic luster layer of the substrate is formed is taken as the reflected Y value. , The laminate according to [1], wherein the absorption Y value calculated by the following formula 1 is 35% or less.
Absorption Y value = 100-Transmission Y value-Reflection Y value ... (Equation 1)
[3]
The laminate according to [1] or [2], wherein the metallic luster layer contains a plurality of portions that are discontinuous with each other at least in part.
[4]
The laminate according to [3], wherein the plurality of portions are formed in an island shape.
[5]
The laminate according to any one of [1] to [4], wherein the metallic luster layer contains aluminum or an aluminum alloy.
[6]
The laminate according to any one of [1] to [5], further comprising an inorganic oxide-containing layer between the substrate and the metallic luster layer.
[7]
The laminate according to [6], wherein the inorganic oxide-containing layer is an indium oxide-containing layer.
[8]
The laminate according to any one of [1] to [7], wherein the optical adjustment layer further includes a low refractive index layer.
[9]
The laminate according to any one of [1] to [8], wherein the metallic luster layer has a thickness of 3 nm to 10 nm.
[10]
The laminate according to any one of [1] to [9], wherein the substrate is any of a substrate film, a resin molded substrate, a glass substrate, or an article to which metallic luster should be imparted.
[11]
The laminate according to any one of [1] to [10], further comprising a pressure-sensitive adhesive layer made of a transparent pressure-sensitive adhesive.
[12]
A decorative member comprising an adherend member and the laminate according to [11], wherein the laminate is attached to the adhered member via the adhesive layer.

According to the present invention, it is possible to provide a laminated body and a decorative member having good metallic luster, excellent transparency, and reduced optical loss.

FIG. 1 is a schematic cross-sectional view of a laminated body according to an embodiment of the present invention. FIG. 2 is a diagram showing an electron micrograph (SEM image) of the surface of the metallic luster layer of the laminate according to the embodiment of the present invention. FIG. 3 is a schematic cross-sectional view of a laminated body according to an embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of a laminated body according to an embodiment of the present invention. FIG. 5 is a diagram for explaining a method for measuring the thickness of the metallic luster layer of the laminated body according to the embodiment of the present invention. FIG. 6 is a diagram showing an electron micrograph (TEM image) of a cross section of a laminated body according to an embodiment of the present invention.

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

<Basic configuration>
The laminate according to the embodiment of the present invention is a laminate including a substrate, a metallic luster layer formed on the substrate, and an optical adjustment layer.
The optical adjustment layer includes a high refractive index layer having a refractive index of 1.75 or more.
When light having a wavelength of 380 nm to 780 nm is incident on the surface of the laminate on the side where the metallic luster layer of the substrate is formed, the transmitted Y value, which is the Y value of the CIE-XYZ color system of transmitted light, is 20%. That is all.

FIG. 1 shows a schematic cross-sectional view of a laminated body 100 according to an embodiment of the present invention. Further, FIG. 2 shows an example of an electron micrograph (SEM image) of the surface of the metallic luster layer of the laminate 100 according to the embodiment of the present invention.

As shown in FIG. 1, the laminate 100 includes a substrate 10, a metallic luster layer 12 formed on the substrate 10, and an optical adjustment layer 13. The laminate 100 may further include an inorganic oxide-containing layer 11 between the substrate 10 and the metallic luster layer 12. The metallic luster layer 12 is preferably formed on the inorganic oxide-containing layer 11. In the laminate 100 according to the embodiment of the present invention, the layer provided between the substrate 10 and the metallic luster layer 12 as needed is not limited to the inorganic oxide-containing layer 11 and is another layer. You can also.

It is preferable that the inorganic oxide-containing layer 11 is provided on the lower surface in a continuous state, in other words, without any gaps.

In the form shown in FIG. 1, the metallic luster layer 12 is laminated on the inorganic oxide-containing layer 11. The metallic luster layer 12 includes a plurality of portions 12a. By being laminated on the inorganic oxide-containing layer 11, these portions 12a are separated from each other by a gap 12b at least in a discontinuous state, that is, in at least a part. Since they are separated by the gap 12b, the sheet resistance of these portions 12a becomes large and the interaction with the radio wave decreases, so that the radio wave can be transmitted. Each of these portions 12a is an aggregate of sputtered particles formed by vapor deposition, sputtering, or the like of a metal. When the sputtered particles form a thin film on a substrate such as the substrate 10, the surface diffusivity of the particles on the substrate affects the shape of the thin film.

In addition, the "discontinuous state" as used herein means a state in which they are separated from each other by a gap 12b, and as a result, they are electrically isolated from each other. By being electrically insulated, the sheet resistance becomes large and the desired electromagnetic wave transmission can be obtained. The discontinuous form is not particularly limited, and includes, for example, islands, cracks, and the like.

Here, the "island-like" means that the particles, which are aggregates of spattered particles, are independent of each other, as shown in the electron micrograph (SEM image) of the surface of the metallic glossy layer of the laminated body in FIG. It means a structure in which these particles are spread so as to be slightly separated from each other or partially in contact with each other.

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

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

The laminate according to the embodiment of the present invention is a CIE-XYZ color system of transmitted light when light having a wavelength of 380 nm to 780 nm is incident on the surface of the laminate on the side where the metallic luster layer of the substrate is formed. The transmission Y value, which is the Y value, is 20% or more.

In the laminated body according to the embodiment of the present invention, the transmitted Y value (visual transmittance) is the visual sensitivity in the measurement wavelength range measured by incident on the surface on the metallic gloss layer side of the laminated body and the light intensity of the light source. It is the average transmittance loaded with.
The transmission Y value is preferably 30% or more from the viewpoint of visibility of the design due to transmission. Further, it is preferably 65% or less from the viewpoint of metallic luster appearance.

By setting the transmission Y value in the laminated body to a specific range, it is possible to obtain excellent electromagnetic wave transmission, metallic luster with suppressed coloring, and good transparency. As a result, when the laminated body is attached to the adhered member to form a decorative member, the laminated body can be visually recognized without damaging the surface shape and color of the adhered member even through the laminated body.

Further, the Y value of the reflected light in the CIE-XYZ color system when light having a wavelength of 380 nm to 780 nm is incident on the surface of the laminate according to the embodiment of the present invention on the side where the metallic luster layer of the substrate is formed. It is preferable that the absorption Y value calculated by the following equation 1 is 35% or less when the reflection Y value is used.
Absorption Y value = 100-Transmission Y value-Reflection Y value ... (Equation 1)

In the laminated body according to the embodiment of the present invention, the absorption Y value is preferably 30% or more from the viewpoint of visibility of the design due to transmission. Further, it is preferably 65% or less from the viewpoint of metallic luster appearance.

The reflection Y value of the laminate according to the embodiment of the present invention can be measured by using a spectrocolorimeter, and the transmission Y value can be measured by using an integrating sphere type spectrotransmittance measuring device according to JIS Z 8722.
The reflected Y value and the transmitted Y value of the laminated body can be adjusted by adjusting the film thickness of the metallic luster layer and the film thickness configuration of the optical adjustment layer 13.

The reflection Y value (visual reflectance) is an average reflectance loaded with the luminosity factor in the measurement wavelength range measured by incident on the surface of the laminated body on the side of the metallic luster layer 12 and the light intensity of the light source.
The reflection Y value is preferably 10% or more from the viewpoint of obtaining an appearance showing metallic luster. Further, it is preferably 25% or less from the viewpoint of designability due to transmission.

Further, the electromagnetic wave permeability of the laminated body has a correlation with the sheet resistance.
The amount of radio wave transmission attenuation in the microwave band (28 GHz) is preferably less than 10 [−dB], more preferably less than 5 [−dB], and even more preferably less than 2 [−dB]. .. When the amount of radio wave transmission attenuation in the microwave band (28 GHz) is 10 [−dB] or more, there is a problem that 90% or more of the radio waves are blocked.

The amount of radio wave transmission attenuation and sheet resistance of the laminated body are affected by the material and thickness of the inorganic oxide-containing layer 11 and the metallic luster layer 12.

<Hypokeimenon>
In the laminated body according to the present embodiment, examples of the substrate 10 include resins, glasses, ceramics, and the like from the viewpoint of electromagnetic wave transmission.
The substrate 10 may be a substrate film, a resin molded substrate, a glass substrate, or an article to be imparted metallic luster.
More specifically, examples of the base film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polyvinyl chloride, polycarbonate (PC), cycloolefin polymer (COP), and polystyrene. , Polypropylene (PP), polyethylene, polycycloolefin, polyurethane, acrylic resin (PMMA), ABS and other homopolymers and copolymers can be used.

According to these members, the brilliance and the electromagnetic wave transmission are not affected. However, from the viewpoint of later forming the inorganic oxide-containing layer 11 and the metallic glossy layer 12, it is preferable that the material can withstand high temperatures such as vapor deposition and spatter. Therefore, among the above materials, for example, polyethylene terephthalate and polyethylene na. Phthalates, acrylics, polycarbonates, cycloolefin polymers, ABS, polypropylene and polyurethane are preferred. Of these, polyethylene terephthalate, cycloolefin polymer, polycarbonate, and acrylic resin are preferable because they have a good balance between heat resistance and cost.

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

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

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

It should be noted here that the base film is only an example of an object (base 10) on which the metallic luster layer 12 can be formed. As described above, the substrate 10 includes a resin molded substrate, a glass substrate, and the article itself to which metallic luster should be imparted, in addition to the substrate film as described above. Examples of the resin molded base material and the article to be imparted with metallic luster include structural parts for vehicles, vehicle-mounted products, housings for electronic devices, housings for home appliances, structural parts, mechanical parts, and various automobiles. Examples include parts for household appliances such as parts for electronic equipment, furniture, kitchen goods, medical equipment, parts for building materials, other structural parts and exterior parts.

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

<Inorganic oxide-containing layer>
Further, as shown in FIG. 1 of the laminated body 100 according to the embodiment, an inorganic oxide-containing layer 11 may be further provided between the substrate 10 and the metallic luster layer 12. The inorganic oxide-containing layer 11 is preferably provided in a continuous state, in other words, without gaps. By being provided in a continuous state, the smoothness and corrosion resistance of the inorganic oxide-containing layer 11, the metallic luster layer 12, and the laminate 100 can be improved, and the inorganic oxide-containing layer 11 can be provided without in-plane variation. It also facilitates film formation.

As described above, the inorganic oxide-containing layer 11 is further provided between the substrate 10 and the metallic luster layer 12, that is, the inorganic oxide-containing layer 11 is formed on the substrate 10, and the metallic luster layer 12 is formed on the inorganic oxide-containing layer 11. Is preferable because it facilitates the formation of the metallic luster layer 12 in a discontinuous state. The details of the mechanism are not always clear, but when sputtered particles due to metal deposition or sputtering form a thin film on the substrate, the surface diffusivity of the particles on the substrate affects the shape of the thin film, and the substrate. It is considered that the higher the temperature, the smaller the wettability of the metallic gloss layer to the substrate, and the lower the melting point of the material of the metallic gloss layer, the easier it is to form a discontinuous structure. It is considered that by providing the inorganic oxide-containing layer 11 on the substrate 10, the surface diffusivity of the metal particles on the surface thereof is promoted, and the metallic luster layer 12 can be easily grown in a discontinuous state.

The inorganic oxide-containing layer 11 is preferably an indium oxide-containing layer, and indium oxide (In ₂ O ₃ ) itself can be used. For example, indium tin oxide (ITO) or indium zinc oxidation can be used. Metal-containing materials such as indium (IZO) can also be used. However, ITO and IZO containing a second metal are more preferable because they have high discharge stability in the sputtering process. By using these inorganic oxide-containing layers 11, a continuous film can be formed along the surface of the substrate, and in this case, the metallic luster laminated on the inorganic oxide-containing layer 11 can be formed. The layer 12 is preferable because it tends to have an island-like discontinuous structure, for example. Further, as will be described later, in this case, not only chromium (Cr) or indium (In) but also aluminum, which is difficult to have a discontinuous structure in the metallic luster layer 12, is difficult to apply to this application. Or it becomes easier to include aluminum alloy.

The content rate (content rate = (SnO ₂ / (In ₂ O ₃ + SnO ₂ )) × 100), which is the mass ratio of tin oxide (SnО ₂ ) contained in ITO, is not particularly limited, but is not particularly limited, for example, 2 It is 5.5% by mass to 30% by mass, more preferably 3% by mass to 10% by mass. Further, the content rate (content rate = (ZnO / (In ₂ O ₃ + ZnO)) × 100), which is the mass ratio of zinc oxide (ZnO) contained in IZO, is, for example, 2% by mass to 20% by mass.
The thickness of the inorganic oxide-containing layer 11 is usually preferably 100 nm or less, more preferably 50 nm or less, still more preferably 20 nm or less, from the viewpoint of sheet resistance, electromagnetic wave transmission, and productivity. On the other hand, in order to facilitate the discontinuous state of the laminated metallic luster layer 12, it is preferably 1 nm or more, and in order to ensure the discontinuous state, it is more preferably 3 nm or more. The above is more preferable.

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

The details of the mechanism by which the metallic luster layer 12 becomes discontinuous on the substrate are not always clear, but it is presumed to be roughly as follows. That is, in the process of forming the thin film of the metallic luster layer 12, the ease of forming the discontinuous structure is related to the surface diffusion on the substrate to which the metallic luster layer 12 is applied, and the temperature of the substrate is high, so that the substrate has a high temperature. The smaller the wettability of the metallic luster layer and the lower the melting point of the material of the metallic luster layer, the easier it is to form a discontinuous structure.

Here, the average particle size of the plurality of portions 12a means the average value of the equivalent circle diameters of the plurality of portions 12a. The circle-equivalent diameter of the portion 12a is the diameter of a perfect circle corresponding to the area of the portion 12a.
The equivalent circle diameter of the portion 12a of the metallic luster layer 12 is not particularly limited, but is usually about 10 to 1000 nm. The distance between the portions 12a is not particularly limited, but is usually about 10 to 1000 nm.

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

It is preferable that the metallic luster layer 12 has a relatively low melting point as well as being able to exhibit sufficient brilliance and good transparency. This is because the metallic luster layer 12 is preferably formed by thin film growth using sputtering.
For this reason, the metallic luster layer 12 is suitable for a metal having a melting point of about 1000 ° C. or lower, and preferably contains aluminum or an aluminum alloy.
The metallic luster layer 12 is particularly preferably Al or an alloy thereof for reasons of brilliance, transparency, price and the like. When an aluminum alloy is used, the aluminum content is preferably 50% by mass or more.

The thickness of the metallic luster layer 12 is preferably 3 nm or more, more preferably 4 nm or more, and further preferably 5 nm or more in order to exhibit sufficient brilliance and good transparency. Further, from the viewpoint of facilitating the transmission Y value within a predetermined range, it is preferably 15 nm or less, more preferably 12 nm or less, and further preferably 10 nm or less.
This thickness is also suitable for forming a uniform film with good productivity, and the appearance of the final product, such as a decorative member or a resin molded product, is also good.

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

The sheet resistance of the laminated body 100 is also preferably 100 Ω / □ or more.
From the viewpoint of electromagnetic wave transmission, the sheet resistance is more preferably 200 Ω / □ or more, further preferably 600 Ω / □ or more, still more preferably 1000 Ω / □ or more. The value of this sheet resistance is greatly affected not only by the material and thickness of the metallic luster layer 12, but also by the material and thickness of the inorganic oxide-containing layer 11.

<Optical adjustment layer>
As described above, the laminate according to the embodiment of the present invention includes a substrate, a metallic luster layer formed on the substrate, and an optical adjustment layer, and the optical adjustment layer has a refractive index of 1.75 or more. Includes a high index of refraction layer.
The laminate according to the embodiment of the present invention may have the metallic luster layer 12 and the optical adjustment layer 13 on the substrate 10 in this order as shown in FIG. 3, and the substrate 10 as shown in FIG. The optical adjustment layer 13 and the metallic luster layer 12 may be provided on top in this order.
The laminate according to the embodiment of the present invention includes an optical adjustment layer 13 including a high refractive index layer having a refractive index of 1.75 or more, thereby adjusting the reflection spectrum depending on the wavelength of light and suppressing optical loss. Make it possible.

The optical adjustment layer 13 is preferably a layer made of a metal oxide and / or a metal nitride. The metal element contained in the metal oxide and the metal nitride referred to here includes a metalloid element such as Si. Further, the metal oxide and / or the metal nitride includes a metal oxynitride. Further, the metal oxide may be an oxide of a single metal element (single oxide) or an oxide of a plurality of metal elements (composite oxide). Similarly, the metal nitride may be a nitride of a single metal element (single nitride) or a nitride of a plurality of metal elements (composite nitride).
Examples of the metal element include Ce, Nb, Si, Sb, Ti, Ta, Zr, Zn and the like.

More specifically, as the material of the optical adjustment layer 13, for example, CeO ₂ (2.30), NbO (2.33), Nb ₂ O ₃ (2.15), Nb ₂ O ₅ (2.20). , SiO ₂ (1.46), SiN (2.03), Sb ₂ O ₃ (2.10), TiO ₂ (2.35), Ta ₂ O ₅ (2.10), ZrO ₂ (2.05) ), ZnO (2.10), ZnS (2.30), etc. (The numerical value in parentheses of each of the above materials is the refractive index).
In particular, the optical adjustment layer 13 preferably contains at least one selected from Nb, Si, and Ti, and preferably contains at least one selected from, for example, NbO, SiO ₂ , and TiO ₂ .

The thickness of the optical adjustment layer 13 is preferably 10 nm to 500 nm. From the viewpoint of cost, it is more preferably 300 nm or less, and further preferably 200 nm or less. Further, it is preferably 15 nm or more, more preferably 20 nm or more, and further preferably 30 nm or more.
The thickness of the optical adjustment layer 13 can be measured, for example, by exposing a cross section in the vertical direction (thickness direction) to the surface and using a transmission electron microscope.

The refractive index of the optical adjustment layer 13 is preferably 1.8 or more, more preferably 2.0 or more.

Further, the optical adjustment layer 13 may be a laminated body of layers having different refractive indexes, or may further include a low refractive index layer.
Examples of the low refractive index material forming the low refractive index layer having a refractive index of about 1.35 to 1.55 include silicon oxide and magnesium fluoride, and silicon oxide is preferable. Further, as a high refractive index material forming a high refractive index layer having a refractive index of about 1.80 to 2.40, titanium oxide, niobium oxide, zirconium oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), etc. However, niobium oxide is preferable.
Further, in addition to the low refractive index layer and the high refractive index layer, as a medium refractive index layer having a refractive index of about 1.50 to 1.85, for example, titanium oxide or a mixture of the low refractive index material and the high refractive index material is used. A thin film made of (a mixture of titanium oxide and silicon oxide, etc.) may be formed.

In the laminate according to the embodiment of the present invention, it is preferable that the optical adjustment layer includes a low refractive index layer and a high refractive index layer.

For example, as shown in FIGS. 3 and 4, the laminate 101 and the laminate 102 include a substrate 10, a metallic luster layer 12, and an optical adjustment layer 13, and the optical adjustment layer 13 has a low refractive index layer 13b. , It may be a laminated body with the high refractive index layer 13a. Further, the laminated body 101 and the laminated body 102 may further have a barrier layer and an inorganic oxide-containing layer 11 described later.

For example, as shown in FIG. 3, the laminate 101 includes a substrate 10, a metallic luster layer 12, and an optical adjustment layer 13 in this order, and a first barrier layer is provided between the substrate 10 and the metallic luster layer 12. It may have 14 and an inorganic oxide-containing layer 11. Further, the second barrier layer 15 may be provided on the surface of the optical adjustment layer 13 opposite to the metallic luster layer 12.

Further, as shown in FIG. 4, the laminated body 102 includes a substrate 10, an optical adjustment layer 13, and a metallic luster layer 12 in this order, and a first barrier layer is provided between the substrate 10 and the optical adjustment layer 13. 14 may have. Further, the inorganic oxide-containing layer 11 may be provided between the optical adjustment layer 13 and the metallic luster layer 12. Further, the second barrier layer 15 may be provided on the surface of the metallic luster layer 12 opposite to the optical adjustment layer 13.

The thickness of the low refractive index layer is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, from the viewpoint of adjusting the transmission Y value to a desired range. Further, from the viewpoint of adjusting the transmission Y value to a desired range, it is preferably 200 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less.
The thickness of the high refractive index layer is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, from the viewpoint of adjusting the transmission Y value to a desired range. Further, from the viewpoint of adjusting the transmission Y value to a desired range, it is preferably 200 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less.

The laminated structure of the optical adjustment layer 13 is a two-layer structure consisting of a high refractive index layer having a film thickness of 240 nm to 260 nm and a low refractive index layer having a film thickness of 120 nm to 140 nm from the substrate 10 side; A three-layer structure consisting of a medium refractive index layer, a high refractive index layer having a film thickness of about 60 nm to 70 nm, and a low refractive index layer having a film thickness of 135 nm to 145 nm; a high refractive index layer having a film thickness of 25 nm to 55 nm and a film. A four-layer structure consisting of a low refractive index layer having a thickness of 35 nm to 55 nm, a high refractive index layer having a film thickness of 80 nm to 240 nm, and a low refractive index layer having a film thickness of 120 nm to 150 nm; a low refractive index layer having a film thickness of 15 nm to 30 nm. A high refractive index layer having a film thickness of 20 nm to 40 nm, a low refractive index layer having a film thickness of 20 nm to 40 nm, a high refractive index layer having a film thickness of 240 nm to 290 nm, and a low refractive index layer having a film thickness of 100 nm to 200 nm. The layer structure and the like can be mentioned. The range of the refractive index and the film thickness of the thin film constituting the optical adjustment layer 13 is not limited to the above examples. Further, the optical adjustment layer 13 may be a laminated body of six or more thin films.

The laminated body 100 may include a plurality of optical adjustment layers 13.
For example, some oxides, such as niobium oxide, are reduced when exposed to ultraviolet light while being laminated with an adhesive, and in order to prevent the reducing action, a layer made of silicon oxide is further laminated as a protective layer. You may be doing it.

The laminate according to the embodiment of the present invention may include other layers depending on the application, in addition to the substrate 10, the metallic luster layer 12, and the optical adjustment layer 13.
Examples of other layers include a hard coat layer, a barrier layer, an easy-adhesion layer, an antireflection layer, a light extraction layer, an anti-glare layer and the like.

<Barrier layer>
The laminated body of this embodiment may include a barrier layer. A plurality of barrier layers can be provided.
As described above, for example, the laminate 101 shown in FIG. 3 may have a first barrier layer 14 and an inorganic oxide-containing layer 11 between the substrate 10 and the metallic luster layer 12. Further, the second barrier layer 15 may be provided on the surface of the optical adjustment layer 13 opposite to the metallic luster layer 12.

The first barrier layer 14 and the second barrier layer 15 will be described. The first barrier layer 14 and the second barrier layer 15 may be made of the same material or different materials, respectively. Further, regarding other conditions, the first barrier layer 14 and the second barrier layer 15 can be set independently.

The first barrier layer 14 and the second barrier layer 15 prevent the invasion of _H2O and _O2 from the substrate 10 side and the opposite side (metallic luster layer side), suppress the oxidation of the metallic luster layer 12, and suppress the oxidation of the metallic luster layer 12. It is possible to improve the reliability over time, especially in a high temperature atmosphere.

The first barrier layer 14 and the second barrier layer 15 are selected from the group consisting of at least one oxide of metal and semi-metal, a nitride, a carbide, a nitride, a carbide, a carbide, a carbide and a carbide. Includes at least one species. As the metal, for example, aluminum, titanium, indium, magnesium and the like can be used, and as the metalloid, for example, silicon, bismuth, germanium and the like can be used.

Specifically, for example, ZnO + Al ₂ O ₃ (AZO), indium zinc oxide (IZO), indium tin oxide (ITO), silicon nitride silicon nitride film (SiOCN), silicon nitride film (SiON), silicon nitride film (SiN). ), SiO _X , AlO _X , AlON, TiO _X and the like can be used. Above all, it is preferable to use at least one selected from the group consisting of AZO, ITO, _AlOX and SiO ₂ .

In order to improve the ability of the first barrier layer 14 and the second barrier layer 15 to suppress the oxidation (corrosion) of the metallic luster layer 12 (hereinafter, also referred to as "barrier property"), the network structure in the barrier layer (hereinafter, also referred to as "barrier property") It is preferable to contain carbon and nitrogen so as to make the network structure) dense. In order to further improve the transparency, it is preferable that oxygen is contained. That is, the barrier layer preferably contains at least one metal and metalloid oxynitride carbide.

Further, in order to improve the barrier property, it is preferable that the first barrier layer 14 and the second barrier layer 15 do not easily permeate water vapor. The water vapor permeability of the first barrier layer 14 and the second barrier layer 15 is preferably 5 g / (m ² · day) or less, more preferably 3 g / (m ² · day) or less. It is more preferably 2 g / (m ² · day) or less.

The thicknesses of the first barrier layer 14 and the second barrier layer 15 are not particularly limited, but are preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more in order to improve the barrier property. Further, in order to improve the electromagnetic wave permeability and the metallic luster of the appearance, 100 nm or less is preferable, 80 nm or less is more preferable, and 60 nm or less is further preferable. The thickness of the barrier layer is measured by the method described in the examples.
When the second barrier layer 15 is laminated on the metallic luster layer 12, the gap 12b does not necessarily have to be completely filled.

In addition to the metallic luster layer 12 and the optical adjustment layer 13 described above, other layers may be provided on the laminated body of the present embodiment as long as the effects of the present invention are exhibited. Examples of the other layer include a resin layer such as an adhesive layer, a protective layer (scratch resistant layer) for improving durability such as moisture resistance and scratch resistance, and the like.

<Resin layer>
The laminate of the present embodiment may further include a resin layer. The resin layer may be provided on the surface of the metallic luster layer 12 opposite to the surface on the substrate 10 side, or may be formed on the metallic luster layer.

The resin layer includes an adhesive layer, an adhesive layer for improving the adhesion to the base or the upper ground, a protective layer (scratch resistant layer) for improving durability such as moisture resistance and scratch resistance, and an easy-adhesion layer. The above-mentioned hard coat layer, antireflection layer, light extraction layer, anti-glare layer and the like may be used.
A plurality of resin layers can be provided.

The laminate of the present embodiment may be used by being attached to an adherend member via an adhesive layer. For example, the adherend can be decorated from the inside by attaching the laminate to the transparent adherend through the pressure-sensitive adhesive layer.

When the laminate is attached via the adhesive layer to the surface of the transparent adherend member on the side opposite to the visible side (hereinafter, also referred to as the outside) (hereinafter, also referred to as the inside). The adhesive layer and the metallic luster layer are visually recognized through the wearing member. As the transparent adherend member, for example, a member made of glass or plastic can be used, but the transparent member is not limited to this.

The pressure-sensitive adhesive layer is preferably a layer made of a transparent pressure-sensitive adhesive. The laminate of the present embodiment may be used by being attached to an adherend member via an adhesive layer.

The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited as long as it is a transparent pressure-sensitive adhesive. , And either of the polyether adhesives can be used alone or in combination of two or more. From the viewpoint of transparency, processability, durability and the like, it is preferable to use an acrylic pressure-sensitive adhesive.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but it should be 100 μm or less because thinning it contributes to thinning of the final product configuration and improves visible light transmission, film thickness accuracy, and flatness. It is more preferably 75 μm or less, and even more preferably 50 μm or less.

The transmitted Y value of the entire pressure-sensitive adhesive layer is not particularly limited, but is preferably 10% or more, more preferably 30% or more, and more preferably 50% or more at an arbitrary visible light wavelength measured according to JIS K7361. Is more preferable. The higher the permeation Y value of the pressure-sensitive adhesive layer, the more preferable.

Further, the transparent adhesive constituting the adhesive layer may be colored.
In this case, the colored pressure-sensitive adhesive layer is visually recognized via the metallic luster layer having good transparency, so that the laminate develops the colored metallic luster without changing the color tone of the pressure-sensitive adhesive layer. be able to.

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

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

The adhesion layer is not particularly limited as long as it is a layer that improves the adhesion to the base or the upper ground, but for example, a transparent layer made of SiOx may be provided by sputtering or the like.

<Manufacturing of laminated body>
An example of a method for manufacturing a laminated body will be described. Although not particularly described, it can be produced by the same method when a substrate other than the substrate film is used.

In forming the metallic luster layer 12 and the optical adjustment layer 13, for example, methods such as vacuum deposition and sputtering can be used.

Further, in forming the first barrier layer 14 and the second barrier layer 15, for example, a method such as vacuum deposition or sputtering can be used.

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

<Decorative members>
The decorative member according to the present embodiment includes an adherend member and the above-mentioned laminate, and the laminate is attached to the adhered member via the adhesive layer.

In the decorative member of the present embodiment, the laminated body is attached to the adherend member via the adhesive layer.
Since the laminate of the present embodiment has excellent metallic luster and visibility in order to suppress optical loss, the adherend is decorated while utilizing the design, color and texture provided on the surface of the adhered member as it is. Members can be obtained.

The laminate may be used by being attached to the inner surface of the transparent adherend member. As the transparent adherend member, for example, a member made of glass or plastic can be used, but the transparent member is not limited to this.

When the pressure-sensitive adhesive layer is provided on the laminate, the pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive composition to the surface on which the pressure-sensitive adhesive layer is provided or by transferring the pressure-sensitive adhesive layer formed on the release film.
The pressure-sensitive adhesive composition can be applied using a conventional coater, for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, or the like. The drying temperature can be appropriately adopted, but is preferably 40 ° C. to 200 ° C., more preferably 50 ° C. to 180 ° C., and particularly preferably 70 ° C. to 120 ° C. As the drying time, an appropriate time may be adopted as appropriate. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.

The method of attaching the laminate to the adherend member is not particularly limited, but the laminate can be attached, for example, by vacuum forming. In vacuum forming, the laminated body is stretched while being heated and softened, the space on the side of the adhered member of the laminated body is depressurized, and the space on the opposite side is pressurized as necessary, so that the laminated body is formed on the surface of the adhered member. This is a method of pasting and laminating while forming along a three-dimensional three-dimensional shape.
As the laminated body, the above description can be used as it is.

<Use of laminated bodies and decorative members>
The laminated body and the decorative member of the present embodiment are preferably used for devices, articles, and parts thereof that transmit and receive electromagnetic waves. For example, applications for household goods such as structural parts for vehicles, vehicle-mounted products, housings for electronic devices, housings for home appliances, structural parts, mechanical parts, various automobile parts, electronic device parts, furniture, kitchen supplies, etc. , Medical equipment, building material parts, other structural parts, exterior parts, etc.

More specifically, in the vehicle field, instrument panels, console boxes, door knobs, door trims, shift levers, pedals, glove boxes, bumpers, bonnets, fenders, trunks, doors, roofs, pillars, seats, steering wheels. , ECU box, electrical parts, engine peripheral parts, drive system / gear peripheral parts, intake / exhaust system parts, cooling system parts and the like.

More specifically as electronic devices and home appliances, home appliances such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, TVs, watches, ventilation fans, projectors, speakers, personal computers, mobile phones , Smartphones, digital cameras, tablet PCs, portable music players, portable game machines, chargers, electronic information devices such as batteries, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. A laminate was prepared and evaluated. As the substrate 10, a substrate film was used.

The details of the evaluation method are as follows.
<Transparency characteristics>
With a spectrophotometer U4100 (manufactured by Hitachi High-Technologies Corporation), visible light in the wavelength range of 380 nm to 780 nm is incident on the surface of the laminate on the metallic luster layer side by a standard light source D65, and the transmittance is measured. (Transmission Y value (%)) was obtained. The obtained transmission Y values are shown in Table 1.

<Reflection characteristics>
With a spectrophotometer U4100 (manufactured by Hitachi High-Technologies Corporation), visible light with a wavelength in the range of 380 nm to 780 nm is incident on the surface of the laminate on the metallic luster layer side by a standard light source D65 to measure the reflectance and reflect characteristics. (Reflection Y value (%)) was obtained. The obtained reflection Y values are shown in Table 1.

<Absorption Y value>
Using the transmission Y value and the reflection Y value obtained above, the absorption Y value (%) was calculated by the following formula 1.
Absorption Y value (%) = 100-Transmission Y value-Reflection Y value ... (Equation 1)

<Thickness of metallic luster layer>
Considering the variation in the metallic luster layer, and more specifically, the variation in the thickness of the portion 12a shown in FIG. 2, the average value of the thickness of the portion 12a was taken as the thickness of the metallic luster layer.
The thickness of each portion 12a was set to the thickness of the thickest part in the vertical direction from the substrate 10. Hereinafter, this average value is referred to as "maximum thickness" for convenience. FIG. 6 shows an example of an electron micrograph (TEM image) of a partial cross section of the laminated body.
In obtaining the maximum thickness, first, in the metallic luster layer appearing on the surface of the laminate as shown in FIG. 6, a square region 3 having a side of 5 cm as shown in FIG. 5 is appropriately extracted, and the square region 3 is obtained. A total of five points "a" to "e" obtained by dividing the center lines A and B of the vertical side and the horizontal side of the above into four equal parts were selected as measurement points.
Next, in the cross-sectional image as shown in FIG. 6 at each of the selected measurement points, a viewing angle region including approximately five portions 12a was extracted. Approximately 5 portions 12a at each of these 5 measurement points, that is, the individual thicknesses (nm) of 25 (5 × 5) portions 12a were obtained, and the average value thereof was set to “maximum”. "Thickness".

<Film thickness of the first barrier layer and the second barrier layer>
For the film thickness of the first barrier layer and the second barrier layer, the points showing the maximum heights of the 25 pieces used to determine the film thickness of the metallic luster layer were set as measurement points, and a cross-sectional TEM image was used. It was calculated as follows.
In the cross-sectional TEM image, the intersection with the upper surface of the first barrier layer when a vertical line is drawn from the substrate 10 toward the portion 12a is defined as the intersection point 1, and the intersection with the lower surface of the first barrier layer is defined as the intersection point 2. The distance between the intersection 1 and the intersection 2 in the case was calculated, and the average value of 25 pieces was taken as the thickness of the first barrier layer.
The points showing the maximum heights of the 25 pieces used to determine the film thickness of the metallic glossy layer, and the second barrier layer when a straight line extending in the direction perpendicular to the substrate 10 is drawn from the points. The distance between the intersection 3 and the intersection 4 when the intersection with the upper surface is the intersection 3 and the intersection with the lower surface of the second barrier layer is the intersection 4, and the average value of 25 pieces is the film of the second barrier layer. It was thick.
When the second barrier layer is provided directly on the metallic luster layer, the points showing the maximum heights of the 25 pieces used to determine the thickness of the metallic luster layer and the points perpendicular to the substrate 10 are shown. The average value of 25 pieces of the distance between the straight line extended to the surface and the intersection with the surface of the second barrier layer was taken as the thickness of the second barrier layer.

[Example 1]
As a substrate, an ultraviolet curable resin layer (hard coat layer) having a thickness of 1.5 μm was formed on a PET film 50-U483 (thickness 50 μm) manufactured by Toray Industries, Inc. to obtain a substrate film with an ultraviolet curable resin layer.
First, a Si target is attached to a magnetron sputtering device, and sputtering is performed while introducing a mixed gas of Ar gas and oxygen gas, so that the SiO ₂ layer as the first barrier layer is formed on the ultraviolet curable resin layer at a thickness of 20 nm. Formed.
Next, an ITO target is attached to a magnetron sputtering apparatus, and by sputtering while introducing Ar gas, an ITO layer as an inorganic oxide-containing layer is formed on a SiO ₂ layer having a thickness of 5 nm along the surface of the base film. Formed in.
Next, an aluminum (Al) target was attached to the magnetron sputtering apparatus, and the Al layer as a metallic luster layer was formed on the ITO layer with a thickness of 6 nm by sputtering while introducing Ar gas. The obtained Al layer was a discontinuous layer as shown in FIG.

Next, by attaching an Nb target to the magnetron sputtering device and performing sputtering while introducing a mixed gas of Ar gas and oxygen gas, an NbOx layer (high refractive index of 2.33) is used as an optical adjustment layer on the Al layer. The layer) was formed to a thickness of 180 nm.

Subsequently, an aluminum (Al) target is attached to the magnetron sputtering apparatus, and the AlOx layer as the second barrier layer is formed on the NbOx layer at a thickness of 20 nm by sputtering while introducing a mixed gas of Ar gas and oxygen gas. It was formed and a laminate was obtained.

From the above, the laminate of Example 1, which is a laminate of a base film, an ultraviolet curable resin layer, a first barrier layer, an inorganic oxide-containing layer, a metallic luster layer, an optical adjustment layer, and a second barrier layer, was obtained. .. The characteristics of the obtained laminate were measured by the above method and are shown in Table 1.

<Manufacturing of decorative materials>
As the adherend member, a glass having a thickness of 0.7 mm having a design on the surface was used.
The laminate obtained above was attached to an adherend member using the pressure-sensitive adhesive CS9861UAS (manufactured by Nitto Denko KK) to obtain a decorative member.

[Example 2]
When forming the optical adjustment layer in Example 1, a Si target is attached to the magnetron sputtering device, and sputtering is performed while introducing a mixed gas of Ar gas and oxygen gas, so that SiO is used as a low refractive index layer on the Al layer. _Two layers (refractive index 1.46) are formed with a thickness of 20 nm, then an Nb target is attached to a magnetron sputtering device, and sputtering is performed while introducing a mixed gas of Ar gas and oxygen gas, thereby forming the two layers on the SiO ₂ layer. The laminate of Example 2 was formed in the same manner as in Example 1 except that an NbOx layer (refractive index 2.33) was formed as a high refractive index layer with a thickness of 180 nm and the material and thickness of the optical adjustment layer were changed. Got

[Examples 3 and 4]
The laminated bodies of Examples 3 and 4 were obtained in the same manner as in Example 2 except that the thickness of the NbOx layer was changed to 100 nm and 70 nm, respectively, when the optical adjustment layer was formed in Example 2.

[Example 5]
A base film with an ultraviolet curable resin layer was obtained in the same manner as in Example 1, and a SiO ₂ layer as a first barrier layer was formed on the ultraviolet curable resin layer with a thickness of 20 nm.
Next, by attaching an Nb target to the magnetron sputtering device and performing sputtering while introducing a mixed gas of Ar gas and oxygen gas, an NbOx layer (refractive index 2.33) is formed as a high refractive index layer on the SiO ₂ layer. It is formed to a thickness of 40 nm, then a Si target is attached to a magnetron sputtering device, and sputtering is performed while introducing a mixed gas of Ar gas and oxygen gas, whereby a SiO ₂ layer (refractive index) is formed on the NbOx layer as a low refractive index layer. A refractive index of 1.46) was formed to a thickness of 20 nm to form an optical adjustment layer.
Next, an ITO target was attached to a magnetron sputtering apparatus, and sputtering was performed while introducing Ar gas to form an ITO layer as an inorganic oxide-containing layer on an optical adjustment layer having a thickness of 5 nm.
Next, an aluminum (Al) target was attached to the magnetron sputtering apparatus, and the Al layer as a metallic luster layer was formed on the ITO layer with a thickness of 6 nm by sputtering while introducing Ar gas. The obtained Al layer was a discontinuous layer as shown in FIG.

Subsequently, an aluminum (Al) target is attached to the magnetron sputtering device, and by sputtering while introducing a mixed gas of Ar gas and oxygen gas, an AlOx layer as a second barrier layer is formed on the Al layer at a thickness of 20 nm. It was formed and a laminate was obtained.

From the above, the laminate of Example 5, which is a laminate of a base film, an ultraviolet curable resin layer, a first barrier layer, an optical adjustment layer, an inorganic oxide-containing layer, a metallic luster layer, and a second barrier layer, was obtained. ..

[Example 6]
A laminate of Example 6 was obtained in the same manner as in Example 5 except that the thickness of the NbOx layer was changed to 70 nm when the optical adjustment layer was formed in Example 5.

[Comparative Example 1]
A laminate of Comparative Example 1 was obtained in the same manner as in Example 5 except that the optical adjustment layer was not formed in Example 1.

The characteristics of the obtained laminate were measured by the above method and are shown in Table 1. The numbers in parentheses in Table 1 indicate the film thickness (nm).

The laminates of Examples 1 to 6 and Comparative Example 1 had good metallic luster and excellent transparency.
Further, as is clear from Table 1, the laminates of Examples 1 to 6 include a substrate, a metallic gloss layer formed on the substrate, and an optical adjustment layer, and the optical adjustment layer has a refractive index of 1. Since it contains a high refractive index layer of .75 or more and has a transmission Y value of 20% or more, the absorption Y value is lower than that of Comparative Example 1. This indicates that less light was absorbed in the laminate and optical loss could be reduced.

The present invention is not limited to the above embodiment, and can be appropriately modified and embodied without departing from the spirit of the invention.

The laminate according to the present invention can be used for devices and articles that transmit and receive electromagnetic waves, parts thereof, and the like. For example, applications for household goods such as structural parts for vehicles, vehicle-mounted products, housings for electronic devices, housings for home appliances, structural parts, mechanical parts, various automobile parts, electronic device parts, furniture, kitchen supplies, etc. It can also be used for various applications that require both design and electromagnetic wave transmission, such as medical equipment, building material parts, other structural parts and exterior parts.

100, 101, 102 Laminated body 10 Base 11 Inorganic oxide-containing layer 12 Metallic luster layer 12a Part 12b Gap 13 Optical adjustment layer 13a High refractive index layer 13b Low refractive index layer 14 First barrier layer 15 Second barrier layer

Claims (12)

A laminate provided with a substrate, a metallic luster layer formed on the substrate, and an optical adjustment layer.
The optical adjustment layer includes a high refractive index layer having a refractive index of 1.75 or more.
When light having a wavelength of 380 nm to 780 nm is incident on the surface of the laminate on the side where the metallic luster layer of the substrate is formed, the transmitted Y value, which is the Y value in the CIE-XYZ color system of the transmitted light, is 20%. The above-mentioned laminated body. When the Y value of the reflected light in the CIE-XYZ color system when light having a wavelength of 380 nm to 780 nm is incident on the surface of the laminate on the side where the metallic luster layer of the substrate is formed is taken as the reflected Y value. The laminate according to claim 1, wherein the absorption Y value calculated by the following formula 1 is 35% or less.
Absorption Y value = 100-Transmission Y value-Reflection Y value ... (Equation 1) The laminate according to claim 1 or 2, wherein the metallic luster layer includes a plurality of portions that are discontinuous with each other at least in part. The laminate according to claim 3, wherein the plurality of portions are formed in an island shape. The laminate according to any one of claims 1 to 4, wherein the metallic luster layer contains aluminum or an aluminum alloy. The laminate according to any one of claims 1 to 5, further comprising an inorganic oxide-containing layer between the substrate and the metallic luster layer. The laminate according to claim 6, wherein the inorganic oxide-containing layer is an indium oxide-containing layer. The laminate according to any one of claims 1 to 7, wherein the optical adjustment layer further includes a low refractive index layer. The laminate according to any one of claims 1 to 8, wherein the metallic luster layer has a thickness of 3 nm to 10 nm. The laminate according to any one of claims 1 to 9, wherein the substrate is any of a substrate film, a resin molded substrate, a glass substrate, or an article to which metallic luster should be imparted. The laminate according to any one of claims 1 to 10, further comprising a pressure-sensitive adhesive layer made of a transparent pressure-sensitive adhesive. A decorative member comprising the adherend member and the laminate according to claim 11, wherein the laminate is attached to the adhered member via the adhesive layer.

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