JPWO2020067052A1 - Radio wave transmitter - Google Patents

Abstract

An object of the present invention is to provide a radio wave transmitter having a metallic feeling and a higher saturation, and the subject is a radio wave transmitter having a base material, a metal layer, and a color tone adjusting layer. This is solved by a radio wave transmitter characterized by having a surface resistance of 1.0 × 105 Ω / □ or more.

Description

The present invention relates to a radio wave transmitter and the like.

In recent years, electronic devices that use radio waves, such as smartphones, have become even more familiar. As the material of these electronic devices, for example, the material constituting the surface, it is necessary to use a material having radio wave transmission. In addition, in order to increase the added value of the product, designability is also required.

An example of enhancing the design is to give a metallic feeling by metallic luster or the like. As an existing technology, it has been possible to achieve both a metallic feel and radio wave transmission by using indium. For example, Patent Document 1 discloses a radar device cover in which an indium layer is arranged on a resin base material.

JP-A-2007-093241

In advancing research, the present inventor has focused on the fact that the radio wave transmitter obtained by the above technique has a metallic feel, but has low saturation and poor design.

Therefore, it is an object of the present invention to provide a radio wave transmitter having a metallic feeling and having a higher saturation.

The present inventor has proceeded intensive studies, the substrate is a radio wave transmission body having a metal layer, and the color tone adjusting layer, a surface resistivity of the radio wave transmission body is a 1.0 × 10 ⁵ Ω / □ or more It has been found that the above-mentioned problems can be solved if the radio wave transmitter is characterized by the above. The present inventor has completed the present invention as a result of further research based on this finding.

That is, the present invention includes the following aspects.

Item 1. Substrate, a metal layer, and a radio wave transmission body having a color tone adjusting layer, a radio wave transmission body, wherein the surface resistivity of the radio wave transmission body is 1.0 × 10 ⁵ Ω / □ or more.

Item 2. Item 2. The radio wave transmitter according to Item 1, wherein the color tone adjusting layer includes a metal element-containing layer and / or a metalloid element-containing layer.

Item 3. Item 2. The radio wave transmitter according to Item 1 or 2, wherein the metal layer is an indium-containing metal layer.

Item 4. Item 2. The radio wave transmitter according to any one of Items 1 to 3, wherein the thickness of the metal layer is 70 nm or less.

Item 5. Item 2. The radio wave transmitter according to any one of Items 1 to 4, wherein the color adjustment layer contains silicon, germanium, gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, indium or niobium. ..

Item 6. Item 4. The radio wave transmitter according to any one of Items 1 to 5, wherein the saturation (√ (a ^{* 2} + b ^{* 2)) is 5 or more.}

Item 7. Item 2. The radio wave transmitter according to any one of Items 1 to 6, wherein the brightness L ^{* is 35 or more.}

Item 8. Item 2. The radio wave transmitter according to any one of Items 1 to 7, which has a base material, a metal layer, and a color tone adjusting layer in this order.

Item 9. Item 8. The radio wave transmitter according to Item 8, wherein the elongation recovery rate of the base material is 90 to 100%.

Item 10. Item 8. The radio wave transmitter according to Item 8 or 9, wherein the base material has a tensile strength of 15 to 50 Mpa and a tensile elongation of 300 to 1500%.

Item 11. Item 2. The radio wave transmitter according to any one of Items 8 to 10, wherein the base material is a polyurethane resin base material.

Item 12. Substrate has a color tone adjusting layer and a metal layer in this order, and the surface resistance of the substrate surface and the metal layer-side surface of the radio wave transmission body is 1.0 × 10 ⁵ Ω / □ or more, in claim 1 The radio wave transmitter according to any one of ~ 7.

Item 13. Item 12. The radio wave transmitter according to Item 12, wherein the visible light transmittance of the base material is 80% or more.

Item 14. Item 12. A decorative housing in which the metal layer side surface of the radio wave transmitting body is arranged so as to face the housing.

According to the present invention, it is possible to provide a radio wave transmitter having a metallic feeling and having a higher saturation. Further, in a preferred embodiment of the present invention, it is possible to provide a radio wave transmitter having further excellent design, specifically, reduced color unevenness.

It is a schematic cross-sectional view which shows an example of the radio wave transmitter 1 of this invention. It is the schematic sectional drawing which shows an example of the radio wave transmitter 2 of this invention. FIG. 5 is a schematic cross-sectional view showing an example of a decorative housing in which the metal layer side surface of the radio wave transmitting body 2 of the present invention is arranged so as to face the housing.

In the present specification, the expressions "contains" and "contains" include the concepts of "contains", "contains", "substantially consists" and "consists of only".

In one aspect of the present invention, the radio wave transmitting body has a base material, a metal layer, and a color tone adjusting layer, and the surface resistance of the radio wave transmitting body is 1.0 × 10 ^ 5 Ω / □ or more ( In the present specification, the present invention relates to a radio wave transmitter (sometimes referred to as “the radio wave transmitter of the present invention”) characterized by “characteristics of the present invention”).

Further, in particular, the present invention is a radio wave transmitter having a base material, a metal layer, and a color tone adjusting layer in this order as one aspect of the radio wave transmitter of the present invention, and the surface resistance of the radio wave transmitter is 1.0. × 10 The ^{present invention relates to a radio wave transmitting body having a value of 5} Ω / □ or more (in the present specification, it may be referred to as “radio wave transmitting body 1 of the present invention”).

Further, the present invention is, in particular, a radio wave transmitter having a base material, a color tone adjusting layer, and a metal layer in this order as one aspect of the radio wave transmitter of the present invention, and the surface of the radio wave transmitter on the base material side and the metal. radio wave transmission body surface resistance of the layer surface is equal to or is 1.0 × 10 ⁵ Ω / □ or more (herein, sometimes referred to as "radio wave transmitting member 2 of the present invention".) about ..

The mechanism for imparting color and metallic luster in the radio wave transmitter of the present invention includes (1) the influence of the color tone adjusting layer and the color of the metal layer, (2) the influence of light absorption by the color tone adjusting layer, and ( 3) It is considered that the influence of optical interference generated by the color tone adjusting layer and the metal layer is involved.
Since it has the above-mentioned structure and mechanism, the radio wave transmitter of the present invention is excellent in designability to be visually recognized from the surface on the base material side or the surface on the side opposite to the base material. That is, the radio wave transmitting body 1 of the present invention is excellent in designability to be visually recognized from the surface opposite to the base material, and the radio wave transmitting body 2 of the present invention is excellent in designing property to be visually recognized from the surface on the base material side.
The radio wave transmitter of the present invention will be described below.

<1. Base material>
The base material is not particularly limited as long as it is in the form of a sheet. In the radio wave transmission body 2 of the present invention, as the substrate, as the surface resistivity at the surface of the base material surface in the radio wave transmission body 2 of the present invention is a sheet-like is 1.0 × 10 ⁵ Ω / □ or more As long as it is, there is no particular limitation. The base material is not particularly limited, and examples thereof include a resin base material and a rubber base material.

The resin base material is a base material containing a resin as a material, and is not particularly limited as long as it is in the form of a sheet. The resin base material may contain components other than the resin as long as the effects of the present invention are not significantly impaired. In that case, the total amount of the resin in the resin base material is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and usually less than 100% by mass. Is.

The resin is not particularly limited, and is, for example, a polyester resin (for example, polyethylene terephthalate (PET), polyethylene naphthalate, modified polyester, etc.), a polyolefin resin (for example, a polyethylene (PE) resin, a polypropylene (PP) resin, a polystyrene resin, etc.). Cyclic olefin resin, etc.), vinyl resin (eg, polyvinyl chloride, polyvinylidene chloride, etc.), polyvinyl acetal resin (eg, polyvinyl butyral (PVB), etc.), polyether ether ketone (PEEK) resin, polysalphon (PSF) resin, Examples thereof include polyether sulfone (PES) resin, polycarbonate (PC) resin, polyamide resin, polyimide resin, acrylic resin, and triacetyl cellulose (TAC) resin. Among these, polyester resins are preferable, PET and the like are more preferable, from the viewpoint of transparency and strength.

In addition to these, examples of the resin include resins having excellent elasticity, such as polyurethane resin, polystyrene resin, polyolefin resin, polyester resin, polyamide resin, and polyvinyl chloride resin, and among them, from the viewpoint of elasticity. , Polyurethane resin, polystyrene resin, polyolefin resin, polyester resin, polyamide resin and polyvinyl chloride resin elastomer are preferable, and polyurethane resin (particularly polyurethane elastomer (TPU)) is particularly preferable. In one aspect of the present invention, the resin having excellent elasticity can be preferably used in the radio wave transmitter 1 of the present invention.

The rubber base material is a base material containing rubber as a material and is not particularly limited as long as it is in the form of a sheet. The rubber base material may contain components other than rubber as long as the effects of the present invention are not significantly impaired. In that case, the total amount of rubber in the rubber base material is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and usually less than 100% by mass. Is. The rubber is not particularly limited, and examples thereof include chloroprene rubber, butadiene rubber, styrene / butadiene rubber, nitrile rubber, isoprene rubber, polyisobutylene rubber, acrylic rubber, fluororubber, ethylenepropylene rubber, and silicone rubber. In one aspect of the invention, the rubber substrate can preferably be used in the radio wave transmitter 1 of the present invention.

In one preferred embodiment of the present invention, the characteristics of the present invention, that is, the surface resistivity of the radio wave transmission body is 1.0 × 10 ⁵ Ω / □ or more, from the viewpoint of easy properties to satisfy that, the substrate (the In one aspect of the present invention, a base material having excellent elasticity is desirable as the base material used in the radio wave transmitter 1 of the present invention). In one aspect of the present invention, the surface resistance can be easily adjusted by laminating a metal layer and a color tone adjusting layer on such a base material and then performing a tensile treatment.

As the base material having excellent extensibility, a base material having one or two or more (preferably all) characteristics in the characteristic group consisting of elongation recovery rate, tensile strength, and tensile elongation is preferable. Used for.

The elongation recovery rate is preferably 90 to 100%, more preferably 92 to 98%, still more preferably 94 to 96%, from the viewpoint of the characteristics of the present invention, the design after the tensile treatment, and the like.

The elongation recovery rate can be measured as follows.
First, a rectangular sample is used as a base material, and the length (L ₀ ) in the length direction is measured. The sample is placed on a measuring machine (manufactured by Shimadzu Corporation, Autograph AGS-1kNX, or an equivalent product thereof) and stretches to an elongation rate of 25% at a tensile speed of 300 mm / min. After that, the stretching is stopped, the sample is removed from the testing machine, and the stretching is recovered for 1 minute. The base material length L ₂ after elongation recovery is measured, and the elongation recovery rate is calculated from the following formula.
Elongation recovery rate (%) = ((L _1- L ₂ ) / (L _1- L ₀ )) x 100
In addition, L ₁ is the length at the time of 25% extension (= 1.25 × L ₀ ).

The tensile strength is preferably 15 to 50 MPa, more preferably 25 to 48 MPa, from the viewpoints of the characteristics of the present invention, the point that it can withstand the tensile treatment, the ease of metal film forming by roll-to-roll, and the like. More preferably, it is 30 to 45 MPa.

The tensile strength (tensile strength) can be measured according to JIS K7311 for a thermoplastic polyurethane elastomer base material, JIS K6251 for a rubber base material, and JIS K7127 for other resin base materials.

The tensile elongation is preferably 300 to 1500%, more preferably 400 to 1000%, from the viewpoints of the characteristics of the present invention, the point that it can withstand the tensile treatment, the ease of metal film forming by roll-to-roll, and the like. It is more preferably 500 to 700%.

The tensile elongation can be measured according to JIS K7311 for a thermoplastic polyurethane elastomer base material, JIS K6251 for a rubber base material, and JIS K7127 for other resin base materials.

The base material (preferably, the base material in the radio wave transmitting body 2 of the present invention) is preferably a transparent base material from the viewpoint of visibility of the design.
The visible light transmittance of the base material is preferably 80% or more, more preferably 90% or more, still more preferably 95% or more. Visible light transmittance is usually 100% or less. The visible light transmittance of the base material further improves the designability of the radio wave transmitter 2 of the present invention to be visually recognized from the base material side surface.
The visible light transmittance of the base material is an average value of the measured values obtained when the transmittance in the wavelength range of 380 nm to 780 nm is measured at 5 nm intervals. The visible light transmittance can be measured using, for example, a spectrophotometer (for example, "U-4100" manufactured by Hitachi High-Tech). An integrating sphere can be used as the detector.

The thickness of the base material is not particularly limited. The thickness of the base material is, for example, 5 to 500 μm. From the viewpoint of productivity, for example, in the radio wave transmitter 1 of the present invention, the thickness is preferably 10 to 200 μm, more preferably 23 to 125 μm, and further preferably 25 to 100 μm. Alternatively, from the viewpoint of productivity, for example, in the radio wave transmitter 2 of the present invention, the thickness is preferably 10 to 200 μm, more preferably 23 to 125 μm, and further preferably 25 to 100 μm.

The layer structure of the base material is not particularly limited. The base material may be composed of one type of base material alone, or may be a combination of two or more types of base materials.

<2. Metal layer>
The metal layer is a layer that is arranged directly on the substrate or via another layer. In the radio wave transmitter 1 of the present invention, the metal layer is a layer arranged between the base material and the color tone adjusting layer. In the radio wave transmitter 2 of the present invention, the metal layer is a layer arranged on the surface of the color tone adjusting layer opposite to the base material.

The metal layer is not particularly limited as long as it is a layer containing metal as a material. The metal layer may contain components other than metal as long as the effects of the present invention are not significantly impaired. In that case, the amount of metal in the metal layer is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and usually less than 100% by mass.

The metal constituting the metal layer is not particularly limited, and examples thereof include titanium, aluminum, copper, iron, silver, gold, platinum, chromium, nickel, molybdenum, gallium, zinc, tin, niobium, and indium. Among these, aluminum, copper, silver, gold, platinum, titanium, indium and the like are preferable, and aluminum, copper, titanium, indium and the like are more preferable from the viewpoint of adjusting the color tone or the brightness. Can be mentioned. The metal may be one kind alone or a combination of two or more kinds (for example, an alloy).

In one preferred embodiment of the present invention, the characteristics of the present invention described later, that is, the surface resistivity of the radio wave transmission body is 1.0 × 10 ⁵ Ω / □ or more, from the viewpoint of characteristics of an indium-containing metal as a metal layer It is desirable to adopt layers. In one aspect of the present invention, the surface resistance can be easily adjusted by adopting the indium-containing metal layer.

The indium-containing metal layer is not particularly limited as long as it is a layer containing indium as a material. The indium-containing metal layer may contain components other than indium as long as the effects of the present invention are not significantly impaired. In that case, the amount of indium element in the indium-containing metal layer is, for example, 25% by mass or more, preferably 50% by mass or more, more preferably 75% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass. As described above, it is particularly preferably 95% by mass or more, very preferably 99% by mass or more, and usually less than 100% by mass. By setting the indium content to 25% by mass or more, the durability can be further improved.

The indium-containing metal layer may be composed of indium or an alloy containing indium, or may be composed of a mixture thereof.

Examples of the metal capable of forming an alloy with indium include tin, lead, zinc, bismuth and the like. When an alloy containing indium is used, it is preferable that the melting point is 500 ° C. or lower and the indium content is 25% or more from the viewpoint of durability.

The metal layer preferably has an island structure.

The area of the island-shaped structure is preferably 2000 nm ² or more and 1 μm ² or less. When it is at least the above lower limit value, it is possible to obtain a laminate having a more favorable metallic luster and metallic feeling (in particular, when an indium metal layer is adopted, a metallic luster peculiar to indium). When it is equal to or less than the above upper limit value, the high frequency electromagnetic wave transmission becomes even better.

Area of the island-like structure is 2500 nm ² or more, and more preferably 250000Nm ² or less.

From the viewpoint of further improving high-frequency electromagnetic wave transmission, the metal layer preferably has grooves. When the groove is provided, the width of the groove is not particularly limited, but is preferably 0.5 nm or more, more preferably 1 nm or more, preferably 100 nm or less, and more preferably 50 nm or less. When the width of the groove is at least the above lower limit, the high frequency electromagnetic wave transmission becomes even better. When the width of the groove is not more than the upper limit, the metal feeling is further improved.

The thickness of the metal layer in the groove is preferably 1 nm or less, and is preferably substantially 0 nm. The island-shaped structure can be observed using, for example, a scanning electron microscope, and the thickness of the metal layer in the groove can be measured by observing the cross section using, for example, a scanning electron microscope.

The thickness of the metal layer is not particularly limited, but is, for example, 1 to 500 nm. From the viewpoint of further enhancing the saturation of the color, the thickness is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 15 nm or more, still more preferably 25 nm or more, still more preferably 35 nm or more. The thickness is preferably 70 nm or less from the viewpoint of radio wave transmission. The range of the thickness can be set by arbitrarily combining the upper limit and the lower limit, but is typically, for example, 5 to 70 nm, preferably 10 to 50 nm, and more preferably 15 to 30 nm.

When the metal layer contains indium, the thickness of the indium-containing metal layer is not particularly limited, but is, for example, 1 to 500 nm. The thickness of the radio wave transmitter 1 of the present invention is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 15 nm or more, still more preferably 25 nm or more, from the viewpoint of further enhancing the color saturation. More preferably, it is 35 nm or more. The thickness is preferably 70 nm or less, more preferably 50 nm or less, still more preferably 30 nm or less, still more preferably 20 nm or less, from the viewpoint of further enhancing the color saturation in the radio wave transmitter 2 of the present invention. More preferably, it is 15 nm or less. In this case, the lower limit of the thickness is, for example, 5 nm, 10 nm, and 15 nm. The thickness is preferably 70 nm or less from the viewpoint of radio wave transmission. The range of the thickness can be set by arbitrarily combining the upper limit and the lower limit, but is typically, for example, 5 to 70 nm, preferably 10 to 50 nm, and more preferably 15 to 30 nm.

When the metal layer is a metal layer containing no indium, the thickness of the metal layer is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, still more preferably, from the viewpoint of ease of production, metal feeling, and the like. Is 40 nm or more, more preferably 60 nm or more. The thickness is preferably 70 nm or less from the viewpoint of radio wave transmission. The range of the thickness can be set by arbitrarily combining the upper limit and the lower limit, but is typically, for example, 5 to 60 nm, preferably 10 to 50 nm, and more preferably 20 to 40 nm.

The thickness of the metal layer can be determined by fluorescent X-ray analysis. Specifically, using a scanning fluorescent X-ray analyzer (for example, Rigaku scanning fluorescent X-ray analyzer ZSX PrimusIII + or an equivalent product), the acceleration voltage is 50 kV, the acceleration current is 50 mA, and the integration time is 60 seconds. Analyze as. The X-ray intensity of the Kα ray of the metal component to be measured is measured, and the intensity at the background position is also measured in addition to the peak position so that the net intensity can be calculated. From the calibration curve created in advance, the measured strength value can be converted into the thickness. The same sample is analyzed 5 times, and the average value is taken as the average thickness.

The layer structure of the metal layer is not particularly limited. The metal layer may be a single layer composed of one layer, or may be a plurality of layers having the same or different compositions. Further, the surface of the metal layer may be formed of a film such as an oxide film on one or both of the two main surfaces.

<3. Color tone adjustment layer>
The color tone adjusting layer is a layer arranged directly on the base material or via another layer. In the radio wave transmitting body 1 of the present invention, the color tone adjusting layer is a layer arranged on the metal layer on the side opposite to the base material side. In the radio wave transmitting body 2 of the present invention, the color tone adjusting layer is a layer arranged between the base material and the metal layer. The color tone adjusting layer preferably includes a metal element-containing layer and / or a metalloid element-containing layer. In this case, the color adjustment layer preferably contains silicon, germanium, gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, indium or niobium, and more preferably silicon.

The color tone adjusting layer preferably contains a metalloid element-containing layer from the viewpoint of radio wave transmission.

The color tone adjusting layer preferably does not contain a pigment and / or a dye in the radio wave transmitter 2 of the present invention. When no pigment or dye is contained, the adhesion between the color tone adjusting layer and the base material and the metal layer can be improved.

When the color tone adjusting layer contains a pigment, preferably, in the radio wave transmitter 2 of the present invention, the content of the pigment in 100% by weight of the color tone adjusting layer is preferably 0.1% by weight or less, more preferably 0. It is 01% by weight or less. When the color tone adjusting layer contains a dye, preferably, in the radio wave transmitter 2 of the present invention, the content of the dye in 100% by weight of the color tone adjusting layer is preferably 0.1% by weight or less, more preferably 0. It is 01% by weight or less. When the content of the pigment or dye is not more than the above upper limit, the adhesion between the color tone adjusting layer and the base material and the metal layer can be improved.

The metal element-containing layer and the metalloid element-containing layer will be described in detail below.

<3-1. Metal element-containing layer>
The metal element-containing layer is arranged on the substrate either directly or via another layer. In the radio wave transmitter 1 of the present invention, the metal element-containing layer is arranged on the metal layer on the side opposite to the base material side. In the radio wave transmitter 2 of the present invention, the metal element-containing layer is arranged between the base material and the metal layer.

The metal element-containing layer is not particularly limited as long as it is a layer containing a metal as a material. The metal element-containing layer may contain components other than metal as long as the effects of the present invention are not significantly impaired. In that case, the amount of metal in the metal element-containing layer is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and usually less than 100% by mass. be.

The metal constituting the metal element-containing layer is not particularly limited, and examples thereof include gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, indium, niobium, chromium, and nickel. Among these, gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, indium, niobium and the like are preferable from the viewpoint of radio wave transmission.

The metal may be one kind alone or a combination of two or more kinds.

The metal element-containing layer may be composed of a metal or alloy composed of the above metal elements, may be composed of a compound containing the above metal elements, or may be composed of a mixture thereof. Examples of the compound containing a metal element include oxides, nitrides, and nitride oxides. In one aspect of the present invention, the color tone adjusting layer contains a metal oxide and / or a metalloid oxide described later. As a result, the absorption of light in the visible light region of the color tone adjusting layer can be suppressed, so that a radio wave transmitter with higher saturation can be obtained.

The oxide is, for example _{, a number satisfying MO X} [in the formula, X is the formula: n / 100 ≦ X <n / 2 (n is the valence of the metal), and M is a metal element. ], Examples thereof include compounds represented by.

The nitride is, for example _{, a number satisfying MN y} [in the formula, Y is the formula: n / 100 ≦ Y ≦ n / 3 (n is the valence of the metal), and M is a metal element. ], Examples thereof include compounds represented by.

Examples of the nitride oxide include MO _X N _y [in the formula, X and Y are n / 100 ≦ X, n / 100 ≦ Y, and X + Y <n / 2 (n is the valence of the metal). And M is a metal element. ], Examples thereof include compounds represented by.

The oxidation number X of the oxide or nitride oxide can be calculated as follows, for example. The cross section of the layer containing MO _x or MO _x N _y is elementally analyzed by FE-TEM-EDX (for example, "JEM-ARM200F" manufactured by JEOL Ltd. or an equivalent product thereof), and contains _{MO x} or MO _x N _y. The valence of oxygen atoms can be calculated by calculating X from the elemental ratio of M and O per area of the cross section of the layer.

The nitrogen oxide number Y of the nitride or nitride oxide can be calculated as follows, for example. The cross section of the layer containing MN _y or MO _x N _y is elementally analyzed by FE-TEM-EDX (for example, "JEM-ARM200F" manufactured by JEOL Ltd. or its equivalent) and contains _{MN y} or MO _x N _y. The valence of nitrogen atoms can be calculated by calculating Y from the elemental ratio of M and N per area of the cross section of the layer.

The metal element-containing layer is a layer containing MO _x or MN _y (in _{the case of MO x} , M indicates an n-valent metal, and x indicates a number of 0 or more and less than n / 2. In the case of _{MN y, it indicates a number.} , M represents an n-valent metal, and y represents a number of 0 or more and less than n / 3).

The thickness of the metal element-containing layer is not particularly limited, and is, for example, 1 to 200 nm. The thickness is preferably 1 to 100 nm, more preferably 3 to 50 nm, and further preferably 5 to 30 nm from the viewpoint of color adjustment, radio wave transmission, and the like.

The thickness of the metal element-containing layer can be determined by fluorescent X-ray analysis. Specifically, using a scanning fluorescent X-ray analyzer (for example, Rigaku scanning fluorescent X-ray analyzer ZSX PrimusIII + or an equivalent product), the acceleration voltage is 50 kV, the acceleration current is 50 mA, and the integration time is 60 seconds. Analyze as. The X-ray intensity of the Kα ray of the metal component to be measured is measured, and the intensity at the background position is also measured in addition to the peak position so that the net intensity can be calculated. From the calibration curve created in advance, the measured strength value can be converted into the thickness. The same sample is analyzed 5 times, and the average value is taken as the average thickness.

The layer structure of the metal element-containing layer is not particularly limited. The metal element-containing layer may be a single layer composed of one layer, or may be a plurality of layers having the same or different compositions. Further, the surface of the metal element-containing layer may be formed of a film such as an oxide film on one or both of the two main surfaces.

<3-2. Metalloid element-containing layer>
The metalloid element-containing layer is arranged directly on the substrate or via another layer. In the radio wave transmitter 1 of the present invention, the metalloid element-containing layer is arranged on the metal layer on the side opposite to the base material side. In the radio wave transmitter 2 of the present invention, the metalloid element-containing layer is arranged between the base material and the metal layer.

The metalloid element-containing layer is not particularly limited as long as it is a layer containing a metalloid element as a material. The metalloid element-containing layer may contain components other than the metalloid element as long as the effects of the present invention are not significantly impaired. In that case, the content of the semi-metal element in the semi-metal element-containing layer is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 75% by mass or more, still more preferably 80% by mass or more, still more preferably. Is 90% by mass or more, particularly preferably 95% by mass or more, very preferably 99% by mass or more, and usually less than 100% by mass.

The metalloid element constituting the metalloid element-containing layer is not particularly limited, and examples thereof include silicon, germanium, antimony, boron, phosphorus, and bismuth. Among these, silicon, germanium and the like are preferably mentioned, and silicon is more preferable, from the viewpoint of radio wave transmission and the like.

It is preferable that the metalloid element contained most in the metalloid element-containing layer is silicon or germanium.

The metalloid element may be used alone or in combination of two or more.

The metalloid-containing layer may be composed of a metalloid or an alloy composed of the above-mentioned metalloid element, may be composed of a compound containing the above-mentioned metalloid element, or may be composed of a mixture thereof. .. Examples of the compound containing a metalloid element include oxides, nitrides, and nitride oxides. In one aspect of the present invention, the color tone adjusting layer contains the above-mentioned metal oxide and / or metalloid oxide. As a result, the absorption of light in the visible light region of the color tone adjusting layer can be suppressed, so that a radio wave transmitter with higher saturation can be obtained.

As the oxide, for example, MO _X [in the formula, X is a number satisfying the formula: n / 100 ≦ X <n / 2 (n is a valence of a metalloid), and M is a metalloid element. .. ], Examples thereof include compounds represented by.

As the above-mentioned nitride, for example, MN _y [in the formula, Y is a number satisfying the formula: n / 100 ≦ Y ≦ n / 3 (n is a valence of a metalloid), and M is a metalloid element. .. ], Examples thereof include compounds represented by.

Examples of the nitride oxide include MO _X N _y [in the formula, X and Y are n / 100 ≦ X, n / 100 ≦ Y, and X + Y <n / 2 (n is a metalloid valence). ), And M is a metalloid element. ], Examples thereof include compounds represented by.

The oxidation number X of the oxide or nitride oxide can be calculated as follows, for example. The cross section of the layer containing MO _x or MO _x N _y is elementally analyzed by FE-TEM-EDX (for example, "JEM-ARM200F" manufactured by JEOL Ltd. or an equivalent product thereof), and contains _{MO x} or MO _x N _y. The valence of oxygen atoms can be calculated by calculating X from the elemental ratio of M and O per area of the cross section of the layer.

The nitrogen oxide number Y of the nitride or nitride oxide can be calculated as follows, for example. The cross section of the layer containing MN _y or MO _x N _y is elementally analyzed by FE-TEM-EDX (for example, "JEM-ARM200F" manufactured by JEOL Ltd. or its equivalent) and contains _{MN y} or MO _x N _y. The valence of nitrogen atoms can be calculated by calculating Y from the elemental ratio of M and N per area of the cross section of the layer.

When metalloid element-containing layer of the MO _x or MN layer containing _y (MO _x is, M represents an n-valent metal or semimetal, and x is .mn _y indicating the number from 0 to less than n / 2 In the case of, M indicates an n-valent metal or a metalloid, and y indicates a number of 0 or more and less than n / 3). In this case, M is preferably silicon or germanium, respectively.

_{When M in MO x} is silicon from the viewpoint of increasing the saturation of color, X preferably represents a number less than 1, more preferably 0.5 or less, and more preferably 0.5. More preferably less than. When _{M in MN y} is silicon, Y preferably represents a number of 4/3 or less.

The thickness of the metalloid element-containing layer is not particularly limited, but is, for example, 1 to 150 nm. The thickness is preferably 1 to 100 nm, more preferably 3 to 50 nm, and further preferably 5 to 30 nm from the viewpoint of increasing the saturation of the color.

The thickness of the metalloid element-containing layer can be determined by fluorescent X-ray analysis. Specifically, using a scanning fluorescent X-ray analyzer (for example, Rigaku scanning fluorescent X-ray analyzer ZSX PrimusIII + or an equivalent product), the acceleration voltage is 50 kV, the acceleration current is 50 mA, and the integration time is 60 seconds. Analyze as. The X-ray intensity of the Kα ray of the metal component to be measured is measured, and the intensity at the background position is also measured in addition to the peak position so that the net intensity can be calculated. From the calibration curve created in advance, the measured strength value can be converted into the thickness. The same sample is analyzed 5 times, and the average value is taken as the average thickness.

The layer structure of the metalloid element-containing layer is not particularly limited. The metalloid element-containing layer may be a single layer composed of one layer, or may be a plurality of layers having the same or different compositions. Further, the surface of the metalloid element-containing layer may be formed of a film such as an oxide film on one or both of the two main surfaces.

<4. Characteristics>
Radio wave transmission body of the present invention is characterized in that the surface resistance of 1.0 × 10 ⁵ Ω / □ or more. Particularly, in the radio wave transmission body 2 of the present invention, wherein a surface resistance of the substrate surface and the metal layer surface is 1.0 × 10 ⁵ Ω / □ or more. As a result, good radio wave transmission can be exhibited.

^{The surface resistance is preferably 1.0 × 10 5 to} 1.0 × 10 ¹² Ω / □, more preferably 1.0 × 10 ^{8 to} 1.0 × 10 ¹⁰ Ω / from the viewpoint of radio wave transmission and the like. □. The surface resistance can be measured by a four-terminal method using a surface resistance meter (manufactured by MITUBISHI CHEMICAL ANALYTECH, trade name: Loresta-EP, or trade name: Hiresta-UP).

In the radio wave transmitter 2 of the present invention, the surface resistance on the surface on the metal layer side is preferably 1.0 × 10 ^{5 to} 1.0 × 10 ¹² Ω / □, more preferably 1 from the viewpoint of radio wave transmission and the like. .0 × 10 ^{8 to} 1.0 × 10 ¹⁰ Ω / □.

In the radio wave transmitter 2 of the present invention, the surface resistance on the surface on the substrate side is preferably 1.0 × 10 ^{5 to} 1.0 × 10 ¹⁸ Ω / □, more preferably 1 from the viewpoint of radio wave transmission and the like. .0 × 10 ^{8 to} 1.0 × 10 ¹⁶ Ω / □, more preferably 1.0 × 10 ^{11 to} 1.0 × 10 ¹⁵ Ω / □.

The radio wave transmitter of the present invention has a higher saturation. The saturation is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, and even more preferably 30 or more. The upper limit of saturation is not particularly limited, and is, for example, 100, 70, 50. The saturation can be calculated from the formula √ (a ^{* 2} + b ^{* 2 ) from L *} , a ^* , and b ^* measured by a spectrophotometer. (L ^* , a ^* , b ^* ) can be measured using a spectrophotometer (Spectrophotometer U-4100 manufactured by Hitachi, Ltd. or its equivalent) under the condition of 90-degree incident and 90-degree light reception.

The radio wave transmitter of the present invention preferably has a ^{higher brightness L * from the viewpoint of metallic feeling.} The brightness L ^* is preferably 35 or more, more preferably 40 to 80, and even more preferably 45 to 70.

The elongation recovery rate of the radio wave transmitter of the present invention (preferably the radio wave transmitter 1 of the present invention) is preferably 90 to 100%, more preferably 92 to 98%, still more preferably 94 to 96%. be.
The elongation recovery rate can be measured in the same manner as the elongation recovery rate of the base material.

The tensile strength of the radio wave transmitting body of the present invention (preferably the radio wave transmitting body 1 of the present invention) is preferably 15 to 50 MPa, more preferably 25 to 48 MPa, and further preferably 30 to 45 MPa.

The tensile elongation of the radio wave transmitter of the present invention (preferably the radio wave transmitter 1 of the present invention) is preferably 300 to 1500%, more preferably 400 to 1000%, still more preferably 500 to 700%. be.

The tensile strength and tensile elongation are measured according to JIS K7311 when the radio wave transmitter of the present invention has a thermoplastic polyurethane elastomer base material, JIS K6251 when it has a rubber base material, and JIS K7127 when it has another resin base material. The value to be used.

<5. Manufacturing method>
In the case of the radio wave transmitter 1 of the present invention, for example, the radio wave transmitter of the present invention has a step of forming a metal layer on a base material and a color tone adjusting layer formed on the metal layer on the side opposite to the base material. It can be obtained by a method including the steps of Further, for example, in the case of the radio wave transmitter 2 of the present invention, a method including a step of forming a color tone adjusting layer on the base material and a step of forming a metal layer on the color tone adjusting layer on the side opposite to the base material. Can be obtained by

Although not particularly limited, the formation can be performed by, for example, a sputtering method, a vacuum vapor deposition method, an ion plating method, a chemical vapor deposition method, a pulse laser deposition method, or the like. Among these, the sputtering method is preferable from the viewpoint of film thickness controllability.

The sputtering method is not particularly limited, and examples thereof include DC magnetron sputtering, high frequency magnetron sputtering, and ion beam sputtering. Further, the sputtering apparatus may be a batch system or a roll-to-roll system.

As described above, in one aspect of the present invention, the surface resistance having the characteristics of the present invention can be easily adjusted by laminating a metal layer and a color tone adjusting layer on a base material having excellent elasticity and then performing a tensile treatment. It is possible. The specific method of this tensile treatment is not particularly limited as long as the characteristics of the present invention can be obtained. For example, in the roll-to-roll method, a nip roll type, a clover roll type, and a continuous stretching type are used. Etc. can be mentioned.

<6. Uses>
The radio wave transmitter of the present invention is excellent in design and radio wave transmission, and can be used as a material and a housing for various electronic devices that use radio waves. Examples of electronic devices include smartphones, tablet terminals, notebook computers, and the like.

<7. Decorative housing ＞
In one aspect of the present invention, the present invention relates to a decorative housing in which the surface of the radio wave transmitting body 2 of the present invention on the metal layer side is arranged so as to face the housing. That is, the present invention relates to a decorative housing in which a base material, a color tone adjusting layer, a metal layer, and a housing are laminated in this order.
By arranging the surface of the radio wave transmitter 2 of the present invention on the metal layer side so as to face the housing, the surface on the base material side faces the outside. As a result, the decorative housing of the present invention is excellent in visibility of the design and also excellent in radio wave transmission. Further, since the surface of the radio wave transmitter of the present invention on the substrate side functions as a protective layer, durability is improved.

The material of the housing is not particularly limited, but from the viewpoint of radio wave transmission, resin or glass is preferable.

The metal layer side surface and the housing can be laminated by any method. Examples of the laminating method include laminating with an optical transparent adhesive, an optical transparent adhesive, an adhesive or an adhesive.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples.

(1) Manufacture of radio wave transmitter (Example 1)
The base material (PET film, thickness 50 μm) was placed in a vacuum apparatus and evacuated ^{until it became 5.0 × 10 -4} Pa or less. Subsequently, argon gas is introduced to form an In layer (average thickness 15.9 nm) as a metal layer on the surface of the base material by a DC magnetron sputtering method, and a laminate of the base material and the metal layer is formed. Obtained.

A laminate of the base material and the metal layer was placed in a vacuum apparatus and evacuated until the value became ^{5.0 × 10 -4 Pa or less.} Subsequently, argon gas is introduced, and a Si layer (average thickness 16.3 nm) is formed as a color tone adjusting layer on the surface of the metal layer opposite to the base material side by the DC magnetron sputtering method, and radio waves are generated. A permeable material was obtained.

(Examples 2 to 10, Comparative Examples 1 to 5)
Radio wave transmission in the same manner as in Example 1 except that the thickness of the metal layer, the thickness of the color tone adjusting layer, the thickness of the base material, the presence or absence of the metal layer, the presence or absence of the color tone adjusting layer, etc. are changed as shown in Tables 1 and 2. I got a body.

(Example 11)
A base material (polyurethane elastomer film (TPU), manufactured by Seadam, DUS202-CDR 6HF (0.1)) was placed in a vacuum apparatus and evacuated until the temperature ^{became 5.0 × 10 -4} Pa or less. Subsequently, argon gas was introduced and a Cu layer (average thickness 28 nm) was formed as a metal layer on the surface of the base material by a DC magnetron sputtering method to obtain a laminate of the base material and the metal layer. ..

A laminate of the base material and the metal layer was placed in a vacuum apparatus and evacuated until the value became ^{5.0 × 10 -4 Pa or less.} Subsequently, argon gas is introduced, and a Si layer (average thickness 10 nm) is formed as a color tone adjusting layer on the surface of the metal layer opposite to the base material side by the DC magnetron sputtering method to form a laminate. Obtained.

The laminated body was subjected to a tensile treatment, and specifically, it was pulled by a tensile tester until the length in the elongation direction became 125%, and then left for 1 minute or more to obtain a radio wave transmitting body.

(Examples 12 to 18, Comparative Examples 6 to 8)
A radio wave transmitter was obtained in the same manner as in Example 11 except that the type of the base material, the metal type of the metal layer, the thickness of the metal layer, the thickness of the color tone adjusting layer, and the like were changed as shown in Table 3. Only in Comparative Example 8, the tensile treatment was not performed. Further, in Comparative Example 7, the film was broken by the tensile treatment.

Details of the base material different from Example 11 are as follows.
Example 14: Polyurethane elastomer film (TPU), manufactured by Fuwafon, HF-3071D
Example 15: Polyurethane elastomer film (TPU), manufactured by Fuwafon, HF-1055AP
Example 16: Polyurethane elastomer film (TPU), manufactured by Fuwafon, HF-4090A
Example 17: Chloroprene rubber sheet, manufactured by Akizu Kogyo Co., Ltd., CB260N
Example 18: Polypropylene film, manufactured by Smilon, EC-7520
Comparative Example 6: Foam sheet (crosslinked polyolefin foam), manufactured by Sekisui Chemical Co., Ltd., Borara (WL05)
Comparative Examples 7 and 8: PET film, manufactured by Toyobo Co., Ltd., A4100 (0.05)

(Example 19)
A base material (PET film, thickness 50 μm, total light transmittance 89%) was placed in a vacuum apparatus and evacuated until the value became ^{5.0 × 10 -4 Pa or less.} Subsequently, argon gas is introduced to form a Si layer (average thickness 10 nm) as a color tone adjusting layer on the surface of the base material by a DC magnetron sputtering method, and a laminate of the base material and the color tone adjusting layer is formed. Obtained.

A laminate of the base material and the color tone adjusting layer was placed in a vacuum apparatus, and evacuated until the value became ^{5.0 × 10 -4 Pa or less.} Subsequently, argon gas is introduced, and an In layer (average thickness 15 nm) is formed as a metal layer on the surface of the color tone adjusting layer opposite to the base material side by the DC magnetron sputtering method to form a radio wave transmitter. Got

(Examples 20 to 24, Comparative Examples 9 to 12)
A radio wave transmitter was obtained in the same manner as in Example 19 except that the thickness of the color tone adjusting layer, the thickness of the metal layer, the type of the base material, the presence or absence of the metal layer, the presence or absence of the color tone adjusting layer, etc. were changed as shown in Table 1. rice field.
In Comparative Example 12, a laminate obtained by sputtering aluminum at 20 nm on one surface of a PET film (thickness 50 μm) was used as a base material. A radio wave transmitter was obtained in the same manner as in Example 19 except that the Si layer was formed on the surface on which the aluminum layer was not formed.

(2) Evaluation (2-1. Measurement of substrate characteristics)
The tensile strength, tensile elongation, and elongation recovery rate (25%) of the base materials of Examples 11 to 18 and Comparative Examples 6 to 8 were measured as follows.

(2-1-1. Tensile strength, tensile elongation)
JIS K7311 for thermoplastic polyurethane elastomer base material (Examples 11 to 16), JIS K6251 for rubber base material (Example 17), and JIS for other resin base materials (Example 18, Comparative Examples 6 to 8) Tensile strength and tensile elongation were measured according to K7127.

(2-1-2. Stretch recovery rate)
The base material was a sample of 5 cm × 10 cm, and the length (L ₀ ) in the length direction was measured. The sample was installed in a measuring machine (manufactured by Shimadzu Corporation, Autograph AGS-1kNX) and stretched to an elongation rate of 25% at a tensile speed of 300 mm / min. After that, the stretching was stopped, the sample was removed from the testing machine, and the stretching was recovered for 1 minute. The base material length L ₂ after elongation recovery was measured, and the elongation recovery rate was calculated from the following formula.
Elongation recovery rate (%) = ((L _1- L ₂ ) / (L _1- L ₀ )) x 100
In addition, L ₁ is the length at the time of 25% extension (= 1.25 × L ₀ ).

(2-2. Measurement of surface resistance)
Surface resistance of each radio wave transmitter (surface resistance of the color tone adjusting layer side surface for Examples 1 to 18 and Comparative Examples 1 to 8, and surface resistance of the base material side surface for Examples 19 to 24 and Comparative Examples 9 to 12 And the surface resistance of the surface on the metal layer side) was measured by a 4-terminal method using a surface resistance tester (manufactured by MITUBISHI CHEMICAL ANALYTECH, trade name: Loresta-EP, or trade name: Hiresta-UP).

^(2-3. Measurement of L *, a ^* , b ^* and saturation)
^{With respect to the obtained radio wave transmitter, L *} , a ^* , and b ^* were measured using a spectrophotometer (Spectrophotometer U-4100 manufactured by Hitachi, Ltd.) with 90-degree incident and 90-degree light reception. The saturation was calculated from ^{√ (a * 2} + b ^{* 2).}

(2-4. Evaluation of metal feeling)
When observing the surface of each radio wave transmitting body, it was visually confirmed whether or not it had a metallic feeling.
The metallic feeling was evaluated according to the following criteria.
◎: There is a considerable metallic feeling.
◯: There is a metallic feeling.
×: There is no metallic feeling.

(2-5. Measurement and evaluation of radio wave transmission)
The obtained radio wave transmitter was measured for electromagnetic wave shielding characteristics at frequencies of 1 MHz to 1000 MHz (= 1 GHz) using the KEC method shield material measurement system (manufactured by Nippon Technos Co., Ltd.) in accordance with the KEC method, and used as the attenuation amount. ..
The KEC method is a method for measuring and evaluating the electromagnetic wave shielding effect of a material by using an electromagnetic wave shielding effect device developed at the Kansai Electronic Development Center.
Radio wave transmission was evaluated according to the following criteria.
◯: The amount of attenuation at frequencies of 10 MHz, 100 MHz, and 1000 MHz is less than 5 dB.
X: The amount of attenuation at any of frequencies 10 MHz, 100 MHz, and 1000 MHz is 5 dB or more.

(2-6. Evaluation of design 1)
When the surfaces of the radio wave transmitters of Examples 1 to 18 and Comparative Examples 1 to 8 were observed, it was visually confirmed whether or not they had a design. The design was evaluated according to the following criteria.
〇: There is no breakage in the base material and there is no color unevenness.
X: The base material is broken or has uneven color.

(2-7. Evaluation of design)
From the saturation values of Examples 19 to 24 and Comparative Examples 9 to 12, the designability was evaluated according to the following criteria.
〇: Saturation is 5 or more.
X: Saturation is less than 5.

The results are shown in Tables 1 to 4.

1 Base material 2 Metal layer 3 Color tone adjustment layer 4 Adhesive layer 5 Housing

Claims (14)

Substrate, a metal layer, and a radio wave transmission body having a color tone adjusting layer, a radio wave transmission body, wherein the surface resistivity of the radio wave transmission body is 1.0 × 10 ⁵ Ω / □ or more. The radio wave transmitter according to claim 1, wherein the color tone adjusting layer includes a metal element-containing layer and / or a metalloid element-containing layer. The radio wave transmitter according to claim 1 or 2, wherein the metal layer is an indium-containing metal layer. The radio wave transmitter according to any one of claims 1 to 3, wherein the thickness of the metal layer is 70 nm or less. The radio wave transmission according to any one of claims 1 to 4, wherein the color adjustment layer contains silicon, germanium, gallium, zinc, silver, gold, titanium, aluminum, tin, copper, iron, molybdenum, indium or niobium. body. The radio wave transmitter according to any one of claims 1 to 5, wherein the saturation (√ (a ^{* 2} + b ^{* 2)) is 5 or more.} The radio wave transmitter according to any one of claims 1 to 6, wherein the brightness L ^{* is 35 or more.} The radio wave transmitter according to any one of claims 1 to 7, which has a base material, a metal layer, and a color tone adjusting layer in this order. The radio wave transmitter according to claim 8, wherein the elongation recovery rate of the base material is 90 to 100%. The radio wave transmitter according to claim 8 or 9, wherein the base material has a tensile strength of 15 to 50 Mpa and a tensile elongation of 300 to 1500%. The radio wave transmitter according to any one of claims 8 to 10, wherein the base material is a polyurethane resin base material. Substrate has a color tone adjusting layer and a metal layer in this order, and the surface resistance of the substrate surface and the metal layer-side surface of the radio wave transmission body is 1.0 × 10 ⁵ Ω / □ or more, claim The radio wave transmitter according to any one of 1 to 7. The radio wave transmitter according to claim 12, wherein the visible light transmittance of the base material is 80% or more. A decorative housing in which the metal layer side surface of the radio wave transmitting body according to claim 12 or 13 is arranged so as to face the housing.

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