WO2018186620A1

WO2018186620A1 - Laminate for sensor cover

Info

Publication number: WO2018186620A1
Application number: PCT/KR2018/003675
Authority: WO
Inventors: 김병삼; 안종준; 천재경
Original assignee: 김병삼
Priority date: 2017-04-07
Filing date: 2018-03-28
Publication date: 2018-10-11
Also published as: KR101824090B1

Abstract

The present invention relates to a laminate, for a sensor cover, comprising: a substrate; a first organic layer positioned on the substrate and comprising an organic material; a germanium layer positioned on the upper surface of the first organic layer and comprising germanium or a germanium alloy; and a second organic layer positioned on the upper surface of the germanium layer and comprising an organic material.

Description

Stacked body for sensor cover

The present invention relates to a laminate for sensor covers, and corresponds to international patent classification B32B5.

Smart Cruise Control (SCC) is a system that allows sensors mounted on the front of the vehicle to measure the distance and the relative speed with the vehicle in front of the vehicle to maintain the proper distance and the vehicle with the vehicle in front of the vehicle.

1 is an exemplary view showing a vehicle equipped with the sensor 2. Since the sensor 2 is mounted inside the front of the vehicle, a sensor cover capable of covering the sensor 2 may be installed at the front grille 3 or at the rear of the emblem 4. . The sensor cover may also be the emblem 4 itself.

2 (a) and 2 (b) show a state in which the sensor cover 1 is installed. 2 (a) and 2 (b), the sensor cover 1 is indicated by a thick line. In FIG. 2A, the sensor cover 1 is provided at the center of the front grill 3, and in FIG. 2B, the sensor cover 1 is itself an emblem.

The sensor cover covers the antenna of the sensor to protect it from collision, debris, wind pressure, and the like. Therefore, the sensor cover should have strength, weather resistance, etc. to protect the antenna of the sensor from external factors. In addition, the sensor cover should be able to transmit radio waves transmitted and received by the antenna of the sensor.

3 shows that after the radio wave L1 transmitted by the antenna of the sensor 2 reaches the front vehicle 5 through the sensor cover 1, the radio wave L2 reflected from the front vehicle 5 is The state of passing through the sensor cover 1 and reaching the antenna of the sensor 2 is shown. Typically, the reference propagation attenuation rate is -1.5 dB or more and less than 0 dB at a frequency of 76 to 77 GHz. However, since the propagation attenuation ratio within the same frequency is allowed to 0.3dB, the reference propagation attenuation ratio may be referred to as -1.8dB or more and less than 0dB at 76 to 77GHz.

The sensor cover must also have continuity with the surroundings. 2 (a) and 2 (b), the color of the front grill 3 is usually dark and / or light color. The front grille 3 is also generally glossy. Therefore, in general, the sensor cover 1 also exhibits a dark-based and / or light-colored color and is continuous with the surrounding front grill 3 only when it is glossy. Specifically, in Fig. 2A, since the X 'portion of the front grill 3 is dark and glossy, it is preferable that the X portion of the sensor cover 1 is also dark and glossy. Also, in Fig. 2A, since the Y 'portion of the front grill 3 is bright and glossy, it is preferable that the Y portion of the sensor cover 1 is also bright and glossy. Generally, the material which contributes to dark or light color and gloss is metal. Thus, the sensor cover 1 may comprise a metal.

When manufacturing a sensor cover using a metal, the sensor cover is continuous with the surroundings to give a sense of unity, but most metals are difficult to transmit the radio waves of the sensor.

Indium (In), tin (Sn), gallium (Ga), etc. are metals that can transmit the radio waves of the sensor while contributing to the appearance of dark or light color and gloss. Japanese Patent No. 3366299 (Patent Document 1) discloses a sensor cover containing indium. However, the sensor cover of patent document 1 is easy to be oxidized and peeled off, and lacks reliability.

(Previous Patent Document) Japanese Patent No. 3366299

SUMMARY OF THE INVENTION An object of the present invention for solving the above problems is to sandwich a germanium layer having radio wave transmission between two organic material layers, thereby providing a sensor cover laminate having excellent reliability. More specifically, it is an object of the present invention to provide a laminate for sensor covers with i) continuity with the periphery, ii) radio wave transmission, and iii) excellent reliability.

However, the problem to be solved by the present invention is not limited to the problem described above, another problem that is not described will be clearly understood by those skilled in the art from the following description.

The configuration of the present invention for achieving the above object is as follows.

Board; A first organic layer disposed on the substrate and composed of an organic material; A germanium layer disposed on an upper surface of the first organic layer and composed of germanium or a germanium alloy; And a second organic layer disposed on the germanium layer and including an organic material.

The sensor cover laminate may further include a chromium oxide layer disposed on an upper surface of the second organic layer and composed of chromium oxide.

The sensor cover laminate may further include a black shielding coating layer disposed on the chromium oxide layer and including a black pigment.

The sensor cover laminate may further include a primer coating layer disposed between the substrate and the first organic layer and including a polymer resin.

The substrate may be a transparent substrate.

The transparent substrate is polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin polymer (COP), polyether sulfone ( PES), polyether ether ketone (PEEK), polyarylate (PAR), ABS (ABS) resin, or silicone resin material.

The germanium alloy may include 50 to 99 wt% of germanium and 1 to 50 wt% of one or more elements belonging to groups 3B to 5A of the periodic table with respect to the total weight of the alloy.

The first organic layer may have a thickness of about 10 to about 3000 kPa.

The germanium layer may have a thickness of about 10 to about 500 kPa.

The second organic material layer may have a thickness of about 10 to about 3000 kPa.

The chromium oxide layer may have a thickness of 50 to 400 kPa.

Board; A ceramic layer disposed on the substrate and composed of ceramic; A first organic layer disposed on an upper surface of the ceramic layer and composed of an organic material; A germanium layer disposed on an upper surface of the first organic layer and composed of germanium or a germanium alloy; And a second organic layer disposed on the germanium layer and including an organic material.

The ceramic layer may include at least one high refractive index layer having a refractive index of 1.7 to 2.6 and at least one low refractive index layer having a refractive index of at least 1.4 and less than 1.7, wherein the high refractive index layer and the low refractive index layer may be alternately positioned. have.

The high refractive index layer and the low refractive index layer may be composed of at least one material selected from the group consisting of oxides, carbides, and nitrides.

The high refractive index layer may be composed of at least one material selected from the group consisting of TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , Ti ₃ O ₅ , Ta ₂ O ₅ , and CrOx, the low refractive index layer is SiO ₂ And it may be composed of at least one material selected from the group consisting of MgF ₂ .

The thickness of the high refractive index layer may be 10 to 1000 kPa, and the thickness of the low refractive index layer may be 10 to 1000 kPa.

Board; A color crystal layer positioned on the substrate; A germanium layer disposed on an upper surface of the color crystal layer and composed of germanium or a germanium alloy; Located on the germanium layer, and comprising a second organic layer composed of an organic material, the color crystal layer is composed of a first-first organic layer and a color conversion layer adjacent to the first-first organic layer in a horizontal direction, the first- One organic layer is composed of an organic material, the color conversion layer is provided with a ceramic layer composed of a ceramic and a first-second organic layer composed of an organic material located on the ceramic layer upper surface is provided, the sensor cover laminate.

According to an embodiment of the present invention having the configuration as described above, the laminate for sensor cover exhibits a color of a dark series and / or a light color series, and is glossy. In particular, according to manufacturing examples, the laminate for a sensor cover may exhibit black among the dark series and silver among the bright series. Therefore, the stack for the sensor cover has a continuity with the surrounding front grille to give a sense of unity. In addition, the laminate for sensor covers of the present invention containing germanium is superior in continuity to conventional sensor covers containing indium, tin, or gallium.

In addition, according to an embodiment of the present invention, the sensor cover stack may transmit radio waves transmitted and received by the antenna of the smart cruise control sensor. In particular, according to the experimental examples, the laminate for the sensor cover can transmit a radio wave of 76 to 77GHz with attenuation rate of -0.7dB or more and less than 0dB.

In addition, according to an embodiment of the present invention, the laminate for a sensor cover is excellent in water resistance.

1 is an exemplary view showing a vehicle equipped with a sensor for smart cruise control.

2 (a) and 2 (b) are exemplary views showing a state in which a sensor cover is installed.

3 is a conceptual diagram showing how radio waves transmitted and received by an antenna of a sensor penetrate the sensor cover.

4 is a schematic diagram showing a laminate for sensor covers according to an embodiment of the present invention.

5 (a) and 5 (b) are schematic diagrams showing a laminated body for a sensor cover according to an embodiment of the present invention.

6 is a schematic diagram showing a laminate for sensor covers according to an embodiment of the present invention.

7 is a graph showing a result of reflectance measurement according to an experimental example of the present invention.

8 is a graph showing a result of reflectance measurement according to an experimental example of the present invention.

9 (a) to 9 (c) are images showing the results of a water resistance test according to an experimental example of the present invention.

10 (a) to 10 (c) are images showing the results of water resistance test according to an experimental example of the present invention.

11 (a) and 11 (b) are images showing the laminated body for a sensor cover manufactured according to one embodiment of the present invention.

One preferred embodiment of the present invention is a substrate; A first organic layer disposed on the substrate and composed of an organic material; A germanium layer disposed on an upper surface of the first organic layer and composed of germanium or a germanium alloy; And a second organic material layer on the germanium layer, the organic material layer comprising an organic material.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. However, the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

For clarity of description of embodiments of the present invention, parts irrelevant to the description are omitted from the accompanying drawings. Similar parts are designated by like reference numerals throughout the present specification.

The terminology used herein is for the purpose of describing various embodiments only and is not intended to be limiting of the invention. When a first component is expressed as being "connected (connected, contacted, coupled)" to a second component, it is said that the first component is "directly connected" to the second component or a third component. Means that it can be "indirectly connected" through. Singular expressions include plural expressions unless the context clearly indicates otherwise. Also, the terms "comprise" or "have" mean that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features, It does not mean that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is excluded.

In the present specification, the laminate 1 for the sensor cover means that the sensor cover 1 shown in FIGS. 1, 2 (a), and 2 (b) may be used as such.

In addition, in the present specification, the color, brightness, glossiness, and the like of the sensor cover stack 1 mean the color, brightness, gloss, etc. seen when the sensor cover stack 1 is viewed from the front vehicle 5 side. (See FIGS. 3 to 5).

In addition, in this specification, each layer which comprises the laminated body for sensor covers 1 is all a thin film form.

In addition, in the present specification, "dark" means black or a color close to black when viewed with the naked eye, and means various colors exhibiting a reflectance of 10 to 45% in an optical wavelength region of 400 to 700 nm.

In addition, in the present specification, "bright color" is a color of white or near white when viewed with the naked eye, and means various colors exhibiting a reflectance of 45 to 80% in an optical wavelength region of 400 to 700 nm.

Example 1 Dark Laminate

4 is a schematic view showing a laminate for sensor cover 1 according to an embodiment of the present invention. In FIG. 4, for the sake of understanding, the radio wave L1 passing through and traveling between the sensor 2, the front vehicle 5, and the sensor 2 and the front vehicle 5, and passing through the stack 1 for the sensor cover, L2) is also shown. 4, the sensor cover laminate 1 according to an embodiment of the present invention is a substrate 10, primer coating layer 20, the first organic layer 30, the germanium layer 40, the second organic layer 50, a chromium oxide layer 60, and a black shielding coating layer 70.

The substrate 10 is a transparent substrate. The transparent substrate is polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin polymer (COP), polyether sulfone ( PES), polyether ether ketone (PEEK), polyarylate (PAR), ABS (ABS) resin, or a silicone resin material, but the present invention is not limited thereto.

The primer coating layer 20 is located on the upper surface of the substrate 10. The primer coating layer 20 includes a polymer resin to improve adhesion between the substrate 10 and the first organic layer 30. The primer coating layer 20 may be formed by mixing a polymer resin, a solvent, and other additives, and then painting, dipping, or spraying the mixture. The primer coating layer 20 is transparent or translucent.

The first organic layer 30 is located on the top surface of the primer coating layer 20. The first organic layer 30 is formed of an organic material to prevent the germanium layer 40 from being oxidized in contact with moisture. The organic material constituting the first organic layer 30 may be Glipoxan ^™ , but is not limited thereto. In addition, the first organic layer 30 may be formed through plasma enhanced chemical vapor deposition (PECVD), but the present invention is not limited thereto.

The first organic layer 30 may be transparent or translucent depending on the type of organic material, the content of the organic material, the layer thickness, or the like. The translucent degree of the first organic layer 30 may also vary according to the type of organic material, the content of the organic material, the layer thickness, and the like. The germanium layer 40 exhibits a dark-based color. When the first organic layer 30 is translucent, the first organic layer 30 has a brightness of the color represented by the germanium layer 40 according to the degree of translucency. To change.

Preferably, the thickness of the first organic layer 30 is 10 to 3000 kPa. If the thickness of the first organic layer 30 is less than 10 mm, it is difficult to prevent the germanium layer 40 from contacting with moisture. When the thickness of the first organic layer 30 is thick, the water resistance of the sensor cover stack 1 may be improved, but radio wave permeability may be deteriorated. If the thickness of the first organic layer 30 exceeds 3000 kPa, the radio waves L1 and L2 do not pass through the sensor cover stack 1 in FIG. 4. However, when the thickness of the first organic material layer 30 exceeds 3000 kPa, the radio wave permeability of the sensor cover stack 1 may be deteriorated. In addition, when the thickness of the first organic layer 30 exceeds 3000 kPa, the first organic layer 30 may damage the gloss of the germanium layer 40 even if the radio wave permeability is not bad.

As the thickness of the first organic layer 30 varies in a range of 10 to 3000 kPa, the brightness of the dark color represented by the germanium layer 40 varies in various ways. Accordingly, the sensor cover stack 1 may exhibit various colors belonging to the dark color series.

The germanium layer 40 is located on an upper surface of the first organic layer 30. The germanium layer 40 is composed of germanium (Ge) or germanium alloy. Instead of indium (In), tin (Sn), or gallium (Ga) used in the prior art, germanium is used in the present invention. Germanium is a metalloid, which exhibits dark color and luster as well as transmission of radio waves. Therefore, the germanium layer 40 contributes to the sensor cover stack 1 having a dark color and gloss.

The germanium alloy includes germanium and at least one element belonging to groups 3B to 5A of the periodic table. The at least one element added to germanium contributes to the strength improvement of the laminate for sensor cover 1. Preferably, the at least one element is gold (Au), silver (Ag), boron (B), aluminum (Al), gallium (Ga), indium (In), tin (Sn), and thallium (Tl). Element selected from the group consisting of. It is preferable that the germanium content is 50 to 99 wt% and the content of the at least one element is 1 to 50 wt% based on the total weight of the germanium alloy. If the germanium content is less than 50wt% or the content of the one or more elements is more than 50wt%, the germanium content may be low and the gloss of the sensor cover laminate 1 may be weak. If the germanium content exceeds 99 wt% or the one or more element content is less than 1 wt%, the added one or more elements may not contribute to the improvement of strength of the laminate for sensor cover 1.

The germanium layer 40 may be formed through electron beam deposition, thermal deposition, sputtering, thermal chemical vapor deposition (CVD), or electroless plating, but the present invention is not limited thereto.

Preferably, the germanium layer 40 has a thickness of 10 to 500 kPa. When the thickness of the germanium layer 40 is less than 10 μm, the germanium layer 40 may be easily peeled off. On the other hand, when the thickness of the germanium layer 40 exceeds 500 kPa, the radio wave permeability of the sensor cover stack 1 may be deteriorated.

The second organic layer 50 is located on the upper surface of the germanium layer 40. The second organic layer 50 is formed of an organic material to prevent the germanium layer 40 from being oxidized in contact with moisture. The organic material constituting the second organic layer 50 may be Glipoxan ^™ , but is not limited thereto. In addition, the second organic layer 50 may be formed through plasma enhanced chemical vapor deposition (PECVD), but the present invention is not limited thereto.

The second organic layer 50 may be transparent or translucent depending on the type of organic material, the content of the organic material, the layer thickness, and the like. The translucent degree of the second organic layer 50 may also vary according to the type of organic material, the content of the organic material, the layer thickness, and the like. When the germanium layer 40 is deposited in a thin film form, the germanium layer 40 may be translucent while showing a dark color. When the germanium layer 40 and the second organic layer 50 are translucent, the second organic layer 50 has a color represented by the germanium layer 40 according to the translucency of the second organic layer 50. Change the brightness

Preferably, the thickness of the second organic layer 50 is 10 to 3000 kPa. When the thickness of the second organic layer 50 is less than 10 mm, it is difficult to prevent the germanium layer 40 from contacting with moisture. When the thickness of the second organic layer 50 exceeds 3000 kPa, the water resistance of the sensor cover stack 1 may be improved while the radio wave permeability may be deteriorated. As the thickness of the second organic layer 50 varies in a range of 10 to 3000 kPa, the brightness of the dark color represented by the germanium layer 40 may vary. Accordingly, the sensor cover stack 1 may exhibit various colors belonging to the dark color series.

The germanium layer 40 is sandwiched between the first organic layer 30 and the second organic layer 50. Germanium transmits radio waves while exhibiting a dark-based color and luster. However, germanium is prone to oxidation by contact with moisture or oxygen. The first organic layer 30 and the second organic layer 50 prevent the germanium layer 40 from being oxidized in contact with water above and below the germanium layer 40. When the organic layer is located on the upper and lower surfaces of the germanium layer 40, the water resistance of the laminate 1 for the sensor cover is further improved than when the organic layer is disposed on the upper or lower surface of the germanium layer 40. do. In addition, the two organic material layers may protect the germanium layer 40 from an external impact. In addition, the two organic layers may vary the brightness of the dark color represented by the germanium layer 40. Accordingly, the sensor cover stack 1 may exhibit various colors belonging to a dark color series.

The chromium oxide layer 60 is located on the upper surface of the second organic layer 50. The chromium oxide layer 60 is composed of chromium oxide (CrOx) to further prevent the germanium layer 40 from being oxidized in contact with moisture. In addition, the chromium oxide layer 60 further protects the germanium layer 40 from external impact. In addition, the chromium oxide layer 60 improves adhesion between the second organic layer 50 and the black shielding coating layer 70. In addition, since the chromium oxide layer 60 exhibits a dark color, the chromium oxide layer 60 may contribute to the color represented by the sensor cover stack 1.

The chromium oxide layer 60 may be formed through electron beam deposition, thermal deposition, sputtering, thermal CVD, or electroless plating, but the present invention is not limited thereto.

Preferably, the thickness of the chromium oxide layer 60 is 50 to 400 kPa. When the thickness of the chromium oxide layer 60 is less than 50 GPa, the chromium oxide layer 60 is difficult to protect the germanium layer 40 from moisture or external impact. When the thickness of the chromium oxide layer 60 exceeds 400 kPa, the radio wave permeability of the sensor cover laminate 1 may be deteriorated.

The black shielding coating layer 70 is located on the top surface of the chromium oxide layer 60. The laminate composed of the remaining layers except for the black shielding coating layer 70 may be translucent. In this case, the sensor 2 of FIG. 4 or the internal parts of the vehicle may be seen on the outside, thereby deteriorating the vehicle appearance. The black shielding coating layer 70 includes a black pigment to shield the visible light so that visible light reaching the sensor cover stack 1 does not pass through the sensor cover stack 1. Of course, the black shielding coating layer 70 does not shield the radio waves. Even if the laminate not including the black shielding coating layer 70 does not harm the appearance of the vehicle, if the black shielding coating layer 70 is added, the black shielding coating layer 70 will protect the underlying layers from external impact. Can be. In addition, since the black shielding coating layer 70 is black, the black shielding coating layer 70 may contribute to the color represented by the laminate for sensor cover 1.

The black shielding coating layer 70 may be formed by mixing a polymer resin, a black pigment, a solvent, and other additives, and then painting, dipping, or spraying the mixture.

The sensor cover laminate 1 of Example 1 exhibits a dark-based color. In Example 1, the first organic layer 30 and the second organic layer 50 may change the brightness of the germanium layer 40. Accordingly, the sensor cover stack 1 may exhibit various colors belonging to the dark color series. However, in the first embodiment, even if the thickness of the first organic layer 30, the thickness of the second organic layer 50, and the like are adjusted, the sensor cover stack 1 may not exhibit bright color. In Example 2, the ceramic cover 80 is added to the sensor cover laminated body 1 of Example 1, and the sensor cover laminated body 1 which shows bright color is demonstrated.

Example 2 Bright Laminate

FIG. 5 (a) is a schematic view showing the sensor cover laminate 1 according to the embodiment of the present invention. 5 (a), for the sake of understanding, a radio wave is transmitted between the sensor 2, the front vehicle 5, and the sensor 2 and the front vehicle 5, passing through the sensor cover stack 1. (L1, L2) are also shown together. Referring to FIG. 5 (a), the laminate for a sensor cover 1 according to an embodiment of the present invention may include a substrate 10, a primer coating layer 20, a ceramic layer 80, a first organic layer 30, The germanium layer 40, the second organic layer 50, the chromium oxide layer 60, and the black shielding coating layer 70 are included.

Details of the substrate 10 have been described above.

The primer coating layer 20 includes a polymer resin to improve adhesion between the substrate 10 and the ceramic layer 80. Other details of the primer coating layer 20 has been described above.

The ceramic layer 80 is located on the upper surface of the substrate 10. The ceramic layer 80 is made of ceramic to change the color of the dark color represented by the germanium layer 40 to the color of the light color.

The ceramic layer 80 includes at least one high refractive index layer and at least one low refractive index layer. The high refractive index layer and the low refractive index layer are alternately located. For example, as illustrated in FIG. 5B, the ceramic layer 80 may include a first high refractive index layer 81, a first low refractive index layer 82, a second high refractive index layer 83, And a second low refractive index layer 84. The first low refractive index layer 82 is located on an upper surface of the first high refractive index layer 81. The second high refractive index layer 83 is located on an upper surface of the first low refractive index layer 82. The second low refractive index layer 84 is located on an upper surface of the second high refractive index layer 83.

The high refractive index layer has a refractive index of 1.7 to 2.6, and the low refractive index layer has a refractive index of 1.4 or more and less than 1.7. The high refractive index layer and the low refractive index layer may be alternately positioned so that the dark color of the germanium layer 40 may change to a bright color. However, the brightness of the bright color represented by the sensor cover stack 1 varies depending on the thickness of the high refractive index layer, the thickness of the low refractive index layer, the number of layers constituting the ceramic layer 80, and the like.

The high refractive index layer and the low refractive index layer are made of ceramic. Specifically, the high refractive index layer may be composed of at least one material selected from the group consisting of oxides, carbides, and nitrides, as well as the low refractive index layer. More specifically, the high refractive index layer may be composed of at least one material selected from the group consisting of TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , Ti ₃ O ₅ , Ta ₂ O ₅ , and CrOx. The low refractive index layer may be made of at least one material selected from the group consisting of SiO ₂ and MgF ₂ .

The high refractive index layer and the low refractive index layer may be formed through electron beam deposition, thermal deposition, sputtering, or thermal CVD, but the present invention is not limited thereto.

Preferably, the thickness of the high refractive index layer is 10 to 1000 GPa. When the thickness of the high refractive index layer is less than 10 GPa, the high refractive index layer is likely to peel off. On the other hand, within the range of the thickness of the high refractive index layer 10 ~ 1000Å, sufficiently various colors belonging to the bright color series can be implemented, it is inefficient to form a high refractive index layer of more than 1000Å thickness. The thickness of the low refractive index layer is also preferably 10 to 1000 kPa, and the reason thereof is also the same as that of the high refractive index layer.

The first organic layer 30 is located on the upper surface of the ceramic layer 80. Other details of the first organic layer 30 have been described above. In addition, the germanium layer 40, the second organic layer 50, the chromium oxide layer 60, and the black shielding coating layer 70 have been described above.

Example 3: Dark-Light Stack

6 is a schematic view showing a sensor cover laminate 1 according to an embodiment of the present invention. Referring to FIG. 6, the laminate for a sensor cover 1 according to an exemplary embodiment of the present invention may include a substrate 10, a primer coating layer 20, a color crystal layer 30a, a germanium layer 40, and a second organic layer. 50, a chromium oxide layer 60, and a black shielding coating layer 70.

The primer coating layer 20 is located on the upper surface of the substrate 10. The color crystal layer 30a is positioned on an upper surface of the primer coating layer 20. The germanium layer 40 is located on the top surface of the color crystal layer 30a. The second organic layer 50 is located on an upper surface of the germanium layer 40. The chromium oxide layer 60 is located on the upper surface of the second organic layer 50. The black shielding coating layer 70 is located on the chromium oxide layer 60.

The color determining layer 30a determines the color of the sensor cover stack 1. The color determination layer 30a includes a first-first organic layer 30c and a color conversion layer 30b adjacent to the first-first organic layer 30c in a horizontal direction. Referring to FIG. 6, the first-first organic layer 30c is located at the left side, and the color conversion layer 30b is located at the right side.

The first-first organic material layer 30c is made of an organic material to change the brightness of the dark color indicated by the upper portion thereof. However, referring to FIG. 6, eventually, the area A of the sensor cover stack 1 exhibits a dark-based color when viewed in the S direction.

The color conversion layer 30b is composed of a ceramic layer 80 and a 1-2 organic layer 30d. The first-second organic layer 30d is disposed on the upper surface of the ceramic layer 80 and is composed of an organic material. The ceramic layer 80 is made of ceramic, and the dark color indicated by the upper portion thereof is changed to bright color. In addition, the ceramic layer 80 may adjust brightness of bright colors. Accordingly, the region B of the sensor cover stack 1 exhibits a light color series color when viewed from the S direction (see FIG. 6).

Therefore, the sensor cover laminate 1 is a laminate of the first embodiment and the laminate of the second embodiment, and combines both dark and light colors. The first-first organic layer 30c is the same as the first organic layer 30 of the first embodiment, and the first-second organic layer 30d is the same as the first organic layer 30 of the second embodiment. Since other contents of the laminate for sensor cover 1 have been described in

Embodiments

1 and 2, detailed description thereof is omitted.

In the following, production examples, comparative examples, and experimental examples will be described.

Production Example 1: Manufacture of Black Laminate

The upper surface of the polycarbonate substrate 10 was coated with a slurry containing an acrylic resin as a main component, and a primer coating layer 20 was formed on the upper surface of the polycarbonate substrate 10.

The polycarbonate substrate having the primer coating layer 20 formed on an upper surface thereof was mounted at the bottom of the vacuum chamber. The degree of vacuum in the vacuum chamber was set to 7 × 10 ⁻⁶ Torr. Glipoxan ^{TM in} monomer state was supplied at 120 sccm through a Mass Flow Controller (MFC) installed in the vacuum chamber. And 3000W electric power was applied to the electrode plate of the plasma generating apparatus installed in the said vacuum chamber. As a result, the Glipoxan ^{TM in the} monomer state was converted into the plasma state, and the materials in the plasma state were polymerized to form the Glipoxan ^TM in the polymer state (Plasma polymerization). Glipoxan ^{TM in a} polymer state was deposited on the upper surface of the primer coating layer 20, and thus a first organic layer 30 was formed on the upper surface of the primer coating layer 20.

The polycarbonate substrate on which the primer coating layer 20 and the first organic layer 30 are formed is mounted on the upper part of the vacuum chamber. Germanium was added to the crucible installed in the vacuum chamber. The degree of vacuum in the vacuum chamber was set to 1 × 10 ⁻⁵ Torr. A voltage of 7.5 kV was supplied to the electron gun installed in the vacuum chamber, and the electron beam was irradiated onto germanium. As a result, the germanium layer 40 was formed on the upper surface of the first organic layer 30.

In the same manner as the deposition method of the first organic layer 30 (PECVD), a second organic layer 50 composed of Glipoxan ^™ was formed on the germanium layer 40.

Next, in the same manner as the deposition method of the germanium layer 40 (electron beam deposition), a chromium oxide layer 60 composed of Cr ₂ O ₃ was formed on the upper surface of the second organic layer 50.

The polycarbonate substrate having the chromium oxide layer 60 formed thereon is coated with a slurry containing an acrylic resin as a main component and a black pigment added thereto to form a black shielding coating layer 70 on an upper surface of the chromium oxide layer 60. It became.

That is, the substrate 10, the primer coating layer 20, the first organic layer 30, the germanium layer 40, the second organic layer 50, the chromium oxide layer 60, the black shielding coating layer 70, the laminate 1 ) Was prepared. The structure of the manufactured laminate is the same as the laminate for sensor cover 1 shown in FIG. The thickness of the first organic layer 30 was 250 kPa, the thickness of the germanium layer 40 was 350 kPa, the thickness of the second organic layer 50 was 250 kPa, and the thickness of the chromium oxide layer 60 was 150 kPa. The laminate thus prepared was black and glossy when viewed visually.

[Comparative Example 1: Except organic layer and chromium oxide layer in the laminate of Preparation Example 1]

A substrate-primer coating layer-germanium layer-black shielding coating layer laminate was prepared. The formation method, material, and thickness of each layer are the same as that of the manufacture example 1.

Comparative Example 2: Excluding Chromium Oxide Layer from Laminate of Preparation Example 1

A substrate-primer coating layer-first organic layer-germanium layer-second organic layer-black shielding coating layer laminate was prepared. The formation method, material, and thickness of each layer are the same as that of the manufacture example 1.

Production Example 2: Preparation of Silver Laminate

Substrate 10-Primer coating layer 20-Ceramic layer 80-First organic layer 30-Germanium layer 40-Second organic layer 50-Chromium oxide layer 60-Black shielding coating layer 70 The laminate 1 was produced. The structure of the manufactured laminate is the same as the laminate for sensor cover 1 shown in Fig. 5A. The ceramic layer 80 was formed in the same manner as the electron beam deposition of Preparation Example 1. Specifically, the ceramic layer 80 is deposited by the first high refractive index layer 81, the first low refractive index layer 82, the second high refractive index layer 83, and the second low refractive index layer 84 in order. Formed. That is, the structure of the ceramic layer 80 is as shown in Figure 5 (b). Ti ₃ O ₅ was used as a constituent material of the first high refractive index layer 81 and the second high refractive index layer 83, and the first low refractive index layer 82 and the second low refractive index layer 84 were used. SiO ₂ was used as a constituent material of. The thickness of the first high refractive index layer 81 is 150Å, the thickness of the first low refractive index layer 82 is 350Å, the thickness of the second high refractive index layer 83 is 400Å, and the second low refractive index layer ( 84) was 500 mm thick. The resulting laminate was silver and glossy when viewed visually.

Forming method, material, and thickness of the remaining layers except for the ceramic layer 80 is the same as in Preparation Example 1.

[Comparative Example 3: Except organic layer and chromium oxide layer in the laminate of Preparation Example 2]

A substrate-primer coating layer-ceramic layer-germanium layer-black shielding coating layer laminate was prepared. The formation method, material, and thickness of each layer are the same as that of the manufacture example 2.

[Comparative Example 4: Except chromium oxide layer in the laminate of Preparation Example 2]

A substrate-primer coating layer-ceramic layer-first organic layer-germanium layer-second organic layer-black shielding coating layer laminate was prepared. The formation method, material, and thickness of each layer are the same as that of the manufacture example 2.

Experimental Example 1: Reflectance Measurement

Reflectances for the laminates 1 prepared in Preparation Examples 1 and 2 were measured (Hitachi spectrophotometer U-3010). 7 shows the reflectance measurement results for the laminate 1 produced in Preparation Example 1. FIG. And FIG. 8 shows the reflectance measurement result for the laminate 1 produced in Preparation Example 2. FIG.

Referring to FIG. 7, the laminate 1 produced in Production Example 1 exhibits an average reflectance of 40%, and thus is confirmed to be black. In addition, the reflectance shown in the graph of FIG. 7 is higher than that of a sensor cover including conventional indium, tin, or gallium. This means that the laminate 1 produced in Preparation Example 1 is more glossy than the conventional sensor cover.

Referring to FIG. 8, the laminate 1 produced in Production Example 2 exhibits an average reflectance of 70% and is thus confirmed to be silver. In addition, the reflectance shown in the graph of FIG. 8 is higher than that of a sensor cover including conventional indium, tin, or gallium. This means that the laminate 1 produced in Preparation Example 2 is more glossy than the conventional sensor cover.

Experimental Example 2: Measurement of Radio Attenuation Rate

Propagation attenuation rates for the laminates 1 prepared in Production Examples 1 and 2 were measured (SM5899). The results are shown in Table 1 below.

Referring to Table 1, the radio wave transmitted through the laminate 1 prepared in Preparation Example 1 was attenuated by -0.62 dB, and the radio wave transmitted through the laminate 1 prepared in Preparation Example 2 was attenuated by -0.66 dB. It was. Considering that the attenuation factor reference value is -1.8 dB or more, it is confirmed that the radio wave transmittance of the laminates 1 produced in Production Examples 1 and 2 is satisfactory.

Experimental Example 3: Water Resistance Experiment

Water resistance tests were performed on the laminates prepared in Preparation Example 1, Preparation Example 2, and Comparative Examples 1 to 4. The prepared laminates were immersed in water at 40 ° C. for 240 hours and then taken out. The extracted laminates were left at room temperature for 1 hour after water removal through air injection. After that, it was confirmed whether the laminates were oxidized.

9 and 10 show images of the laminates subjected to the water resistance test. Fig. 9 (a) shows the laminate 1 of Production Example 1, Fig. 9 (b) shows the laminate of Comparative Example 1, and Fig. 9 (c) shows the laminate of Comparative Example 2, and Fig. 10 (a). 10 shows a laminate 1 of Production Example 2, FIG. 10B shows a laminate of Comparative Example 3, and FIG. 10C shows a laminate of Comparative Example 4. FIG.

Table 2 below shows the results of the water resistance experiment.

9, 10, and Table 2, except for Preparation Examples 1 and 2, oxidation occurred in all other cases. 9 (b) and 9 (c), the laminate prepared in Comparative Example 1 was more oxidized than the laminate prepared in Comparative Example 2. 10 (b) and 10 (c), the laminate prepared in Comparative Example 3 was more oxidized than the laminate prepared in Comparative Example 4. This result means that the first organic layer 30, the second organic layer 50, and the chromium oxide layer 60 are required for excellent water resistance of the laminate for sensor cover 1.

Summarizing Experimental Examples 1 to 3, the laminates 1 prepared in Preparation Examples 1 and 2 were (i) black or silver, glossy, and (ii) capable of transmitting radio waves to a satisfactory level. And (iii) that the water resistance is excellent.

Production Example 3: Preparation of Black-Silver Laminate

A laminate having the same structure as the laminate for sensor cover 1 of FIG. 6 was produced. Each layer was formed in the same manner as in Preparation Examples 1 and 2. 11 (a) shows an image of the manufactured laminate 1. Referring to Fig. 11 (a), a glossy laminate 1 is confirmed, showing both black and silver colors. Such a laminate can be used as the sensor cover 1 of the type shown in FIG.

Preparation Example 4 Production of Black Background-Silver Emblem Laminate

Using Example 3, a laminate composed of a black background and a silver emblem was produced. 11 (b) shows an image of the prepared laminate. A person skilled in the art will know how to manufacture the laminate shown in FIG. 11 (b) without further explanation. The manufactured laminate may be used as the sensor cover 1 of the type shown in FIG. 2 (b).

Although the present invention has been described with reference to the embodiments shown in the drawings, this is merely exemplary, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. will be. Therefore, the true technical protection scope of the present invention will be defined by the appended claims.

1: laminated body for sensor cover, sensor cover

10: substrate

20: primer coating layer

30: first organic layer

30a: color crystal layer 30b: color conversion layer

30c: 1-1st organic layer 30d: 1-2nd organic layer

40: germanium layer

50: second organic layer

60: chromium oxide layer

70: black shielding coating layer

80: ceramic layer

Claims

Board;

A first organic layer disposed on the substrate and composed of an organic material;

A germanium layer disposed on an upper surface of the first organic layer and composed of germanium or a germanium alloy; And

Located on the germanium layer upper surface, comprising a second organic layer composed of an organic material, a sensor cover laminate.
The method of claim 1,

Located on the second organic layer upper surface, further comprising a chromium oxide layer consisting of chromium oxide, the sensor cover laminate.
The method of claim 2,

Located on the top of the chromium oxide layer, further comprising a black shielding coating layer containing a black pigment, the laminate for a sensor cover.
The method of claim 1,

A laminate for sensor cover, further comprising a primer coating layer positioned between the substrate and the first organic layer and comprising a polymer resin.
The method of claim 1,

The substrate is a laminate for sensor cover, which is a transparent substrate.
The method of claim 5,

The transparent substrate is polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin polymer (COP), polyether sulfone ( PES), polyether ether ketone (PEEK), polyarylate (PAR), ABS (ABS) resin, or a silicone resin laminated body for a sensor cover.
The method of claim 1,

Wherein the germanium alloy, based on the total weight of the alloy, 50 to 99wt% germanium and 1 to 50wt% of one or more elements belonging to Groups 3B to 5A of the periodic table, the laminate for a sensor cover.
The method of claim 1,

The thickness of the said 1st organic material layer is 10-3000 GPa, The laminated body for sensor covers.
The method of claim 1,

The germanium layer has a thickness of 10 to 500 kPa, The laminate for sensor cover.
The method of claim 1,

The thickness of the said 2nd organic material layer is 10-3000 GPa, The laminated body for sensor covers.
The method of claim 2,

The thickness of the chromium oxide layer is 50 to 400 Pa, the sensor cover laminate.
Board;

A ceramic layer disposed on the substrate and composed of ceramic;

A first organic layer disposed on an upper surface of the ceramic layer and composed of an organic material;

A germanium layer disposed on an upper surface of the first organic layer and composed of germanium or a germanium alloy; And

Located on the germanium layer upper surface, comprising a second organic layer composed of an organic material, a sensor cover laminate.
The method of claim 12,

The ceramic layer comprises at least one high refractive index layer having a refractive index of 1.7 to 2.6 and at least one low refractive index layer having a refractive index of at least 1.4 and less than 1.7,

Said high refractive index layer and said low refractive index layer are alternately located, The laminated body for a sensor cover.
The method of claim 13,

And the high refractive index layer and the low refractive index layer are made of at least one material selected from the group consisting of oxides, carbides, and nitrides.
The method of claim 14,

The high refractive index layer is composed of at least one material selected from the group consisting of TiO 2 , ZrO 2 , Nb 2 O 5 , Ti 3 O 5 , Ta 2 O 5 , and CrOx,

The low refractive index layer is composed of at least one material selected from the group consisting of SiO 2 and MgF 2 , the laminate for a sensor cover.
The method of claim 13,

The thickness of the high refractive index layer is 10 to 1000Å,

The thickness of the said low refractive index layer is 10-1000 GPa, The laminated body for sensor covers.
Board;

A color crystal layer positioned on the substrate;

A germanium layer disposed on an upper surface of the color crystal layer and composed of germanium or a germanium alloy;

Located on the germanium layer upper surface, comprising a second organic layer composed of an organic material,

The color crystal layer is composed of a first-first organic layer and a color conversion layer adjacent to the first-first organic layer in a horizontal direction,

The first-first organic layer is composed of an organic material,

Wherein the color conversion layer is composed of a ceramic layer composed of a ceramic and a first-second organic layer composed of an organic material located on the ceramic layer upper surface, the laminate for a sensor cover.