(19)
(11)EP 3 641 516 A1

(12)EUROPEAN PATENT APPLICATION
published in accordance with Art. 153(4) EPC

(43)Date of publication:
22.04.2020 Bulletin 2020/17

(21)Application number: 18817041.9

(22)Date of filing:  27.03.2018
(51)International Patent Classification (IPC): 
H05K 9/00(2006.01)
B32B 9/00(2006.01)
B32B 7/02(2019.01)
B32B 15/08(2006.01)
(86)International application number:
PCT/JP2018/012603
(87)International publication number:
WO 2018/230093 (20.12.2018 Gazette  2018/51)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
KH MA MD TN

(30)Priority: 13.06.2017 JP 2017116297

(71)Applicant: Nitto Denko Corporation
Ibaraki-shi, Osaka 567-8680 (JP)

(72)Inventors:
  • YAMAGATA Kazuto
    Ibaraki-shi Osaka 567-8680 (JP)
  • MACHINAGA Hironobu
    Ibaraki-shi Osaka 567-8680 (JP)
  • UEDA Eri
    Ibaraki-shi Osaka 567-8680 (JP)
  • UKEI Hiroichi
    Ibaraki-shi Osaka 567-8680 (JP)
  • UI Takehiro
    Ibaraki-shi Osaka 567-8680 (JP)

(74)Representative: Grünecker Patent- und Rechtsanwälte PartG mbB 
Leopoldstraße 4
80802 München
80802 München (DE)

  


(54)ELECTROMAGNETIC-WAVE ABSORBER AND MOLDED ARTICLE PROVIDED WITH ELECTROMAGNETIC-WAVE ABSORBER


(57) An electromagnetic wave absorber (1) includes a dielectric layer (10), a resistive layer (20), and an electrically conductive layer (30). The resistive layer (20) is disposed on one principal surface of the dielectric layer (10). The electrically conductive layer (30) is disposed on the other principal surface of the dielectric layer (10) and has a sheet resistance lower than a sheet resistance of the resistive layer (20). The resistive layer (20) has a sheet resistance of 200 to 600 Ω/□. When the resistive layer (20) is subjected to an immersion treatment in which the resistive layer (20) is immersed in a 5 weight% aqueous solution of NaOH for 5 minutes, an absolute value of a difference between a sheet resistance of the resistive layer (20) before the immersion treatment and a sheet resistance of the resistive layer (20) after the immersion treatment is less than 100 Ω/□.




Description

TECHNICAL FIELD



[0001] The present invention relates to an electromagnetic wave absorber and an electromagnetic wave absorber-attached molded article.

BACKGROUND ART



[0002] In recent years, electromagnetic waves in a range of millimeter waves having a wavelength of about 1 to 10 mm and a frequency of 30 to 300 GHz and quasi-millimeter waves have been used as information communication media. The use of such electromagnetic waves in anti-collision systems has been under consideration. An anti-collision system is a system, for example, installed in a vehicle, detecting obstacles to automatically put on the brakes, or measuring the speed of vehicles around the vehicle equipped with the system and distance between the vehicle and another vehicle to adjust the speed of the vehicle and distance between the two vehicles. To allow anti-collision systems to normally operate, reception of as few unnecessary electromagnetic waves as possible is important for prevention of false recognition. Therefore, it is conceivable to use an electromagnetic wave absorber in anti-collision systems to absorb unnecessary electromagnetic waves.

[0003] There are various types of electromagnetic wave absorbers classified according to their principles of electromagnetic wave absorption. For example, an electromagnetic wave absorber provided with an electromagnetic wave reflective layer, a dielectric layer having a thickness of λ/4 (λ is a wavelength of an electromagnetic wave to be absorbed), and a resistive film layer (such an electromagnetic wave absorber may be referred to as "λ/4 electromagnetic wave absorber") can be produced at a low cost owing to relatively inexpensive materials and ease of design. For example, Patent Literature 1 proposes, as a λ/4 electromagnetic wave absorber, an electromagnetic wave absorber exercising its function in a wide incident angular range.

CITATION LIST


Patent Literature



[0004] Patent Literature 1: JP 2003-198179 A

SUMMARY OF INVENTION


Technical Problem



[0005] Patent Literature 1 fails to specifically discuss the durability (for example, chemical resistance) typically required in environments where electromagnetic wave absorbers are used.

[0006] Therefore, the present invention provides an electromagnetic wave absorber including a resistive layer that is advantageous for exhibiting good chemical resistance. The present invention also provides an electromagnetic wave absorber-attached molded article including such an electromagnetic wave absorber.

Solution to Problem



[0007] The present invention provides an electromagnetic wave absorber, including:

a dielectric layer;

a resistive layer that is disposed on one principal surface of the dielectric layer; and

an electrically conductive layer that is disposed on the other principal surface of the dielectric layer and has a sheet resistance lower than a sheet resistance of the resistive layer, wherein

the resistive layer has a sheet resistance of 200 to 600 Ω/□, and

when the resistive layer is subjected to an immersion treatment in which the resistive layer is immersed in a 5 weight% aqueous solution of NaOH for 5 minutes, an absolute value of a difference between a sheet resistance of the resistive layer before the immersion treatment and a sheet resistance of the resistive layer after the immersion treatment is less than 100 Ω/□.



[0008] The present invention also provides an electromagnetic wave absorber-attached molded article, including:

a molded article; and

the above electromagnetic wave absorber attached to the molded article.


Advantageous Effects of Invention



[0009] In the above electromagnetic wave absorber, the resistive layer has good chemical resistance.

BRIEF DESCRIPTION OF DRAWINGS



[0010] 

FIG. 1 is a cross-sectional view showing an example of an electromagnetic wave absorber of the present invention.

FIG. 2 is a side view showing an example of an electromagnetic wave absorber-attached molded article of the present invention.


DESCRIPTION OF EMBODIMENTS



[0011] Hereinafter, embodiments of the present invention will be described with reference to the drawings. The following description describes examples of the present invention, and the present invention is not limited to the following embodiments.

[0012] The present inventors have newly found the following problem in the course of considering application of electromagnetic wave absorbers to anti-collision systems. For example, when an electromagnetic wave absorber is used in an anti-collision system, the electromagnetic wave absorber is installed on a vehicle such as an automobile. A chemical such as a cleaner can be used sometimes for vehicle maintenance. For example, an alkaline solution can be used sometimes to wash vehicles. Thus, electromagnetic wave absorbers installed on vehicles are likely to have contact with such a chemical while the vehicles are being washed. In particular, a resistive layer in a λ/4 electromagnetic wave absorber tends to be affected by such a chemical because the resistive layer is located near the surface of the electromagnetic wave absorber. This means that if a resistive layer of an electromagnetic wave absorber has good chemical resistance, a high-value added λ/4 electromagnetic wave absorber can be provided.

[0013] Thus, through a lot of trial and error, the present inventors have identified a material capable of imparting good chemical resistance to a resistive layer. The present inventors have invented an electromagnetic wave absorber according to the present invention based on this new finding. The present inventors also examined whether good chemical resistance can be imparted to a resistive layer of a λ/4 electromagnetic wave absorber with the use of an ITO used in technical fields of, for example, flat panel displays and solar cells. The examination revealed that it is difficult to impart good chemical resistance to a resistive layer with the use of such an ITO.

[0014] As shown in FIG. 1, an electromagnetic wave absorber 1 includes a dielectric layer 10, a resistive layer 20, and an electrically conductive layer 30. The resistive layer 20 is disposed on one principal surface of the dielectric layer 10. The electrically conductive layer 30 is disposed on the other principal surface of the dielectric layer 10 and has a sheet resistance lower than a sheet resistance of the resistive layer 20. The resistive layer 20 has a sheet resistance of 200 to 600 Ω/□. When the resistive layer 20 of the electromagnetic wave absorber 1 is subjected to an immersion treatment in which the resistive layer 20 is immersed in a 5 weight% aqueous solution of NaOH for 5 minutes, an absolute value of a difference between a sheet resistance of the resistive layer 20 before the immersion treatment and a sheet resistance of the resistive layer 20 after the immersion treatment is less than 100 Ω/□. Thus, the sheet resistance of the resistive layer 20 is unlikely to be changed by contact of the resistive layer 20 with a chemical such as an alkaline cleaner and the electromagnetic wave absorber 1 can maintain desired electromagnetic wave absorption properties even after the contact with the chemical. As just described, the resistive layer 20 has good chemical resistance; accordingly, the electromagnetic wave absorber 1 has good chemical resistance.

[0015] The electromagnetic wave absorber 1 is a λ/4 electromagnetic wave absorber. The λ/4 electromagnetic wave absorber is designed so that incidence of an electromagnetic wave having a wavelength (λO) to be absorbed will result in interference between the electromagnetic wave reflected by the surface of the resistive layer 20 (front surface reflection) and the electromagnetic wave reflected by the electrically conductive layer 30 (back surface reflection). In the λ/4 electromagnetic wave absorber, the wavelength (λO) of an electromagnetic wave to be absorbed is determined according to the thickness (t) of the dielectric layer 10 and the relative permittivity (εr) of the dielectric layer 10, as shown in the following equation (1). That is, an electromagnetic wave having a wavelength to be absorbed can be set by appropriately adjusting the material and thickness of the dielectric layer 10. In the equation (1), sqrt(εr) means a square root of the relative permittivity (εr).



[0016] When a resistive layer for a λ/4 electromagnetic wave absorber has a sheet resistance closer to the characteristic impedance of air (about 377 Ω/□), good electromagnetic wave absorbing properties are more likely to be obtained. Therefore, in view of maintaining the desired electromagnetic wave absorption properties even after contact of the electromagnetic wave absorber 1 with a chemical, it is very important that the sheet resistance of the resistive layer 20 is unlikely to be changed by contact of the resistive layer 20 with a chemical.

[0017] The resistive layer 20 includes, for example, at least one of tin oxide, titanium oxide, and indium oxide as a main component. The term "main component" as used herein refers to a component whose content is highest on a weight basis.

[0018] When the resistive layer 20 includes any one of tin oxide, titanium oxide, and indium oxide as its main component, the resistive layer 20 may include only one of tin oxide, titanium oxide, and indium oxide. Moreover, when the resistive layer 20 includes any one of tin oxide, titanium oxide, and indium oxide as its main component, the resistive layer 20 may further include a dopant that includes at least one element other than a metal element included in the main component. In such cases, the specific resistance of the material forming the resistive layer 20 is more easily adjusted to be within a desired range. Adjustment of the specific resistance of the material forming the resistive layer 20 to be within a desired range leads the resistive layer thickness required to impart the desired sheet resistance to the resistive layer 20 to be within a desired range and allows achievement of both the chemical resistance of the resistive layer 20 and the ease of production of the resistive layer 20.

[0019] The element included in the above dopant is, for example, at least one element selected from the group consisting of tin, silicon, magnesium, titanium, nitrogen, fluorine, antimony, and niobium.

[0020] When the main component of the resistive layer 20 is tin oxide, the element included in the dopant is, for example, fluorine or antimony. When the main component of the resistive layer 20 is titanium oxide, the element included in the dopant is, for example, niobium. When the main component of the resistive layer 20 is indium oxide, the element included in the dopant is, for example, tin, silicon, magnesium, titanium, or nitrogen. In such cases, the specific resistance of the material forming the resistive layer 20 is more easily adjusted to be within a desired range.

[0021] As described above, the resistive layer 20 has a sheet resistance of 200 to 600 Ω/□. Thus, the sheet resistance of the resistive layer 20 is close to a characteristic impedance of air and the electromagnetic wave absorber 1 can exhibit good electromagnetic wave absorption performance. For example, selective absorption of an electromagnetic wave having a wavelength generally employed by a millimeter-wave radar or quasi-millimeter-wave radar is made easy. For example, the electromagnetic wave absorber 1 can effectively attenuate an electromagnetic wave having a frequency of 50 to 100 GHz, particularly 60 to 90 GHz, employed by a millimeter-wave radar.

[0022] The resistive layer 20 desirably has a sheet resistance of 260 to 500 Ω/□. This allows the electromagnetic wave absorber 1 to more reliably exhibit good electromagnetic wave absorption performance.

[0023] The resistive layer 20 has a specific resistance of, for example, 5 × 10-4 Ω • cm or more. Consequently, the resistive layer 20 has the desired sheet resistance even when the resistive layer 20 has a thickness of a given value (for example, 15 nm) or more. The resistive layer 20 thus has good chemical resistance.

[0024] The resistive layer 20 has a specific resistance of, for example, 100 × 10-4 Ω • cm or less. In this case, the resistive layer thickness required to impart the desired sheet resistance to the resistive layer 20 can be adjusted to a given value (for example, 500 nm) or less, and the time required to form the resistive layer 20 can be shortened. The specific resistance of the resistive layer 20 is desirably 50 × 10-4 Ω • cm or less and more desirably 30 × 10-4 Ω • cm or less.

[0025] The resistive layer 20 has a thickness of, for example, 15 to 500 nm. This allows the resistive layer 20 to have good chemical resistance and can shorten the time required to form the resistive layer 20. The resistive layer 20 desirably has a thickness of 15 to 200 nm.

[0026] When the resistive layer 20 includes indium oxide only or the resistive layer 20 is an ITO including indium oxide as the main component and less than 13 weight% of tin oxide, the resistive layer 20 desirably has a polycrystalline structure. This allows the resistive layer 20, even with a relatively small thickness, to have good chemical resistance. When the resistive layer 20 is an ITO including 5 weight% or more and less than 13 weight% of tin oxide, the resistive layer 20 desirably further includes a dopant that is silicon, magnesium, titanium, or nitrogen. This makes it likely that even when the resistive layer 20 has a polycrystalline structure, the resistive layer 20 has a specific resistance of 5 × 10-4 Ω • cm or more. When the resistive layer 20 is an ITO including indium oxide as the main component and 25 weight% or more of tin oxide, the resistive layer 20 typically has an amorphous structure. In this case, the amorphous structure of the ITO is extremely stable. The resistive layer 20 made of such an ITO has good chemical resistance.

[0027] The resistive layer 20 can be formed by sputtering such as DC magnetron sputtering, physical vapor deposition such as vacuum deposition, ion plating, or pulsed laser deposition, chemical vapor deposition such as thermal CVD, or spray pyrolysis deposition, for example, depending on the material of the resistive layer 20.

[0028] When the resistive layer 20 is an ITO having a polycrystalline structure, a film formed by sputtering and having an amorphous structure may be subjected to a heat treatment (annealing treatment) to form the resistive layer 20 having a polycrystalline structure. It should be noted that by adjusting the sputtering conditions such as a film formation temperature, the resistive layer 20 made of an ITO having a polycrystalline structure can be formed without the heat treatment after the sputtering.

[0029] As shown in FIG. 1, the resistive layer 20 is, for example, laminated on the polymer film 25 at an opposite surface to a surface at which the resistive layer 20 is in contact with the dielectric layer 10. The polymer film 25 functions as a support of the resistive layer 20. In the case where the resistive layer 20 is produced, for example, by sputtering, the polymer film 25 desirably has heat resistance high enough to resist heat applied in the film formation or a subsequent annealing treatment and is desirably made of a material providing a smooth surface. Moreover, since the polymer film 25 is disposed to cover the resistive layer 20, the polymer film 25 having high chemical resistance imparts high chemical resistance to the electromagnetic wave absorber 1. Therefore, examples of the material of the polymer film 25 include: polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); acrylic resins such as polymethyl methacrylate (PMMA); polycarbonate (PC); cycloolefin polymer (COP); aromatic polyetherketones such as polyetheretherketone (PEEK); aromatic polyamides (aramids); and polyimides. The material of the support of the resistive layer 20 is desirably PET in terms of the balance among good chemical resistance, the dimensional stability, and cost.

[0030] The polymer film 25 has a thickness of, for example, 10 to 150 µm, desirably 20 to 100 µm, and more desirably 30 to 80 pm. This can decrease the flexural rigidity of the polymer film 25, and can reduce occurrence of a crease or deformation in the case where the resistive layer 20 is formed on the polymer film 25.

[0031] The dielectric layer 10 has a relative permittivity of, for example, 1 to 10. This allows the electromagnetic wave absorber 1 to exhibit good electromagnetic wave absorption performance in a wide bandwidth (for example, a bandwidth of 2 GHz or more in the frequency band from 50 to 100 GHz). The relative permittivity of the dielectric layer 10 can be measured, for example, by cavity resonator perturbation.

[0032] The dielectric layer 10 may be a single layer, or may be a laminate consisting of a plurality of layers. When the dielectric layer 10 is a laminate consisting of a plurality of layers, the relative permittivity of the dielectric layer 10 can be determined by measuring the respective layers for the relative permittivity, multiplying the obtained relative permittivity values of the respective layers by the proportions of the thicknesses of the respective layers to the thickness of the whole dielectric layer 10, and adding the resultant values.

[0033] The material of the dielectric layer 10 is not limited to a particular one, but the dielectric layer 10 is made of, for example, a polymeric material. Examples of the polymeric material of the dielectric layer 10 include synthetic resins (including thermoplastic elastomers) such as acrylic resin, ethylene-vinyl acetate copolymer (EVA), polyvinyl chloride, polyurethane, acrylic urethane resin, polyolefin, polypropylene, polyethylene, silicone resin, polyethylene terephthalate, polyester, polystyrene, polyimide, polycarbonate, polyamide, polysulfone, polyethersulfone, and epoxy resin and synthetic rubbers such as polyisoprene rubber, polystyrene-butadiene rubber, polybutadiene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, butyl rubber, acrylic rubber, ethylene propylene rubber, and silicone rubber. One of these is used alone as the polymeric material of the dielectric layer 10, or a combination of two or more thereof is used as the polymeric material of the dielectric layer 10.

[0034] The dielectric layer 10 may be a foam in some cases. This makes it likely that the dielectric layer 10 has a low relative permittivity. Moreover, this can make the dielectric layer 10 lighter. Examples of the foam include olefin foams and polyester foams.

[0035] The thickness of the dielectric layer 10 is, for example, 50 to 2000 pm and desirably 100 to 1000 pm. This makes it easy to achieve both high dimensional accuracy and low cost.

[0036] In the vicinity of the rear surface of the electromagnetic wave absorber, the electrically conductive layer 30 reflects an electromagnetic wave to be absorbed by the electromagnetic wave absorber 1. The electrically conductive layer 30 has a sheet resistance of, for example, 0.001 to 30 Ω/□. This makes it easy for the electromagnetic wave absorber 1 to exhibit the desired electromagnetic wave absorption performance. For example, the electromagnetic wave absorber 1 can effectively attenuate an electromagnetic wave having a frequency of 50 to 100 GHz, particularly 60 to 90 GHz, employed by a millimeter-wave radar.

[0037] The material of the electrically conductive layer 30 includes, for example, at least one of aluminum, an aluminum alloy, aluminum nitride, copper, a copper alloy, copper nitride, and indium tin oxide. This allows the electromagnetic wave absorber 1 to exhibit the desired electromagnetic wave absorption performance. When the electrically conductive layer 30 includes ITO, the electrically conductive layer 30 is desirably an ITO including 5 to 15 weight% of tin oxide.

[0038] As shown in FIG. 1, the electrically conductive layer 30 may be laminated on the polymer film 35. The polymer film 35 functions as a support supporting the electrically conductive layer 30. In this case, the material of the polymer film 35 may be any one of those mentioned as examples of the material of the polymer film 25, or may be polyester, polypropylene, polyurethane, urethane acrylic resin, biaxially-oriented polypropylene (CPP), or vinylidene chloride resin. The polymer film 35 can be omitted in some cases.

[0039] A certain coating may be provided on a principal surface which is of either the resistive layer 20 or electrically conductive layer 30 and which faces the dielectric layer 10. This can prevent the component included in the dielectric layer 10 from spreading to the resistive layer 20 or electrically conductive layer 30 and affecting the properties of the resistive layer 20 or electrically conductive layer 30. Examples of the material of such a coating include silicon oxide such as SiO2, silicon nitride, aluminum oxide such as Al2O3, aluminum nitride (AlN), niobium oxide such as Nb2O5, strontium titanate (STO), and aluminum zinc oxide (AZO). In particular, when the material of the coating is AlN or AZO, the durability of the resistive layer 20 or electrically conductive layer 30 can be advantageously enhanced.

[0040] As shown in FIG. 1, the electromagnetic wave absorber 1 further includes, for example, an adhesive layer 40 and a separator 50. The adhesive layer 40 is disposed on an external side of the electrically conductive layer 30. The separator 50 is disposed in contact with the adhesive layer 40. The electromagnetic wave absorber 1 can be easily attached to an article such as a molded article by peeling off the separator 50 to bare the adhesive layer 40 and pressing the adhesive layer 40 against the article. The adhesive layer 40 can be protected by the separator 50 until the electromagnetic wave absorber 1 is attached to an article.

[0041] The adhesive layer 40 includes, for example, a pressure sensitive adhesive such as an acrylic adhesive, a rubber adhesive, a silicone adhesive, or an urethane adhesive.

[0042] As shown in FIG. 2, an electromagnetic wave absorber-attached molded article 100, for example, can be produced using the electromagnetic wave absorber 1. The electromagnetic wave absorber-attached molded article 100 includes a molded article 70 and the electromagnetic wave absorber 1 attached to the molded article 70. Examples of the molded article 70 include automotive parts such as a bumper.

[0043] An example of a method for producing the electromagnetic wave absorber 1 will be described. The resistive layer 20 is formed on the polymer film 25 by a film formation method such as sputtering. In addition, a laminate in which the electrically conductive layer 30 is formed on the polymer film 35 is prepared.

[0044] Next, a resin composition molded to have a predetermined thickness and forming the dielectric layer 10 is put on one principal surface of the electrically conductive layer 30. After that, one principal surface of the resistive layer 20 is placed on the resin composition forming the dielectric layer 10. The resin composition is cured if necessary. The electromagnetic wave absorber 1 can be produced in this manner. According to this method, the thickness of the dielectric layer 10 is controlled easily, and thus the electromagnetic wave absorber 1 can be produced so that the electromagnetic wave absorber 1 can effectively absorb an electromagnetic wave having a wavelength to be absorbed. Moreover, since the resistive layer 20 and electrically conductive layer 30 are formed separately, the time required to produce the electromagnetic wave absorber 1 is short and the production cost of the electromagnetic wave absorber 1 is low. An adhesive or a pressure sensitive adhesive may be used to adhere the dielectric layer 10 and electrically conductive layer 30 or resistive layer 20.

EXAMPLES



[0045] Hereinafter, the present invention will be described in more detail by examples. The present invention is not limited to the examples given below. First, methods for measuring the properties of resistive layers according to Examples and Comparative Examples and a method for evaluating samples according to Examples and Comparative Examples will be described.

[X-ray diffraction]



[0046] In Examples and Comparative Examples, the thickness was measured for the resistive layers by X-ray reflectivity using an X-ray diffractometer (manufactured by Rigaku Corporation, product name: RINT2200). X-ray diffraction patterns of the resistive layers were also obtained using the X-ray diffractometer. CuKα radiation was used as the X-ray. Whether the resistive layers have a polycrystalline structure or an amorphous structure was confirmed from the obtained X-ray diffraction patterns. The results are shown in Table 1.

[Sheet resistance]



[0047] The sheet resistance of the resistive layers according to Examples and Comparative Examples not having undergone a chemical immersion treatment was measured by an eddy current method according to Japanese Industrial Standards (JIS) Z 2316 using a non-contact resistance measurement apparatus (manufactured by NAPSON CORPORATION, product name: NC-80MAP). The results are shown in Table 1. Additionally, the resistive layers having undergone a chemical immersion treatment were also measured for the sheet resistance.

[Specific resistance]



[0048] In each of Examples and Comparative Examples, the specific resistance of the resistive layer was determined by calculating a product of the thickness measured as above for the resistive layer and the sheet resistance measured as above for the resistive layer not having undergone a chemical immersion treatment. The results are shown in Table 1.

[Relative permittivity]



[0049] The relative permittivity of the dielectric layers according to Examples and Comparative Examples at 10 GHz was measured by cavity resonator perturbation using a network analyzer (manufactured by Agilent Technologies, Inc., product name: N5230C) and cavity resonator (Cavity Resonator CP-531, manufactured by Kanto Electronics Application Development Inc.).

[Electromagnetic wave absorption properties]



[0050] The return loss (absolute value of the amount of reflection) was measured according to JIS R 1679:2007 using a 76-GHz millimeter wave perpendicularly incident on a surface of each of a sample A (not having undergone a chemical immersion treatment) and sample B (having undergone a chemical immersion treatment) according to each of Examples and Comparative Examples. The results are shown in Table 1. Moreover, comprehensive evaluation was performed for Examples and Comparative Examples according to the following measures. The results are shown in Table 1.
a: Both the sample A and sample B have a return loss of 20 dB or more.
b: Either the sample A or sample B or both the sample A and sample B have a return loss of 10 dB or more and less than 20 dB.
x: Either the sample A or sample B or both the sample A and sample B have a return loss of less than 10 dB.

<Example 1>



[0051] A film made of amorphous In2O3 was formed on a 38-µm-thick PET film (DIAFOIL manufactured by Mitsubishi Chemical Corporation) by a DC magnetron sputtering method using a target material made of In2O3. The film was subjected to a heat treatment in air at a temperature of 150°C for 3 hours to crystallize the In2O3. A resistive layer according to Example 1 was formed in this manner. The thickness, sheet resistance, and specific resistance of the resistive layer according to Example 1 are shown in Table 1. A dielectric layer according to Example 1 was produced by press-molding an acrylic resin having a relative permittivity of 2.6 to have a thickness of 560 µm. As an electrically conductive layer according to Example 1, an aluminum foil having a sheet resistance of 0.002 Ω/□ was prepared. The resistive layer according to Example 1 not having undergone a chemical immersion treatment was adhered to one principal surface of the dielectric layer according to Example 1 so that the resistive layer according to Example 1 was in contact with the principal surface. Additionally, the electrically conductive layer according to Example 1 was brought into contact with and adhered to the other principal surface of the dielectric layer according to Example 1. A sample A according to Example 1 was produced in this manner.

[0052] A resistive layer as formed above in Example 1 was formed on a PET film as used above. A chemical immersion treatment was performed in which the PET film having the resistive layer formed thereon was immersed in a 5 weight% aqueous solution of NaOH for 5 minutes, followed by air drying to produce a resistive layer having undergone the chemical immersion treatment. The temperature of the aqueous NaOH solution used in the chemical immersion treatment was 40°C. A sample B according to Example 1 was prepared in the same manner as for the sample A, except that the resistive layer having undergone the chemical immersion treatment was used instead of the resistive layer according to Example 1 not having undergone the chemical immersion treatment.

<Examples 2 and 3>



[0053] Resistive layers according to Examples 2 and 3 made of In2O3 were formed in the same manner as in Example 1, except that the sputtering conditions were changed so that the thickness of the resistive layers and the sheet resistance of the resistive layers would be as shown in Table 1. In the formation of the resistive layers according to Examples 2 and 3, the film made of amorphous In2O3 and obtained by the sputtering was crystallized by a heat treatment performed under the same conditions as in Example 1. Samples A (not having undergone the chemical immersion treatment) and samples B (having undergone the chemical immersion treatment) according to Examples 2 and 3 were produced in the same manner as in Example 1, except that the resistive layer according to Example 2 or 3 was used instead of the resistive layer according to Example 1.

<Example 4>



[0054] A resistive layer according to Example 4 made of an ITO including 2.5 weight% of tin oxide was formed in the same manner as in Example 1, except that ITO was used as a target material and the sputtering conditions were changed so that the thickness of the resistive layer and the sheet resistance of the resistive layer would be as shown in Table 1. In the formation of the resistive layer according to Example 4, the amorphous ITO film obtained by the sputtering was crystallized by a heat treatment performed under the same conditions as in Example 1. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 4 were produced in the same manner as in Example 1, except that the resistive layer according to Example 4 was used instead of the resistive layer according to Example 1.

<Example 5>



[0055] A resistive layer according to Example 5 made of an ITO including 3.3 weight% of tin oxide was formed in the same manner as in Example 1, except that ITO was used as a target material and the sputtering conditions were changed so that the thickness of the resistive layer and the sheet resistance of the resistive layer would be as shown in Table 1. In the formation of the resistive layer according to Example 5, the amorphous ITO film obtained by the sputtering was crystallized by a heat treatment performed under the same conditions as in Example 1. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 5 were produced in the same manner as in Example 1, except that the resistive layer according to Example 5 was used instead of the resistive layer according to Example 1.

<Example 6>



[0056] A resistive layer according to Example 6 made of a material including 7.5 weight% of SnO2 and 2.5 weight% of SiO2 in addition to In2O3 was formed in the same manner as in Example 1, except that a target material including In2O3, SnO2, and SiO2 was used and the sputtering conditions were changed so that the thickness of the resistive layer and the sheet resistance of the resistive layer would be as shown in Table 1. In the formation of the resistive layer according to Example 6, the amorphous film obtained by the sputtering was crystallized by a heat treatment performed under the same conditions as in Example 1. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 6 were produced in the same manner as in Example 1, except that the resistive layer according to Example 6 was used instead of the resistive layer according to Example 1.

<Example 7>



[0057] A resistive layer according to Example 7 made of a material including 7.5 weight% of SnO2 and 2.5 weight% of MgO in addition to In2O3 was formed in the same manner as in Example 1, except that a target material including In2O3, SnO2, and MgO was used and the sputtering conditions were changed so that the thickness of the resistive layer and the sheet resistance of the resistive layer would be as shown in Table 1. In the formation of the resistive layer according to Example 7, the amorphous film obtained by the sputtering was crystallized by a heat treatment performed under the same conditions as in Example 1. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 7 were produced in the same manner as in Example 1, except that the resistive layer according to Example 7 was used instead of the resistive layer according to Example 1.

<Example 8>



[0058] A resistive layer according to Example 8 made of a material including 7.5 weight% of SnO2 and 2.5 weight% of TiO2 in addition to In2O3 was formed in the same manner as in Example 1, except that a target material including In2O3, SnO2, and TiO2 was used and the sputtering conditions were changed so that the thickness of the resistive layer and the sheet resistance of the resistive layer would be as shown in Table 1. In the formation of the resistive layer according to Example 8, the amorphous film obtained by the sputtering was crystallized by a heat treatment performed under the same conditions as in Example 1. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 8 were produced in the same manner as in Example 1, except that the resistive layer according to Example 8 was used instead of the resistive layer according to Example 1.

<Example 9>



[0059] A resistive layer according to Example 9 made of a material including 7.5 weight% of SnO2 and 3 atomic% of nitrogen in addition to In2O3 was formed in the same manner as in Example 1, except that a target material including In2O3 and SnO2 and a reactive gas including nitrogen gas were used and the sputtering conditions were changed so that the thickness of the resistive layer and the sheet resistance of the resistive layer would be as shown in Table 1. In the formation of the resistive layer according to Example 9, the amorphous film obtained by the sputtering was crystallized by a heat treatment performed under the same conditions as in Example 1. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 9 were produced in the same manner as in Example 1, except that the resistive layer according to Example 9 was used instead of the resistive layer according to Example 1.

<Example 10>



[0060] A resistive layer according to Example 10 made of a material including 10 weight% of SnO2 and 5 weight% of SiO2 in addition to In2O3 was formed in the same manner as in Example 1, except that a target material including In2O3, SnO2, and SiO2 was used and the sputtering conditions were changed so that the thickness of the resistive layer and the sheet resistance of the resistive layer would be as shown in Table 1. In the formation of the resistive layer according to Example 10, the amorphous film obtained by the sputtering was crystallized by a heat treatment performed under the same conditions as in Example 1. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 10 were produced in the same manner as in Example 1, except that the resistive layer according to Example 10 was used instead of the resistive layer according to Example 1.

<Example 11>



[0061] A resistive layer according to Example 11 made of an amorphous ITO including 30 weight% of SnO2 was formed on a 38-µm-thick PET film (DIAFOIL manufactured by Mitsubishi Chemical Corporation) by a DC magnetron sputtering method using ITO as a target material. In the formation of the resistive layer according to Example 11, a heat treatment was not performed after the sputtering. A dielectric layer according to Example 11 was produced by press-molding an acrylic resin having a relative permittivity of 2.5 to have a thickness of 560 µm. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 11 were produced in the same manner as in Example 1, except that the resistive layer and dielectric layer according to Example 11 were used instead of the resistive layer and dielectric layer according to Example 1.

<Example 12>



[0062] A resistive layer according to Example 12 made of an amorphous ITO including 50 weight% of tin oxide was formed in the same manner as in Example 11, except that ITO was used as a target material and the sputtering conditions were changed so that the thickness of the resistive layer and the sheet resistance of the resistive layer would be as shown in Table 1. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 12 were produced in the same manner as in Example 11, except that the resistive layer according to Example 12 was used instead of the resistive layer according to Example 11.

<Example 13>



[0063] A film made of an amorphous ITO including 10 weight% of tin oxide was formed on a 38-µm-thick PET film (DIAFOIL manufactured by Mitsubishi Chemical Corporation) by a DC magnetron sputtering method. The film was crystallized by a heat treatment in air at a temperature of 150°C for 3 hours. An electrically conductive layer according to Example 13 was formed in this manner. The thickness of the electrically conductive layer according to Example 13 was 120 nm. The sheet resistance of the electrically conductive layer according to Example 13 was 20 Ω/□. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 13 were produced in the same manner as in Example 1, except that the electrically conductive layer according to Example 13 was used instead of the electrically conductive layer according to Example 1.

<Example 14>



[0064] A film made of SnO2 was formed on a 50-µm-thick polyimide film (Upilex manufactured by Ube Industries, Ltd.) by an RF magnetron sputtering method (substrate temperature: room temperature) using SnO2 as a target material. This film was crystallized by a heat treatment (annealing treatment) at 300°C for 1 hour. A resistive layer according to Example 14 made of SnO2 was formed in this manner. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 14 were produced in the same manner as in Example 11, except that the resistive layer according to Example 14 was used instead of the resistive layer according to Example 11.

<Example 15>



[0065] A resistive layer according to Example 15 made of fluorine-doped tin oxide (fluorine content: 5 atomic%) was formed on a 50-µm-thick polyimide film (Upilex manufactured by Ube Industries, Ltd.) by an RF magnetron sputtering method (substrate temperature: 200°C) using a mixture of SnF2 powder and SnO2 powder as a target material. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 15 were produced in the same manner as in Example 11, except that the resistive layer according to Example 15 was used instead of the resistive layer according to Example 11.

<Example 16>



[0066] A resistive layer according to Example 16 made of antimony-doped tin oxide (antimony content: 4 atomic%) was formed on a 50-µm-thick polyimide film (Upilex manufactured by Ube Industries, Ltd.) by a reactive MF-AC magnetron sputtering method (frequency of power source: 200 kHz; substrate temperature: 200°C) using a Sn-Sb alloy as a target material and oxygen gas as a reactive gas. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 16 were produced in the same manner as in Example 11, except that the resistive layer according to Example 16 was used instead of the resistive layer according to

Example 11.


<Example 17>



[0067] A resistive layer according to Example 17 made of niobium-doped titanium oxide (niobium content: 8 atomic%) was formed on a 50-µm-thick polyimide film (Upilex manufactured by Ube Industries, Ltd.) by an RF magnetron sputtering method (substrate temperature: room temperature) using Nb-containing TiO2 as a target material. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Example 17 were produced in the same manner as in Example 11, except that the resistive layer according to Example 17 was used instead of the resistive layer according to Example 11.

<Comparative Example 1>



[0068] A resistive layer according to Comparative Example 1 made of a polycrystalline material including ZnO as a main component and 3 weight% of Ga2O3 was formed on a 38-µm-thick PET film (DIAFOIL manufactured by Mitsubishi Chemical Corporation) using a target material including ZnO and Ga2O3 by a DC magnetron sputtering method, in which the sputtering conditions were adjusted so that the thickness of the resistive layer and sheet resistance of the resistive layer would be as shown in Table 1. In the formation of the resistive layer according to Comparative Example 1, a heat treatment was not performed after the sputtering. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Comparative Example 1 were produced in the same manner as in Example 1, except that the resistive layer according to Comparative Example 1 was used instead of the resistive layer according to Example 1.

<Comparative Example 2>



[0069] A resistive layer according to Comparative Example 2 made of an amorphous ITO including 10 weight% of tin oxide was formed on a 38-µm-thick PET film (DIAFOIL manufactured by Mitsubishi Chemical Corporation) using ITO as a target material by a DC magnetron sputtering method, in which the sputtering conditions were adjusted so that the thickness and sheet resistance of the resistive layer would be as shown in Table 1. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Comparative Example 2 were produced in the same manner as in Example 1, except that the resistive layer according to Comparative Example 2 was used instead of the resistive layer according to Example 1.

<Comparative Example 3>



[0070] A resistive layer according to Comparative Example 3 made of an amorphous ITO including 7.5 weight% of tin oxide was formed in the same manner as in Comparative Example 2, except that ITO was used as a target material and the sputtering conditions were changed so that the thickness of the resistive layer and the sheet resistance of the resistive layer would be as shown in Table 1. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Comparative Example 3 were produced in the same manner as in Example 1, except that the resistive layer according to Comparative Example 3 was used instead of the resistive layer according to Example 1.

<Comparative Example 4>



[0071] A resistive layer according to Comparative Example 4 made of an ITO including 2.5 weight% of tin oxide was formed in the same manner as in Example 1, except that ITO was used as a target material and the sputtering conditions were changed so that the thickness of the resistive layer and the sheet resistance of the resistive layer would be as shown in Table 1. In the formation of the resistive layer according to Comparative Example 4, the amorphous ITO film obtained by the sputtering was crystallized by a heat treatment performed under the same conditions as in Example 1. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Comparative Example 4 were produced in the same manner as in Example 1, except that the resistive layer according to Comparative Example 4 was used instead of the resistive layer according to Example 1.

<Comparative Example 5>



[0072] A resistive layer according to Comparative Example 5 made of an ITO including 7.5 weight% of tin oxide was formed in the same manner as in Example 1, except that ITO was used as a target material and the sputtering conditions were changed so that the thickness of the resistive layer and the sheet resistance of the resistive layer would be as shown in Table 1. In the formation of the resistive layer according to Comparative Example 5, the amorphous ITO film obtained by the sputtering was crystallized by a heat treatment performed under the same conditions as in Example 1. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Comparative Example 5 were produced in the same manner as in Example 1, except that the resistive layer according to Comparative Example 5 was used instead of the resistive layer according to Example 1.

<Comparative Example 6>



[0073] A resistive layer according to Comparative Example 6 made of a polycrystalline material including ZnO as a main component and 3 weight% of Al2O3 was formed in the same manner as in Comparative Example 1, except that a target material including ZnO and Al2O3 was used and the sputtering conditions were changed so that the thickness of the resistive layer and the sheet resistance of the resistive layer would be as shown in Table 1. In the formation of the resistive layer according to Comparative Example 6, a heat treatment was not performed after the sputtering. A sample A (not having undergone the chemical immersion treatment) and sample B (having undergone the chemical immersion treatment) according to Comparative Example 6 were produced in the same manner as in Example 1, except that the resistive layer according to Comparative Example 6 was used instead of the resistive layer according to Example 1.

[0074] As shown in Table 1, it is indicated that when the resistive layer is made of any of the given materials, good chemical resistance can be exhibited.
[Table 1]
 Resistive layerElectrically conductive layerReturn lossComparative evaluation
MaterialStructureThickness [nm]Initial sheet resistance [Ω/□]Initial specific resistance [× 10-4 Ω•cm]Sheet resistance after chemical immersion treatment [Ω/□]Absolute value of sheet resistance difference occurring from chemical immersion treatment [Ω/□]MaterialSheet resistance [Ω/□]Sample A not having undergone chemical immersion treatment [dB]Sample B having undergone chemical immersion treatment [dB]
Main componentDopant
Example 1 In2O3 - - Polycrystalline 26 370 9.6 379 9 Al 0.002 32 31 a
Example 2 In2O3 - - Polycrystalline 23 450 10 462 12 Al 0.002 21 20 a
Example 3 In2O3 - - Polycrystalline 32 295 9.4 294 1 Al 0.002 20 20 a
Example 4 In2O3 SnO2 2.5 wt% - Polycrystalline 20 390 7.8 402 12 Al 0.002 27 25 a
Example 5 In2O3 SnO2 3.3 wt% - Polycrystalline 17 342 5.8 355 13 Al 0.002 26 28 a
Example 6 In2O3 SnO2 7.5wt% SiO2 2.5 wt% Polycrystalline 22 390 8.6 395 5 Al 0.002 27 26 a
Example 7 In2O3 SnO2 7.5 wt% MgO 2.5 wt% Polycrystalline 20 360 7.2 362 2 Al 0.002 29 29 a
Example 8 In2O3 SnO2 7.5 wt% TiO2 2.5 wt% Polycrystalline 28 418 12 428 10 Al 0.002 23 22 a
Example 9 In2O3 SnO2 7.5 wt% Nitrogen 3 at% Polycrystalline 27 354 9.6 360 6 Al 0.002 27 28 a
Example 10 In2O3 SnO2 10 wt% SiO2 5 wt% Polycrystalline 85 430 37 428 2 Al 0.002 22 22 a
Example 11 In2O3 SnO2 30 wt% - Amorphous 45 405 18 435 30 Al 0.002 24 22 a
Example 12 In2O3 SnO2 50 wt% - Amorphous 101 345 35 354 9 Al 0.002 26 27 a
Example 13 In2O3 - - Polycrystalline 26 370 9.6 379 9 ITO 20 30 30 a
Example 14 SnO2 - - Polycrystalline 205 440 90 438 2 Al 0.002 21 21 a
Example 15 SnO2 Fluorine 5 at% - Polycrystalline 97 390 38 393 3 Al 0.002 28 27 a
Example 16 SnO2 Antimony 4 at% - Polycrystalline 49 405 20 401 4 Al 0.002 24 25 a
Example 17 TiO2 Niobium 8 at% - Polycrystalline 19 372 7 382 10 Al 0.002 31 30 a
Comparative Example 1 ZnO Ga2O3 3 wt%   Polycrystalline 72 415 30 2360 1945 Al 0.002 23 1 x
Comparative Example 2 In2O3 SnO2 10 wt%   Amorphous 27 354 9.6 980 626 Al 0.002 28 2 x
Comparative Example 3 In2O3 SnO2 7.5 wt%   Amorphous 28 401 11 863 462 Al 0.002 24 3 x
Comparative Example 4 In2O3 SnO2 2.5 wt%   Polycrystalline 14 679 9.5 802 123 Al 0.002 9 6 x
Comparative Example 5 In2O3 SnO2 7.5 wt%   Polycrystalline 11 412 4.5 611 199 Al 0.002 24 11 b
Comparative Example 6 ZnO Al2O3 3 wt%   Polycrystalline 145 398 58 1826 1428 Al 0.002 25 1 x



Claims

1. An electromagnetic wave absorber, comprising:

a dielectric layer;

a resistive layer that is disposed on one principal surface of the dielectric layer; and

an electrically conductive layer that is disposed on the other principal surface of the dielectric layer and has a sheet resistance lower than a sheet resistance of the resistive layer, wherein

the resistive layer has a sheet resistance of 200 to 600 Ω/□, and

when the resistive layer is subjected to an immersion treatment in which the resistive layer is immersed in a 5 weight% aqueous solution of NaOH for 5 minutes, an absolute value of a difference between a sheet resistance of the resistive layer before the immersion treatment and a sheet resistance of the resistive layer after the immersion treatment is less than 100 Ω/□.


 
2. The electromagnetic wave absorber according to claim 1, wherein the resistive layer comprises at least one of tin oxide, titanium oxide, and indium oxide as a main component.
 
3. The electromagnetic wave absorber according to claim 2, wherein the resistive layer further comprises a dopant that comprises at least one element other than a metal element included in the main component.
 
4. The electromagnetic wave absorber according to any one of claims 1 to 3, wherein the resistive layer has a specific resistance of 5 × 10-4 Ω • cm or more.
 
5. The electromagnetic wave absorber according to any one of claims 1 to 4, wherein the resistive layer has a thickness of 15 to 500 nm.
 
6. The electromagnetic wave absorber according to any one of claims 1 to 5, wherein the resistive layer is laminated on a polymer film at an opposite surface to a surface at which the resistive layer is in contact with the dielectric layer.
 
7. The electromagnetic wave absorber according to any one of claims 1 to 6, wherein the dielectric layer has a relative permittivity of 1 to 10.
 
8. The electromagnetic wave absorber according to any one of claims 1 to 7, wherein the dielectric layer is made of a polymeric material.
 
9. The electromagnetic wave absorber according to any one of claims 1 to 8, wherein the electrically conductive layer has a sheet resistance of 0.001 to 30 Ω/□.
 
10. The electromagnetic wave absorber according to any one of claims 1 to 9, wherein the electrically conductive layer is made of at least one of aluminum, an aluminum alloy, aluminum nitride, copper, a copper alloy, copper nitride, and indium tin oxide.
 
11. An electromagnetic wave absorber-attached molded article, comprising:

a molded article; and

the electromagnetic wave absorber according to any one of claims 1 to 10 attached to the molded article.


 




Drawing







Search report










Cited references

REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description