WO2013002276A1 - 近傍界ノイズ抑制フィルム - Google Patents
近傍界ノイズ抑制フィルム Download PDFInfo
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- WO2013002276A1 WO2013002276A1 PCT/JP2012/066417 JP2012066417W WO2013002276A1 WO 2013002276 A1 WO2013002276 A1 WO 2013002276A1 JP 2012066417 W JP2012066417 W JP 2012066417W WO 2013002276 A1 WO2013002276 A1 WO 2013002276A1
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
Definitions
- the present invention relates to an inexpensive noise suppression film capable of absorbing electromagnetic waves of several hundred MHz to several GHz in the near field in portable information terminals such as mobile phones and smartphones, electronic devices such as personal computers, and the like.
- noise suppression films contain a magnetic material and / or a conductive material.
- Japanese Patent Application Laid-Open No. 2010-153542 discloses a base material, a conductive layer made of a conductive coating material containing metal or carbon particles such as Cu, scales, or fine wires, and a soft magnetic material such as ferrite, sendust, and permalloy.
- the electromagnetic wave noise suppression film which has a magnetic layer which consists of a magnetic coating material containing this is disclosed.
- JP-A-2006-278433 describes, for example, a calendar process comprising a soft magnetic powder such as amorphous flakes having a composition of Fe bal —Cu 1 —Si 12.5 —Nb 3 —Cr 1 —B 12 (atomic%) and a resin.
- a composite electromagnetic wave noise suppression film in which two or more sheets are laminated and integrated by calendering is disclosed.
- none of the noise suppression films disclosed in Japanese Patent Application Laid-Open No. 2010-153542 or Japanese Patent Application Laid-Open No. 2006-278433 does not have a sufficient ability to absorb near-field noise, and a magnetic material and / or a conductive material is kneaded into a resin. Therefore, there is a problem that it is difficult to reduce the thickness and the manufacturing cost is high.
- Japanese Patent Laid-Open No. 2006-279912 discloses that the reflection coefficient (S 11 ) is -10 dB or less and the noise suppression effect ( ⁇ P loss / P in ) is 0.5 or more for electromagnetic noise generated in the quasi-microwave band.
- sputtered thin films such as AlO, CoAlO, and CoSiO are disclosed as near-field electromagnetic wave noise suppressing thin films whose resistance values are controlled to 10 to 1000 ⁇ / ⁇ to match the spatial characteristic impedance Z (377 ⁇ ).
- the electromagnetic wave absorbing ability of the near-field electromagnetic noise suppression thin film is not sufficient.
- Japanese Patent Laid-Open No. 2008-53383 describes a graphite film having different thermal conductivity in the plane direction and thickness direction, and soft magnetic materials such as Fe, Co, FeSi, FeNi, FeCo, FeSiAl, FeCrSi, and FeBSiC formed thereon
- an electromagnetic wave absorbing / shielding film excellent in heat dissipation characteristics comprising a soft magnetic layer containing Mn-Zn-based, Ba-Fe-based, Ni-Zn-based ferrite, and carbon particles.
- the electromagnetic wave absorbing ability of this radio wave absorbing / shielding film is not sufficient.
- Japanese Patent Laid-Open No. 05-226873 describes in Example 1 that after depositing 12 nm thick nickel on a 50 ⁇ m thick polyimide film, it was heated in air at 200 ° C. for 1 hour. An electromagnetic wave absorber laminated through an adhesive is disclosed. However, in Japanese Patent Laid-Open No. 05-226873, (1) When the surface resistance of a Ni thin film formed by vapor deposition on a polyethylene terephthalate film is about several tens of ohms / ⁇ , it has an excellent ability to absorb near-field electromagnetic noise.
- Japanese Patent Application Laid-Open No. 05-226873 does not have the purpose of reducing the variation in electromagnetic wave absorption ability and the change with time, and thus having an excellent electromagnetic wave absorption ability stably. Therefore, the heat treatment conditions in JP-A-05-226873 are as wide as 50 to 400 ° C. and 30 minutes to 5 hours, and in Example 1, it is 1 hour at 200 ° C. Furthermore, Japanese Patent Application Laid-Open No. 05-226873 does not consider any problem of heat shrinkage of the film during the heat treatment of the Ni thin film. Therefore, Japanese Patent Laid-Open No.
- Ni, thin film base materials such as polyimide, polyethylene terephthalate (PET), polyphenylene sulfide, vinyl chloride and other plastic sheets, brass, copper, iron, stainless steel, aluminum and other metals.
- PET polyethylene terephthalate
- polyphenylene sulfide polyphenylene sulfide
- vinyl chloride plastic sheets
- brass copper, iron, stainless steel, aluminum and other metals.
- a heat resistant resin called a polyimide film that does not thermally shrink at a heat treatment temperature is used.
- JP-A-2006-295101 is a noise suppressor having a support and a nickel thin film formed on the support, and has a volume resistivity R1 ( ⁇ ⁇ ) converted from an actual measurement value of the surface resistance of the nickel thin film. cm) and the volume resistivity R0 ( ⁇ ⁇ cm) of nickel satisfy a condition of 0.5 ⁇ logR1 ⁇ logR0 ⁇ 3, and disclose an noise suppressor having an average thickness of 2 to 100 nm. Nickel is a fine cluster in the thin film.
- JP-A-2006-295101 does not describe anything about heat treatment.
- Japanese Patent Laid-Open No. 08-59867 discloses that a transparent polymer film base material is made of a metal such as gold, silver, copper, indium oxide, tin oxide, indium oxide-tin oxide mixture and / or a metal oxide on at least one side.
- a transparent conductive film provided with a conductive layer is disclosed.
- Japanese Patent Application Laid-Open No. 08-59867 describes that it is desirable to perform annealing treatment at a temperature of about 120 ° C. to 200 ° C. for about 1 to 30 minutes after the transparent conductive layer is provided.
- the transparent conductive layer to be heat-treated in JP-A-08-59867 is not an electromagnetic wave absorbing layer, and the transparent conductive layer shown in the examples is only ITO (metal oxide).
- an object of the present invention is to provide an inexpensive noise suppression film that stably has high absorptivity for electromagnetic wave noise of several hundred MHz to several GHz and is suitable for portable information terminals, electronic devices, and the like. .
- a stretched plastic film made of polyethylene terephthalate is significantly inferior in heat resistance compared to metal and may be subject to large heat shrinkage due to heating.
- Ni deposited thin film formed on plastic film is heat-treated at a temperature in the range of 110 to 170 ° C for 10 minutes to 1 hour, not only the electromagnetic wave absorbing ability of Ni thin film is improved but also the electromagnetic wave absorbing ability is improved.
- the present inventors have found that a noise suppressing film can be obtained that has reduced variations and changes over time, and thus stably has excellent electromagnetic wave absorption ability, and has arrived at the present invention.
- the noise suppression film of the present invention in which the variation in electromagnetic wave noise absorption ability is reduced is obtained by forming a Ni thin film by vapor deposition on one surface of a stretched plastic film made of polyethylene terephthalate, and then within a range of 110 to 170 ° C.
- the light transmittance of the Ni thin film (laser light with a wavelength of 660 nm) is 3 to 50%, and (b) 10 cm x 10 cm of the Ni thin film.
- the heat treatment temperature of the Ni thin film is preferably 130 to 160 ° C.
- the heat treatment time for the Ni thin film is preferably 20 to 40 minutes.
- a protective film is laminated on the surface of the Ni thin film.
- the noise suppression film of the present invention is formed by heat treatment after vapor deposition of a Ni thin film, it has high absorptivity with respect to electromagnetic noise of several hundred MHz to several GHz, and the surface resistance is stabilized and the change over time is substantially reduced. Therefore, there is no change in electromagnetic wave absorption ability with time.
- the noise suppression film of the present invention having such features is effective in absorbing electromagnetic noise of several hundred MHz to several GHz in the near field in various portable information terminals such as mobile phones and smartphones and electronic devices such as personal computers. It is.
- FIG. 3 (a) is a plan view showing a state in which the surface resistance of the noise suppression film is measured using the apparatus shown in FIG.
- FIG. 3B is a cross-sectional view taken along line AA of FIG.
- FIG. 3B is a cross-sectional view taken along line AA of FIG.
- FIG. 3B is a cross-sectional view taken along line AA of FIG.
- It is a fragmentary sectional front view which shows the system which evaluates the electromagnetic wave absorption ability of a noise suppression film.
- FIG. 5 (a) is a plan view showing a state in which heat treatment is performed on a Ni vapor deposition film using the apparatus of FIG. 5 (a).
- 2 is a graph showing the maximum value and the minimum value of Rtp at 0.1 to 6 GHz of the deposited film samples of Example 1 and Comparative Example 1.
- 2 is a graph showing an Rtp distribution at 6 GHz of the deposited film sample of Example 1.
- FIG. 6 is a graph showing the distribution of Rtp at 6 GHz in the deposited film sample of Comparative Example 1.
- 6 is a graph showing the maximum value and the minimum value of Rtp at 0.1 to 6 GHz of the deposited film samples of Example 2 and Comparative Example 2.
- 4 is a graph showing the distribution of Rtp at 6 GHz in the deposited film sample of Example 2.
- 6 is a graph showing the distribution of Rtp at 6 GHz in the deposited film sample of Comparative Example 2.
- 6 is a graph showing the maximum value and the minimum value of Rtp at 0.1 to 6 GHz of the deposited film samples of Example 3 and Comparative Example 3.
- 4 is a graph showing an Rtp distribution at 6 GHz of the deposited film sample of Example 3.
- FIG. 6 is a graph showing the distribution of Rtp at 6 GHz in the deposited film sample of Comparative Example 3.
- 6 is a graph showing the maximum value and the minimum value of Rtp at 0.1 to 6 GHz of the deposited film samples of Example 4 and Comparative Example 4.
- 4 is a graph showing the distribution of Rtp at 6 GHz in the deposited film sample of Example 4.
- 6 is a graph showing the distribution of Rtp at 6 GHz in the deposited film sample of Comparative Example 4.
- 6 is a graph showing P loss / P in of a deposited film sample of Example 4 at 0.1 to 6 GHz.
- 7 is a graph showing Rtp at 0.1 to 6 GHz of a vapor-deposited film sample subjected to heat treatment of Comparative Example 5 and a vapor-deposited film sample not subjected to heat treatment.
- 6 is a graph showing the maximum and minimum values of Rtp at 0.1 to 6 GHz of a vapor-deposited film sample subjected to heat treatment of Comparative Example 6 and a vapor-deposited film sample not subjected to heat treatment.
- a noise suppression film 10 of the present invention is obtained by forming a Ni thin film 2 on one surface of a stretched plastic film 1 made of polyethylene terephthalate and then heat-treating it.
- the stretched plastic film 1 made of polyethylene terephthalate has sufficient insulation, heat resistance and strength.
- the thickness of the plastic film 10 may be about 10 to 100 ⁇ m, and particularly preferably 10 to 30 ⁇ m.
- Ni thin film 2 can be formed by a known method such as a sputtering method or a vacuum deposition method.
- the thickness of the Ni thin film 2 is represented by the transmittance of laser light having a wavelength of 660 nm (simply called “light transmittance”).
- the light transmittance is obtained by averaging measured values at a plurality of arbitrary locations on the Ni thin film 2. When the number of measurement points is 5 or more, the average value of the light transmittance is stable.
- the thickness of the plastic film 1 is 30 ⁇ m or less, the light transmittance of the plastic film 1 itself is almost 100%, so that the light transmittance of the noise suppression film 10 matches the light transmittance of the Ni thin film 2.
- a value obtained by subtracting the light transmittance of the plastic film 1 from the light transmittance of the noise suppression film 10 is the light transmittance of the Ni thin film 2.
- the light transmittance of Ni thin film 2 needs to be in the range of 3-50%. When the light transmittance is less than 3%, the Ni thin film 2 becomes too thick to behave like a metal foil, the electromagnetic wave reflectance is high, and the electromagnetic wave noise absorption ability is low. On the other hand, if the light transmittance is more than 50%, the Ni thin film 2 is too thin and the electromagnetic wave absorbing ability is insufficient.
- the light transmittance of the Ni thin film 2 is preferably 5 to 45%, more preferably 8 to 30%.
- the length 10 cm ⁇ width A pair of electrodes 11 and 11 each having a 1 cm ⁇ 0.5 mm-thick electrode body 11a and a 1 cm wide ⁇ 0.5 mm-thick electrode extension 11b extending from the central side of the electrode body 11a are placed.
- a transparent acrylic plate 12 of 10 cm ⁇ 10 cm ⁇ 5 mm thickness is placed on the test piece TP1 and both electrodes 11 and 11 so as to completely cover them, and a circle of 10 cm in diameter is placed on the transparent acrylic plate 12 After placing the columnar weight 13 (3.85 kg), the surface resistance is obtained from the current flowing between the electrode extension portions 11b and 11b.
- the surface resistance of the Ni thin film 2 after the heat treatment needs to be in the range of 10 to 200 ⁇ / ⁇ .
- the surface resistance is less than 10 ⁇ / ⁇ , the Ni thin film 2 is too thick to behave like a metal foil, and the ability to absorb electromagnetic noise is low.
- the surface resistance is more than 200 ⁇ / ⁇ , the Ni thin film 2 is too thin and the electromagnetic wave absorbing ability is still insufficient.
- the surface resistance of the Ni thin film 2 after the heat treatment is preferably 15 to 150 ⁇ / ⁇ , more preferably 20 to 120 ⁇ / ⁇ , and most preferably 30 to 100 ⁇ / ⁇ .
- the Ni thin film 2 with a light transmittance of 3 to 50% and a surface resistance of 10 to 200 ⁇ / ⁇ has an uneven thickness as shown in Fig. 2, and is a relatively thick region. 2a and a relatively thin (or no thin film) region 2b. It is considered that the relatively thin region 2b acts as a magnetic gap and a high resistance region, and attenuates magnetic flux and current flowing in the Ni thin film 2 due to near-field noise.
- the state of such a thin Ni thin film 2 varies greatly depending on the manufacturing conditions, and it has been found that it is very difficult to stably form the Ni thin film 2 having a constant light transmittance and surface resistance.
- the surface resistance can be adjusted by changing the heat treatment conditions. For example, for the Ni thin film 2 having a high surface resistance, the surface resistance can be lowered to a desired value by increasing the heat treatment temperature or increasing the heat treatment time. On the contrary, for the Ni thin film 2 having a low surface resistance, the decrease in the surface resistance can be suppressed by lowering the heat treatment temperature or shortening the heat treatment time.
- the deposited film Even if the deposited film has the same surface resistance, there is a significant difference in the electromagnetic wave absorption ability between the non-heat treated film and the heat treated film, and the deposited film adjusted to the desired surface resistance by the heat treatment has a higher electromagnetic wave absorbing capacity. I found it to have. The reason for this is not clear. This is because it is very difficult to evaluate changes in the state (particularly the structure) of a very thin Ni thin film due to heat treatment. As a result of the experiment, it has been found that the electromagnetic wave absorbing ability of the Ni thin film changes according to the heat treatment temperature. Therefore, in the present invention, the structure state of the Ni thin film is defined by the heat treatment temperature.
- the heat treatment temperature is in the range of 110 to 170 ° C.
- the heat treatment temperature is less than 110 ° C.
- the effect of improving the electromagnetic wave absorption ability and the variation by the heat treatment cannot be substantially obtained.
- the heat treatment temperature is higher than 170 ° C., not only the surface oxidation of the Ni thin film 2 occurs but also the thermal shrinkage becomes too large in the polyethylene terephthalate film that does not have sufficient heat resistance.
- the heat treatment temperature is preferably 120 to 170 ° C, more preferably 130 to 160 ° C.
- the heat treatment time varies depending on the heat treatment temperature, but is generally 10 minutes to 1 hour, preferably 20 to 40 minutes.
- the same film as the polyethylene terephthalate film 1 may be used.
- Transmission attenuation factor Rtp supports 50 ⁇ microstrip line MSL (64.4 mm x 4.4 mm) and microstrip line MSL as shown in Fig. 4 (a) and Fig. 4 (b).
- the power loss P loss is obtained by subtracting the power of the reflected wave S 11 and the power of the transmitted wave S 12 from the power incident on the system shown in FIGS. 4 (a) and 4 (b). obtaining noise absorption ratio P loss / P in by dividing P loss in incident power P in.
- Example 1 An Ni thin film 2 having a target light transmittance (wavelength 660 nm) of 9% was formed on a polyethylene terephthalate (PET) film 1 having a thickness of 16 ⁇ m by a vacuum vapor deposition method to produce a long vapor deposition film.
- Five test pieces TP1 each having a size of 10 cm ⁇ 10 cm were cut from an arbitrary portion of the deposited film.
- the light transmittance at any five locations of each test piece TP1 was measured with a laser beam having a wavelength of 660 nm using a transmission laser sensor (IB-05) manufactured by Keyence Corporation, and averaged. Further, the surface resistance of each test piece TP1 was measured by a pressure two-terminal method as shown in FIG.
- Each electrode 11 is composed of an electrode body portion 11a having a length of 10 cm, a width of 1 cm, and a thickness of 0.5 mm, and an electrode extension portion 11b having a width of 1 cm and a thickness of 0.5 mm, and the transparent acrylic plate 12 is 10 cm ⁇ 10 cm.
- X Thickness 5 mm, cylindrical weight 13 had a diameter of 10 cm and was 3.85 kg.
- Both electrodes 11 and 11 were connected to a resistance meter (model name: 3565) manufactured by Tsuruga Electric Co., Ltd., and the surface resistance was obtained from the obtained current value.
- the average light transmittance of all the test pieces TP1 was 9.1%, and the average surface resistance was 43 ⁇ / ⁇ .
- Each of 20 test pieces TP2 (55.2 mm x 4.7 mm) cut out from an arbitrary part of a long vapor-deposited film is adhesive to the microstrip line MSL of the system shown in Fig. 4 (a) and Fig. 4 (b).
- FIG. 6 shows the maximum value and the minimum value of the transmission attenuation rate Rtp of 20 test pieces TP2 that were not heat-treated as Comparative Example 1.
- A4 size (210 mm x 297 mm) sample S were cut out from any part of the long vapor-deposited film, and each sample S was cut as shown in Fig. 5 (a) and Fig. 5 (b).
- the Ni thin film 2 is placed on the hot plate 41 of the heating device 40, and an A4 size 3 mm thick Teflon (registered trademark) heat insulating sheet 42 and an A4 size 2 mm thick iron plate 43 are provided.
- heat treatment was performed at 150 ° C. for 30 minutes. The heat shrinkage due to the heat treatment was about 1%.
- the light transmittance and surface resistance of the five test pieces TP1 of 10 cm ⁇ 10 cm cut out from each heat-treated sample S were measured by the same method as described above. As a result, the average light transmittance of the heat-treated test piece TP1 was 8.9%, and the average surface resistance was 39 ⁇ / ⁇ . Further, for each test piece TP2 (55.2 mm ⁇ 4.7 mm) cut from each of the 20 heat-treated deposited film samples S, the power and transmitted wave of the reflected wave S 11 in the frequency range of 0.1 to 6 GHz are the same as described above. The power of S 12 was measured, and the transmission attenuation rate Rtp in the frequency range of 0.1 to 6 GHz was obtained from the above equation (1). The highest value and the lowest value of the transmission attenuation rate Rtp of the 20 heat-treated specimens TP2 are shown in FIG.
- the frequency of each Rtp is represented by the number of test pieces having Rtp in the range of 30 dB ⁇ Rtp ⁇ 31 dB (the same applies hereinafter).
- the Rtp of the test piece of Example 1 made of the heat-treated vapor-deposited film is not only higher than the Rtp of the test piece of Comparative Example 1 made of the non-heat-treated vapor-deposited film, and its distribution was also narrow (the variation was small).
- Example 2 Comparative Example 2 Except that the target light transmittance (wavelength 660 nm) of the Ni thin film 2 was set to 15%, a long vapor-deposited film was prepared in the same manner as in Example 1, and each of the five test pieces TP1 cut out from any portion was prepared. On the other hand, the light transmittance and the surface resistance were measured by the same method as in Example 1. The average light transmittance of all the test pieces TP1 was 15.5%, and the average surface resistance was 52 ⁇ / ⁇ .
- Example 2 For each of 20 test pieces TP2 (55.2 mm ⁇ 4.7 mm) cut out from an arbitrary part of the long vapor-deposited film, the reflected wave S 11 in the frequency range of 0.1 to 6 GHz was obtained in the same manner as in Example 1. The power and the power of the transmitted wave S 12 were measured, and the transmission attenuation rate Rtp in the frequency range of 0.1 to 6 GHz was obtained by the above equation (1).
- FIG. 8 shows the maximum value and the minimum value of the transmission attenuation rate Rtp of 20 test pieces TP2 that were not heat-treated as Comparative Example 2.
- Example 2 20 A4-sized (210 mm ⁇ 297 mm) sample S were cut from an arbitrary portion of the long vapor-deposited film, and heat-treated at 150 ° C. for 30 minutes in the same manner as in Example 1.
- the heat shrinkage due to the heat treatment was about 1%.
- the light transmittance and the surface resistance were measured in the same manner as in Example 1 for five test pieces TP1 of 10 cm ⁇ 10 cm that were cut out from each heat-treated sample S.
- the average light transmittance of the heat-treated test piece TP1 was 15.2%, and the average surface resistance was 48 ⁇ / ⁇ .
- the transmission attenuation rate Rtp in the frequency range of 0.1 to 6 GHz was determined for the test piece TP2 (55.2 mm ⁇ 4.7 mm) cut from each of the 20 heat-treated vapor deposited film samples S in the same manner as in Example 1.
- the maximum value and the minimum value of the transmission attenuation rate Rtp of the 20 heat-treated test pieces TP2 are shown in FIG.
- the Rtp of the test piece of Example 2 made of the heat-treated vapor-deposited film is not only higher than the Rtp of the test piece of Comparative Example 2 made of the non-heat-treated vapor-deposited film, and its distribution was also narrow (the variation was small).
- Example 3 Comparative Example 3 Except for setting the target light transmittance (wavelength 660 nm) of the Ni thin film 2 to 28%, a long vapor-deposited film was prepared in the same manner as in Example 1, and each of the five test pieces TP1 cut out from any part was prepared. On the other hand, the light transmittance and the surface resistance were measured by the same method as in Example 1. The average light transmittance of all the test pieces TP1 was 27.0%, and the average surface resistance was 107 ⁇ / ⁇ .
- Example 3 For each of 20 test pieces TP2 (55.2 mm ⁇ 4.7 mm) cut out from an arbitrary part of the long vapor-deposited film, the reflected wave S 11 in the frequency range of 0.1 to 6 GHz was obtained in the same manner as in Example 1. The power and the power of the transmitted wave S 12 were measured, and the transmission attenuation rate Rtp in the frequency range of 0.1 to 6 GHz was obtained by the above equation (1).
- FIG. 10 shows the maximum value and the minimum value of the transmission attenuation rate Rtp of 20 test pieces TP2 that were not heat-treated as Comparative Example 3.
- Example 2 20 A4-sized (210 mm ⁇ 297 mm) sample S were cut from an arbitrary portion of the long vapor-deposited film, and heat-treated at 150 ° C. for 30 minutes in the same manner as in Example 1.
- the heat shrinkage due to the heat treatment was about 1%.
- the light transmittance and the surface resistance were measured in the same manner as in Example 1 for five test pieces TP1 of 10 cm ⁇ 10 cm that were cut out from each heat-treated sample S.
- the average light transmittance of the heat-treated test piece TP1 was 26.5%, and the average surface resistance was 99 ⁇ / ⁇ .
- the transmission attenuation rate Rtp in the frequency range of 0.1 to 6 GHz was determined for the test piece TP2 (55.2 mm ⁇ 4.7 mm) cut from each of the 20 heat-treated vapor deposited film samples S in the same manner as in Example 1. The highest value and the lowest value of the transmission attenuation rate Rtp of the 20 heat-treated test pieces TP2 are shown in FIG.
- the Rtp of the test piece of Example 3 made of the heat-treated vapor-deposited film is not only higher than the Rtp of the test piece of Comparative Example 3 made of the non-heat-treated vapor-deposited film, and its distribution was also narrow (the variation was small).
- Example 4 Comparative Example 4 Except for setting the target light transmittance (wavelength 660 nm) of the Ni thin film 2 to 48%, a long vapor-deposited film was prepared in the same manner as in Example 1, and each of the five test pieces TP1 cut out from any part was prepared. On the other hand, the light transmittance and the surface resistance were measured by the same method as in Example 1. The average light transmittance of all the test pieces TP1 was 47.5%, and the average surface resistance was 217 ⁇ / ⁇ .
- the reflected wave S 11 in the frequency range of 0.1 to 6 GHz was obtained in the same manner as in Example 1.
- the power and the power of the transmitted wave S 12 were measured, and the transmission attenuation rate Rtp in the frequency range of 0.1 to 6 GHz was obtained by the above equation (1).
- the maximum value and the minimum value of the transmission attenuation rate Rtp of the 20 test pieces TP2 that have not been heat-treated are shown in FIG.
- Example 2 20 A4-sized (210 mm ⁇ 297 mm) sample S were cut from an arbitrary portion of the long vapor-deposited film, and heat-treated at 150 ° C. for 30 minutes in the same manner as in Example 1.
- the heat shrinkage due to the heat treatment was about 1%.
- the light transmittance and the surface resistance were measured in the same manner as in Example 1 for five test pieces TP1 of 10 cm ⁇ 10 cm that were cut out from each heat-treated sample S.
- the average light transmittance of the heat-treated test piece TP1 was 46.5%, and the average surface resistance was 185 ⁇ / ⁇ .
- the transmission attenuation rate Rtp in the frequency range of 0.1 to 6 GHz was determined for the test piece TP2 (55.2 mm ⁇ 4.7 mm) cut from each of the 20 heat-treated vapor deposited film samples S in the same manner as in Example 1.
- the maximum value and the minimum value of the transmission attenuation rate Rtp of the 20 heat-treated test pieces TP2 are shown in FIG.
- the Rtp of the test piece of Example 4 made of the heat-treated vapor deposition film is not only higher than the Rtp of the test piece of Comparative Example 4 made of the non-heat-treated vapor deposition film, but its distribution was also narrow (the variation was small).
- test piece TP2 of Example 4 consisting of the deposition film was heat-treated, affixed by adhesive to the microstrip line MSL system shown in FIG. 4 (a) and 4 (b), the power of the reflected wave S 11 and the transmitted wave The power of S 12 was measured, and the noise absorption rate P loss / P in was determined by the method of [3] (2) above. The results are shown in FIG. As is apparent from FIG. 14, the test piece TP2 of Example 4 showed a good noise absorption rate P loss / P in in the frequency range of 0.1 to 6 GHz.
- Comparative Example 5 Except for setting the target light transmittance (wavelength 660 nm) of the Ni thin film 2 to 0.3%, a long vapor-deposited film was prepared in the same manner as in Comparative Example 1, and for each of the five test pieces TP1 cut out from any part Then, the light transmittance and the surface resistance were measured by the same method as in Example 1. The average light transmittance of all the test pieces TP1 was 0.3%, and the average surface resistance was 3.8 ⁇ / ⁇ .
- One sample S of A4 size (210 mm ⁇ 297 mm) was cut from an arbitrary part of the long vapor-deposited film, and the transmission attenuation rate Rtp was measured. The results are shown in FIG.
- Example 2 The same sample S was heat-treated at 150 ° C. for 30 minutes in the same manner as in Example 1, and then the light transmittance and surface resistance were measured in the same manner as in Example 1. The average light transmittance was 0.3%, and the average surface resistance was 3.7 ⁇ / ⁇ . Furthermore, the transmission attenuation factor Rtp in the frequency range of 0.1 to 6 GHz was determined for the test piece TP2 (55.2 mm ⁇ 4.7 mm) cut from the heat-treated sample S by the same method as in Example 1. The results are shown in FIG.
- Comparative Example 6 Except that the target light transmittance (wavelength 660 nm) of the Ni thin film 2 was set to 60%, a long vapor-deposited film was prepared in the same manner as in Comparative Example 1, and for each of the five test pieces TP1 cut out from any part. Then, the light transmittance and the surface resistance were measured by the same method as in Example 1. The average light transmittance of all the test pieces TP1 was 60.5%, and the average surface resistance was 390 ⁇ / ⁇ .
- the transmission attenuation rate Rtp in the frequency range of 0.1 to 6 mm is obtained in the same manner as in Example 1. Asked.
- FIG. 16 shows the maximum value and the minimum value of the transmission attenuation rate Rtp of the 20 test pieces TP2 that were not heat-treated.
- Example 2 20 A4-sized (210 mm ⁇ 297 mm) sample S were cut from an arbitrary portion of the long vapor-deposited film, and heat-treated at 150 ° C. for 30 minutes in the same manner as in Example 1.
- the heat shrinkage due to the heat treatment was about 1%.
- the light transmittance and the surface resistance were measured in the same manner as in Example 1 for five test pieces TP1 of 10 cm ⁇ 10 cm that were cut out from each heat-treated sample S.
- the average light transmittance of the heat-treated test piece TP1 was 59.0%, and the average surface resistance was 350 ⁇ / ⁇ .
- the transmission attenuation rate Rtp in the frequency range of 0.1 to 6 GHz was determined for the test piece TP2 (55.2 mm ⁇ 4.7 mm) cut from each of the 20 heat-treated vapor deposited film samples S in the same manner as in Example 1.
- FIG. 16 shows the maximum value and the minimum value of the transmission attenuation rate Rtp of the 20 heat-treated specimens TP2.
- Example 5 The vapor deposition film of Comparative Example 2 (light transmittance: 15.5%) was subjected to heat treatment at 80 ° C., 110 ° C., 120 ° C., 150 ° C., 170 ° C., and 190 ° C. for 30 minutes.
- the transmission attenuation factor Rtp was measured for each of 20 test pieces TP2 (55.2 mm ⁇ 4.7 mm) cut out from an arbitrary part of the long vapor-deposited film in the same manner as in Example 1.
- Table 2 shows the range and average value of the transmission attenuation rate Rtp of the test piece at each heat treatment temperature.
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Abstract
Description
(1) プラスチックフィルムに蒸着法により形成したNi薄膜の表面抵抗が数十Ω/□程度であると、近傍界電磁波ノイズに対して優れた吸収能を有するが、このように薄いNi薄膜を精度良く形成することは非常に困難であり、実際に形成されるNi薄膜の表面抵抗は大きくばらつく。
(2) このように薄いNi薄膜の表面抵抗は大きな経時変化を受け、完全に安定するのに長期間を要するだけでなく、その間の環境条件(温度、湿度等)により表面抵抗の経時変化が異なる。
図1に示すように、本発明のノイズ抑制フィルム10はポリエチレンテレフタレートからなる延伸プラスチックフィルム1の一方の面にNi薄膜2を形成した後、熱処理したものである。
ポリエチレンテレフタレートからなる延伸プラスチックフィルム1は十分な絶縁性、耐熱性及び強度を有する。プラスチックフィルム10の厚さは10~100μm程度で良く、特に10~30μmが好ましい。
Ni薄膜2はスパッタリング法、真空蒸着法等の公知の方法により形成することができる。
Ni薄膜2は非常に薄いために、図2に示すように、厚さが不均一であり、厚く形成された領域2aと、薄く形成された領域又は全く形成されていない領域2bとがある。そのため、Ni薄膜2の厚さを正確に測定するのは困難である。そこで、本発明ではNi薄膜2の厚さを波長660 nmのレーザ光の透過率(単に「光透過率」という。)で表す。光透過率はNi薄膜2の任意の複数箇所の測定値を平均して求める。測定箇所数が5以上であると、光透過率の平均値は安定する。プラスチックフィルム1の厚さが30μm以下であるとプラスチックフィルム1自身の光透過率はほぼ100%であるので、ノイズ抑制フィルム10の光透過率がNi薄膜2の光透過率と一致する。しかし、プラスチックフィルム1がそれより厚い場合には、ノイズ抑制フィルム10の光透過率からプラスチックフィルム1の光透過率を引いた値がNi薄膜2の光透過率である。
光透過率が3~50%と薄いNi薄膜2の表面抵抗は測定方法により大きく異なることが分った。そのため、Ni薄膜2と電極との接触面積をできるだけ大きくするとともに、Ni薄膜2と電極とができるだけ均一に密着するように、図3に示す装置を用いて、加圧下での直流二端子法(単に「加圧二端子法」と言う)により表面抵抗を測定する。具体的には、硬質な絶縁性平坦面上にNi薄膜2を上にして載置した10 cm×10 cmのノイズ抑制フィルム10の正方形試験片TP1の対向辺部に、長さ10 cm×幅1 cm×厚さ0.5 mmの電極本体部11aと、電極本体部11aの中央側部から延びる幅1 cm×厚さ0.5 mmの電極延長部11bとからなる一対の電極11,11を載置し、試験片TP1と両電極11,11を完全に覆うようにそれらの上に10 cm×10 cm×厚さ5 mmの透明アクリル板12を載せ、透明アクリル板12の上に直径10 cmの円柱状重り13(3.85 kg)を載せた後で、両電極延長部11b,11b間を流れる電流から表面抵抗を求める。
光透過率が3~50%で、表面抵抗が10~200Ω/□と非常に薄いNi薄膜2は、図2に示すように全体的に厚さムラがあり、比較的厚い領域2aと比較的薄い(又は薄膜がない)領域2bとを有する。比較的薄い領域2bは磁気ギャップ及び高抵抗領域として作用し、近傍界ノイズによりNi薄膜2内を流れる磁束及び電流を減衰させると考えられる。しかし、このような薄いNi薄膜2の状態は製造条件により大きく異なり、一定の光透過率及び表面抵抗を有するNi薄膜2を安定的に形成するのは非常に困難であることが分った。そこで鋭意研究した結果、蒸着法により形成したNi薄膜2に対して、延伸ポリエチレンテレフタレートプラスチックフィルム1を熱収縮が起こり得る100℃超の温度で熱処理すると、Ni薄膜2の表面抵抗は若干低下するとともに安定化し、経時変化が実質的になくなることが分った。熱収縮が起こり得る延伸ポリエチレンテレフタレートフィルムに対して100℃を超す温度で熱処理を行うということは、従来では全く考えられないことであった。しかし、110~170℃の範囲内の温度で短時間(10分~1時間)熱処理すると、ポリエチレンテレフタレートフィルム1が僅かに熱収縮するだけで、Ni薄膜2の表面抵抗が僅かに低下するとともに安定化し、もって電磁波ノイズ吸収能も安定化することが分った。ここで、電磁波ノイズ吸収能の安定化とは、電磁波ノイズ吸収能の経時変化が実質的になくなるだけでなく、製造条件によるばらつき及び製造ロット間のばらつきも低下することを意味する。
(1) 伝送減衰率
伝送減衰率Rtpは、図4(a) 及び図4(b) に示すように、50ΩのマイクロストリップラインMSL(64.4 mm×4.4 mm)と、マイクロストリップラインMSLを支持する絶縁基板20と、絶縁基板20の下面に接合された接地グランド電極21と、マイクロストリップラインMSLの両端に接続された導電性ピン22,22と、ネットワークアナライザNAと、ネットワークアナライザNAを導電性ピン22,22に接続する同軸ケーブル23,23とで構成されたシステムを用い、マイクロストリップラインMSLにノイズ抑制フィルムの試験片TP2を粘着剤により貼付し、0.1~6 GHzの入射波に対して、反射波S11の電力及び透過波S12の電力を測定し、下記式(1):
Rtp=-10×log[10S21/10/(1-10S11/10)]・・・(1)
により求める。
図4(a) 及び図4(b) に示すシステムに入射した電力から反射波S11の電力及び透過波S12の電力を差し引くことにより、電力損失Plossを求め、Plossを入射電力Pinで割ることによりノイズ吸収率Ploss/Pinを求める。
厚さ16μmのポリエチレンテレフタレート(PET)フィルム1に真空蒸着法により目標光透過率(波長660 nm)9%のNi薄膜2を形成し、長尺の蒸着フィルムを作製した。蒸着フィルムの任意の部分から10 cm×10 cmの試験片TP1を5枚切り出した。各試験片TP1の任意の5箇所の光透過率を、株式会社キーエンス製の透過型レーザセンサ(IB-05)を使用し、波長660 nmのレーザ光で測定し、平均した。また各試験片TP1の表面抵抗を図3に示すように加圧二端子法により測定した。各電極11は長さ10 cm×幅1 cm×厚さ0.5 mmの電極本体部11aと幅1 cm×厚さ0.5 mmの電極延長部11bとからなり、透明アクリル板12は10 cm×10 cm×厚さ5 mmであり、円柱状重り13は10 cmの直径を有し、3.85 kgであった。両電極11,11を鶴賀電機株式会社製の抵抗計(型名:3565)に接続し、得られた電流値から表面抵抗を求めた。全試験片TP1の平均光透過率は9.1%であり、平均表面抵抗は43Ω/□であった。
Ni薄膜2の目標光透過率(波長660 nm)を15%とした以外実施例1と同じ方法で長尺の蒸着フィルムを作製し、その任意の部分から切り出したそれぞれ5枚の試験片TP1に対して、実施例1と同じ方法で光透過率及び表面抵抗を測定した。全試験片TP1の平均光透過率は15.5%であり、平均表面抵抗は52Ω/□であった。
Ni薄膜2の目標光透過率(波長660 nm)を28%とした以外実施例1と同じ方法で長尺の蒸着フィルムを作製し、その任意の部分から切り出したそれぞれ5枚の試験片TP1に対して、実施例1と同じ方法で光透過率及び表面抵抗を測定した。全試験片TP1の平均光透過率は27.0%であり、平均表面抵抗は107Ω/□であった。
Ni薄膜2の目標光透過率(波長660 nm)を48%とした以外実施例1と同じ方法で長尺の蒸着フィルムを作製し、その任意の部分から切り出したそれぞれ5枚の試験片TP1に対して、実施例1と同じ方法で光透過率及び表面抵抗を測定した。全試験片TP1の平均光透過率は47.5%であり、平均表面抵抗は217Ω/□であった。
Ni薄膜2の目標光透過率(波長660 nm)を0.3%とした以外比較例1と同様に長尺の蒸着フィルムを作製し、その任意の部分から切り出したそれぞれ5枚の試験片TP1に対して、実施例1と同じ方法で光透過率及び表面抵抗を測定した。全試験片TP1の平均光透過率は0.3%であり、平均表面抵抗は3.8Ω/□であった。また長尺の蒸着フィルムの任意の部分からA4サイズ(210 mm×297 mm)のサンプルSを1枚切り取り、伝送減衰率Rtpを測定した。結果を図15に示す。
Ni薄膜2の目標光透過率(波長660 nm)を60%とした以外比較例1と同様に長尺の蒸着フィルムを作製し、その任意の部分から切り出したそれぞれ5枚の試験片TP1に対して、実施例1と同じ方法で光透過率及び表面抵抗を測定した。全試験片TP1の平均光透過率は60.5%であり、平均表面抵抗は390Ω/□であった。
比較例2の蒸着フィルム(光透過率:15.5%)に対して80℃、110℃、120℃、150℃、170℃及び190℃の各温度で30分間の熱処理を行った。実施例1と同じ方法で長尺の蒸着フィルムの任意の部分から切り出した20枚の試験片TP2(55.2 mm×4.7 mm)の各々に対して、伝送減衰率Rtpを測定した。各熱処理温度での試験片の伝送減衰率Rtpの範囲及び平均値を表2に示す。
Claims (4)
- 電磁波ノイズ吸収能のばらつきが低減されたノイズ抑制フィルムであって、ポリエチレンテレフタレートからなる延伸プラスチックフィルムの一方の面に蒸着法によりNi薄膜を形成した後、熱収縮が起こり得る110~170℃の範囲内の温度で10分~1時間熱処理してなり、(a) 前記Ni薄膜の光透過率(波長660 nmのレーザ光)が3~50%であり、(b) 前記Ni薄膜の10 cm×10 cmの正方形の試験片TPの対向辺部に、辺全体を覆う長さの一対の電極を配置し、平坦な加圧板を介して3.85 kgの荷重をかけて測定した表面抵抗が10~200Ω/□であることを特徴とするノイズ抑制フィルム。
- 請求項1に記載のノイズ抑制フィルムにおいて、前記Ni薄膜の熱処理温度が130~160℃であることを特徴とするノイズ抑制フィルム。
- 請求項1又は2に記載のノイズ抑制フィルムにおいて、前記Ni薄膜の熱処理時間が20~40分であることを特徴とするノイズ抑制フィルム。
- 請求項1~3のいずれかに記載のノイズ抑制フィルムにおいて、前記Ni薄膜の表面に保護フィルムが積層されていることを特徴とするノイズ抑制フィルム。
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- 2012-06-27 KR KR1020147002488A patent/KR101906981B1/ko active IP Right Grant
- 2012-06-27 WO PCT/JP2012/066417 patent/WO2013002276A1/ja active Application Filing
- 2012-06-27 US US14/129,839 patent/US20140141267A1/en not_active Abandoned
- 2012-06-27 CN CN201280032039.0A patent/CN103636299B/zh active Active
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2015
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JPH0859867A (ja) | 1994-08-19 | 1996-03-05 | Oji Kako Kk | 透明導電性フィルム |
JP2000006299A (ja) * | 1998-06-23 | 2000-01-11 | Mitsui Chemicals Inc | 透明導電性積層体 |
JP2000357893A (ja) * | 1999-04-13 | 2000-12-26 | Nippon Paint Co Ltd | 電磁波シールド膜および電磁波シールド塗料 |
JP2001135516A (ja) * | 1999-11-05 | 2001-05-18 | Tdk Corp | 磁性複合組成物及び磁性成形物 |
JP2002094281A (ja) * | 2000-09-11 | 2002-03-29 | Kitagawa Ind Co Ltd | シールド構造 |
JP2006295101A (ja) | 2005-03-14 | 2006-10-26 | Shin Etsu Polymer Co Ltd | ノイズ抑制体、配線用部材および多層回路基板 |
JP2006279912A (ja) | 2005-03-28 | 2006-10-12 | Res Inst Electric Magnetic Alloys | 近傍界電磁波ノイズ抑制材料 |
JP2006278433A (ja) | 2005-03-28 | 2006-10-12 | Hitachi Metals Ltd | 複合電磁波ノイズ抑制シート |
JP2008053383A (ja) | 2006-08-23 | 2008-03-06 | Kaneka Corp | 放熱・電波吸収・シールドフィルム |
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Non-Patent Citations (1)
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Also Published As
Publication number | Publication date |
---|---|
US20140141267A1 (en) | 2014-05-22 |
KR20140048222A (ko) | 2014-04-23 |
EP2728989A4 (en) | 2014-12-24 |
CN103636299B (zh) | 2016-12-14 |
JP2013016543A (ja) | 2013-01-24 |
EP2728989B1 (en) | 2016-03-30 |
US9907218B2 (en) | 2018-02-27 |
US20150173257A1 (en) | 2015-06-18 |
KR101906981B1 (ko) | 2018-10-11 |
JP5069365B1 (ja) | 2012-11-07 |
CN103636299A (zh) | 2014-03-12 |
EP2728989A1 (en) | 2014-05-07 |
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