WO2011099444A1 - Film de revêtement métallique pour transmission d'ondes électromagnétiques, procédé de formation d'un film de revêtement métallique pour transmission d'ondes électromagnétiques et dispositif radar embarqué - Google Patents

Film de revêtement métallique pour transmission d'ondes électromagnétiques, procédé de formation d'un film de revêtement métallique pour transmission d'ondes électromagnétiques et dispositif radar embarqué Download PDF

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WO2011099444A1
WO2011099444A1 PCT/JP2011/052513 JP2011052513W WO2011099444A1 WO 2011099444 A1 WO2011099444 A1 WO 2011099444A1 JP 2011052513 W JP2011052513 W JP 2011052513W WO 2011099444 A1 WO2011099444 A1 WO 2011099444A1
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WIPO (PCT)
Prior art keywords
electromagnetic wave
metal coating
adhesion layer
catalyst adhesion
conductive substrate
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PCT/JP2011/052513
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English (en)
Japanese (ja)
Inventor
充広 渡辺
晃 寺西
正勝 後藤
哲司 太田
佳子 北村
順子 高橋
Original Assignee
関東化成工業株式会社
株式会社きもと
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Application filed by 関東化成工業株式会社, 株式会社きもと filed Critical 関東化成工業株式会社
Publication of WO2011099444A1 publication Critical patent/WO2011099444A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/42—Housings not intimately mechanically associated with radiating elements, e.g. radome
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/44—Details of, or arrangements associated with, antennas using equipment having another main function to serve additionally as an antenna, e.g. means for giving an antenna an aesthetic aspect
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01S—RADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
    • G01S13/00—Systems using the reflection or reradiation of radio waves, e.g. radar systems; Analogous systems using reflection or reradiation of waves whose nature or wavelength is irrelevant or unspecified
    • G01S13/88—Radar or analogous systems specially adapted for specific applications
    • G01S13/93—Radar or analogous systems specially adapted for specific applications for anti-collision purposes
    • G01S13/931—Radar or analogous systems specially adapted for specific applications for anti-collision purposes of land vehicles
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01S—RADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
    • G01S7/00—Details of systems according to groups G01S13/00, G01S15/00, G01S17/00
    • G01S7/02—Details of systems according to groups G01S13/00, G01S15/00, G01S17/00 of systems according to group G01S13/00
    • G01S7/03—Details of HF subsystems specially adapted therefor, e.g. common to transmitter and receiver

Definitions

  • the present invention relates to an electromagnetic wave-transmitting metal film formed on a non-conductive substrate and capable of transmitting an electromagnetic wave, a method of forming an electromagnetic wave transmitting metal film, and an in-vehicle radar device having a cover member provided with the metal film.
  • a millimeter wave radar device for distance measurement has been installed on the front grill or emblem of an automobile.
  • the front grill, the emblem, or the like is a non-conductive base material such as resin formed with a metal film
  • the metal film blocks the millimeter wave or greatly attenuates the millimeter wave. Therefore, the metal film provided on the millimeter wave path of the millimeter wave radar device needs to have millimeter wave permeability.
  • an electromagnetic wave transmitting metal film for example, an indium film formed in an island shape by a vacuum deposition method is known (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3).
  • the indium film formed in an island shape on the non-conductive substrate has a sufficient metallic luster in appearance, and the gap between the islands can be a millimeter wave transmission path.
  • an object of the present invention is to provide an electromagnetic wave transmitting metal film, a method of forming an electromagnetic wave transmitting metal film, and a vehicle-mounted radar device that can be manufactured at low cost using a metal other than indium.
  • the inventors of the present invention have achieved the above-mentioned problems by employing the following metal film for electromagnetic wave transmission, a method for forming an electromagnetic wave transmission metal film, and an on-vehicle radar device. .
  • the metal film for electromagnetic wave transmission according to the present invention is a metal film capable of transmitting electromagnetic waves provided on the surface of a non-conductive substrate, and the metal film is provided on the surface of the non-conductive substrate.
  • a metal film is formed in an island shape by an electroless plating method on a catalyst adhesion layer containing a water-soluble polyester resin, and one gap between islands serving as an electromagnetic wave transmission path is formed in a unit area (1 mm 2 ). It is characterized by the presence of ⁇ 5000 and having a metallic luster.
  • the thickness of the catalyst adhesion layer is preferably 0.05 ⁇ m to 2.0 ⁇ m.
  • the thickness of the metal film is preferably 0.01 ⁇ m to 1.0 ⁇ m.
  • the electromagnetic wave transmitting metal coating of the present invention preferably contains at least one selected from nickel, nickel alloy, copper, copper alloy, silver, silver alloy, tin, tin alloy, gold and gold alloy.
  • the non-conductive base material is preferably a kind selected from an insulating resin, ceramics, paper, glass, and fibers.
  • the method for forming an electromagnetic wave transmitting metal film according to the present invention is an electromagnetic wave transmitting metal film forming method for forming the above electromagnetic wave transmitting metal film on the surface of a non-conductive substrate, comprising the following steps: It is characterized by. (1) A catalyst adhesion layer forming step of forming a catalyst adhesion layer containing a water-insoluble polyester resin on the surface of a non-conductive substrate. (2) An electroless plating step in which a metal coating is formed in an island shape on the surface of the non-conductive substrate on the catalyst adhesion layer formed in the catalyst adhesion layer formation step by an electroless plating method.
  • the on-vehicle radar device uses a cover member provided with the above-described metal film for electromagnetic wave transmission on the surface of a non-conductive substrate.
  • the metal film for electromagnetic wave transmission can be manufactured at low cost by using inexpensive nickel or nickel alloy instead of expensive indium.
  • a catalyst adhesion layer containing a water-insoluble polyester resin is provided on the surface of a non-conductive substrate, and the surface of the catalyst adhesion layer is not subjected to electroless plating.
  • a metal film is formed in an island shape on the surface of a conductive substrate, and a metal film having a gap between islands of 1 to 5000 as an electromagnetic wave transmission path existing in a unit area (1 mm 2 ). Can be formed.
  • the metal film 100 for electromagnetic wave transmission which concerns on this invention is demonstrated.
  • the electromagnetic wave transmitting metal coating 100 according to the present invention is provided on the surface of the non-conductive substrate 10 via the catalyst adhesion layer 20, and has a metallic luster.
  • the electromagnetic wave transmitting metal coating 100 according to the present invention has a gap which becomes an electromagnetic wave transmission path by depositing nickel or a nickel alloy in an island shape on the catalyst adhesion layer 20. Is formed.
  • the electromagnetic wave transmitting metal coating 100 of the present embodiment is capable of transmitting electromagnetic waves (millimeter waves) having a wavelength of 10 mm to 1 mm and a frequency of 20 GHz to 300 GHz through this gap, and a millimeter wave radar device ( It can be suitably used as a metal film that covers a cover member of an on-vehicle radar device (not shown).
  • electromagnetic waves millimeter waves
  • It can be suitably used as a metal film that covers a cover member of an on-vehicle radar device (not shown).
  • the non-conductive substrate 10, the catalyst adhesion layer 20, and the metal coating 30 will be described in this order.
  • Non-conductive substrate 10 As the non-conductive substrate 10 according to the present invention, one selected from resin, ceramics, paper, glass and fiber can be used. In addition, when the metal coating 30 is formed on the surface of the nonconductive substrate 10, a transparent substrate such as a resin or glass is preferably used in that a good metallic luster is observed from the nonconductive substrate 10 side. Can be used.
  • a resin when used as the non-conductive substrate 10, either a thermoplastic insulating resin or a thermosetting insulating resin may be used, and the material of the resin is not particularly limited as long as it is an insulating resin. .
  • ABS acrylonitrile-butadiene-styrene
  • AES acrylonitrile-ethylene-styrene
  • acrylic resin polyacetal resin
  • polyamide resin polyamideimide resin
  • polyimide resin polyurethane resin
  • polyester Resin polyethylene resin, polyethylene naphthalate resin, polyethersulfone, polyetheretherketone, liquid crystal polymer (LCP)
  • polyvinyl chloride resin polyolefin resin
  • polycarbonate resin polystyrene resin
  • polysulfone resin polysulfone resin
  • cellulose resin polyphenylene sulfide resin
  • thermoplastic insulating resins or thermosetting insulating resins can be used.
  • these enumerated resins are only examples, and the non-conductive substrate 10 according to the present invention is not limited to these resins.
  • the catalyst adhering layer 20 is a layer formed using a water-insoluble polyester, and serves to adhere metal particles having catalytic activity to the non-conductive substrate 10, It plays the role of depositing nickel or nickel alloys in islands.
  • the catalyst adhesion layer 20 by providing the catalyst adhesion layer 20 on the surface of the non-conductive substrate 10, the catalyst can be easily adhered to the non-conductive substrate 10 having a smooth surface such as the resin, glass, ceramics, etc. described above. It is possible to form a metal film having a metallic luster and electromagnetic wave permeability on the surface of the non-conductive substrate 10.
  • the catalyst adhesion layer 20 is formed using a water-insoluble polyester resin, it prevents that the catalyst adhesion layer 20 elutes into a plating solution or a catalyst liquid, and prevents the catalyst adhesion layer 20 from peeling. be able to. Furthermore, by preventing elution of the catalyst adhesion layer 20 from the plating solution and the catalyst solution, the life of the plating solution and the catalyst solution can be extended. Furthermore, by providing the catalyst adhesion layer 20, it is possible to prevent darkening of the metal film formed on the surface thereof.
  • the contact angle of the surface of the catalyst adhesion layer 20 with pure water is preferably 40 degrees to 60 degrees.
  • the contact angle is preferably 40 degrees to 60 degrees.
  • nickel or a nickel alloy can be deposited in an island shape on the surface of the non-conductive substrate 10 via the catalyst adhesion layer 20.
  • the contact angle is less than 40 degrees, it is difficult to deposit nickel or a nickel alloy in a uniform and island shape even when the conditions for electroless plating are adjusted.
  • the contact angle of the surface of the catalyst adhesion layer 20 with pure water 60 degrees or less, the surface of the catalyst adhesion layer 20 can be made hydrophilic and the catalyst adhesion can be improved.
  • the contact angle with respect to pure water on the surface of the catalyst adhesion layer 20 exceeds 60 degrees, the catalyst adhesion is reduced, which is not preferable.
  • the contact angle of the surface of the catalyst adhesion layer 20 with pure water is more preferably 55 degrees or less.
  • the contact angle with respect to pure water on the surface of the catalyst adhesion layer 20 is adjusted to 40 degrees to 60 degrees by adjusting the hydrophilicity of the water-insoluble polyester resin.
  • Examples of the method for adjusting the hydrophilicity of the water-insoluble polyester resin include the following methods (A) to (C).
  • A) Types of polyvalent carboxylic acid and polyhydric alcohol used when producing the polyester resin Choose the appropriate one.
  • B) The hydroxyl value of the polyester resin is adjusted.
  • C) The polyester resin is modified.
  • a polyester resin is generally produced by condensation polymerization of a polyvalent carboxylic acid and a polyhydric alcohol.
  • the contact angle of the surface of the catalyst adhesion layer 20 with respect to pure water can be adjusted by appropriately selecting the following polyvalent carboxylic acid and polyhydric alcohol. .
  • divalent carboxylic acids divalent or higher polybasic acids such as phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, trimesic acid, pyromellitic acid and biphenyltetracarboxylic acid, and anhydrides thereof. It is preferable to select from among them.
  • Polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentadiol, 1,6-hexanediol, 2,2-diethyl-1,3 -Propanediol, neopentyl glycol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, hydroxypivalic acid neopentyl glycol ester, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl- It is preferable to select from dihydric alcohols such as 1,5-pentadiol, 2,2,4-trimethylpentanediol and hydrogenated bisphenol A.
  • the hydroxyl value of the polyester resin is preferably 10 mgKOH / g to 400 mgKOH / g in order to adjust the contact angle of the surface of the catalyst adhesion layer 20 with pure water within the above range.
  • the polyester resin is made water-insoluble, and the elution of the catalyst adhesion layer 20 to the plating solution and the catalyst solution is better prevented, and the darkening of the metal coating is prevented. can do.
  • the hydroxyl value of the polyester resin can be adjusted, for example, by substituting a part of the dihydric alcohol described above with a trihydric or higher alcohol or a polyhydric alcohol containing a diepoxy compound. That is, the hydroxyl value of the polyester resin can be adjusted by adjusting an alternative amount of the trihydric or higher alcohol or the polyhydric alcohol containing the diepoxy compound.
  • trihydric or higher alcohols examples include trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, glucose, mannitol, sucrose, and glucose.
  • examples of the polyhydric alcohol containing a diepoxy compound include glycidyl ether of bisphenol A, glycidyl ether of bisphenol F, glycidyl ester dimer, and aliphatic glycidyl ether.
  • Modification of the polyester resin is, for example, a graft polymerization of a polyester resin having a polymerizable unsaturated double bond and a monomer having a polymerizable unsaturated double bond, and a polyester resin constituting the trunk portion of the graft polymer, or This can be carried out by introducing a hydrophilic group into any of the monomers constituting the branch portion of the graft polymer.
  • the hydrophilicity of the surface of the catalyst adhesion layer 20 can be improved by introducing the hydrophilic group into the graft polymer of the polyester resin.
  • the hydrophilic group may be introduced into either the trunk portion or the branch portion, but it is more preferable to introduce the hydrophilic group into the branch portion constituted by the monomer polymer.
  • a hydrophilic group is introduced into the branch portion, the hydrophilicity of the catalyst adhesion layer 20 can be increased, and the adhesion of the catalyst to the catalyst adhesion layer 20 can be improved. On the other hand, elution of the catalyst adhesion layer 20 can be easily prevented.
  • a polyester resin having a polymerizable unsaturated double bond can be obtained by introducing unsaturated groups such as maleic acid, maleic anhydride, itaconic acid, fumaric acid, crotonic acid, and tetrahydrophthalic acid into the polyester resin.
  • monomers having a polymerizable unsaturated double bond can be used as the monomer to be graft polymerized with the polyester resin.
  • Such monomers are listed below separately for those having a hydrophilic group and those having a hydrophobic group.
  • Examples of the monomer having a hydrophilic group include those having a hydrophilic group such as a carboxyl group, a hydroxyl group, a hydroxymethyl group, an amino group, a sulfonic acid group, a polyethylene oxide group, a sulfate ester base, and a phosphate ester base.
  • (meth) acrylates having a hydroxyl group such as 2-hydroxylethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate
  • acrylic acid containing carboxyl group methacrylic acid, maleic acid or the like
  • Ethylenically unsaturated carboxylic acids such as monoalkyl esters, itaconic acid or monoalkyl esters thereof, fumaric acid or monoalkyl esters thereof ”,“ acrylamides, N-methylol (meth) acrylamides, (meth) ) Acrylamides ”,“ N-methylaminoethyl methacrylate, N-methylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl Alkyl amino esters of acrylic acid or methacrylic acid such as tacrylate
  • alkyl such as“ N- (2-dimethylaminoethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide, N, N-dimethylaminopropylacrylamide ” “Unsaturated amides having an amino group”, “monovinylpyridines such as vinylpyridine”, “vinyl ethers having an alkylamino group such as dimethylaminoethyl vinyl ether”, “vinylsulfonic acid, styrenesulfonic acid and salts thereof, 2- Examples thereof include those having a sulfone group such as acryloylamino-2-methylpropanesulfonic acid and salts thereof, and “vinylpyrrolidone”.
  • examples of the monomer having a hydrophobic group include those having a lipophilic hydrocarbon group, an aromatic ring group, or an alicyclic group.
  • a polyester polyol may be used as the polyester resin, and the polyester polyol and polyisocyanate may be reacted to form a polyester polyurethane.
  • the hydrophilicity of the water-insoluble polyester resin can be adjusted by the exemplified methods, and the contact angle with respect to pure water on the surface of the catalyst adhesion layer 20 can be adjusted to 60 degrees or less by these methods.
  • the number average molecular weight of the polyester resin forming the catalyst adhesion layer 20 is preferably 2,000 to 30,000.
  • the catalyst adhesion layer 20 can be formed into a strong film. Further, by forming the catalyst adhesion layer 20 using a polyester resin having a number average molecular weight of 30,000 or less, the occurrence of curling can be prevented.
  • the catalyst adhesion layer 20 may contain a resin other than the polyester resin described above. Specifically, polyvinyl butyral, acrylic resin, polyurethane resin, and the like can be included. Resins other than these polyester resins may be hydrophilic or hydrophobic, but are preferably water-insoluble resins from the viewpoint of preventing elution of the catalyst adhesion layer 20. You may adjust the contact angle with respect to the pure water of the surface of the catalyst adhesion layer 20 using resin other than these polyester resins. However, when the catalyst adhesion layer 20 is formed using a resin other than the polyester resin together with the polyester resin, the above-described polyester resin is preferably used in an amount of 50% by weight or more of the total resin components constituting the catalyst adhesion layer 20. It is more preferable to use at least 90% by weight and even more preferable to use at least 90% by weight.
  • the thickness of the catalyst adhesion layer 20 according to the present invention varies depending on the type of monomer constituting the polyester resin, but is preferably in the range of 0.05 ⁇ m to 2.0 ⁇ m, preferably 0.1 ⁇ m to 1. The range of 0 ⁇ m is more preferable.
  • nickel or a nickel alloy can be deposited in an island shape, and there is a gap between islands serving as an electromagnetic wave transmission path. It becomes easy to form 1 to 5000 per unit area (1 mm 2 ).
  • the thickness of the catalyst adhesion layer 20 is less than 0.05 ⁇ m, the adhesion ability of the catalyst is lowered.
  • the thickness of the catalyst adhesion layer 20 exceeds 2 ⁇ m, the metallic luster is lowered and the appearance color is liable to occur.
  • the thickness of the catalyst adhesion layer 20 in the range of 0.1 ⁇ m to 1.0 ⁇ m, the catalyst adhesion ability is excellent, and the metal gloss and appearance color of the resulting metal coating 30 are more excellent. Can do.
  • the metal coating 30 according to the present invention is a metal coating 30 having electromagnetic wave permeability and metallic luster as described above. As shown in FIG. 1A, the metal coating 30 is obtained by depositing nickel or a nickel alloy in an island shape on the surface of the non-conductive substrate 10. However, in FIG. 1A, the gap 32 between the islands 31 is indicated by a black line. Thus, the gap 32 between the islands 31 can be used as an electromagnetic wave transmission path by discontinuously covering the surface of the non-conductive substrate 10 with the metal coating 30.
  • Gap 32 In the present invention, it is preferable that 1 to 5000 gaps 32 between the islands 31 exist in a unit area (1 mm 2 ). By having one to 5,000 gaps in the unit area (1 mm 2 ), in the thickness direction of the metal coating 30, millimeter waves are passed from the one surface side to the other surface side through the gap 32. Or it can permeate
  • the electromagnetic wave permeability becomes insufficient.
  • one gap refers to the following.
  • a gap that does not intersect with the other gap in the length direction of the gap and is in contact with the end of the other gap only at both ends of the gap is defined as one gap. That is, in the present invention, one gap refers to a gap that does not have a contact with an end of another gap or an intersection with another gap in the length direction of the gap.
  • the film thickness of the metal coating 30 that is an aggregate of the islands 31 is preferably 0.01 ⁇ m to 1.0 ⁇ m.
  • the film thickness is less than 0.01 ⁇ m, the glitter is lowered, and there is a case where sufficient metallic luster cannot be expressed in appearance.
  • the film thickness exceeds 1 ⁇ m, the electromagnetic wave incident on the gap 32 between the islands 31 may be incident on the end face of the island 31 depending on the incident angle and may be attenuated. The function of cannot be fully demonstrated.
  • the electromagnetic wave transmitting metal film according to the present invention preferably includes the following steps.
  • the metal film for electromagnetic wave transmission which concerns on this invention can be easily manufactured using cheap nickel by the following processes.
  • Catalyst adhering layer forming step In the catalyst adhering layer forming step, a coating solution prepared by dissolving the above-mentioned water-insoluble polyester resin and other resins added as necessary in an appropriate solvent is prepared by dipping or bar coating. It can form by apply
  • Electroless plating step Next, the electroless plating step according to the present invention will be described.
  • nickel or a nickel alloy is deposited in an island shape on the catalyst adhesion layer 20 provided on the surface of the non-conductive substrate 10 to form a metal film 30 having electromagnetic wave permeability and metallic luster.
  • the electroless plating process includes the following catalyzer process, accelerator process, activator process, and electroless plating process.
  • each step will be described.
  • Catalyzer process In the catalyzer process, the non-conductive substrate 10 provided with the catalyst adhesion layer 20 is immersed in the above-described colloidal catalyst (catalyzer) of palladium and tin, so that palladium metal as a catalyst is deposited on the surface of the catalyst adhesion layer 20. It is the process of adhering. At this time, a small amount of tin adheres to the surface of the catalyst adhesion layer 20 as a divalent or tetravalent tin salt.
  • the colloidal catalyst used in this step is conventionally known, for example, a method in which a hydrate of tin and a hydrate of palladium are dissolved in water, a surfactant is added, and a reducing agent is added while stirring vigorously. It can be adjusted by this method. Moreover, what is generally marketed as a catalyzer can also be used. Further, it may be immersed in an aqueous palladium solution after being immersed in an aqueous tin solution. In the present invention, as described above, the contact angle with respect to pure water on the surface of the catalyst adhesion layer 20 is in the range of 40 to 60 degrees, so that the adhesion of the catalyst is high. For example, the process can be performed in a short time. Can do.
  • the degreasing treatment such as acid / alkali washing as a pretreatment.
  • the contact angle with respect to the pure water of the surface of the catalyst adhesion layer 20 is in the above-mentioned range, the degreasing treatment can be performed in a very short time.
  • a step called conditioning or pre-dip is performed as a pretreatment.
  • the contact angle of the surface of the catalyst adhesion layer 20 with respect to pure water is as described above.
  • Accelerator step In the accelerator step, the above non-conductive group is added to an accelerator (accelerator) made of sulfuric acid having a concentration of about 0.1% to 10% or a sodium hydrogen sulfate solution having a concentration of about 0.1 g / l to 400 g / l.
  • accelerator an accelerator
  • Activator process Although the activator process is not an essential process, initial plating deposition is performed by immersing the non-conductive substrate 10 in a palladium chloride solution of about 0.1 g / l to 1 g / l. May be carried out in order to react more uniformly.
  • the catalyst metal nucleus for depositing nickel or nickel alloy can be firmly adsorbed to the catalyst adhesion layer 20. it can.
  • Electroless plating step metal is deposited in an island shape on the surface of the catalyst adhesion layer 20 by an electroless plating method.
  • this step it is preferable to use at least one selected from nickel, nickel alloy, copper, copper alloy, silver, silver alloy, tin, tin alloy, gold and gold alloy as the metal constituting the metal coating.
  • the non-conductive substrate 10 described above is added to a nickel plating solution constituting a conventionally known nickel plating bath such as a Ni—P bath, a Ni—B bath, a Ni—Cu—P bath, or the like. Is deposited on the surface of the catalyst adhesion layer 20 using the palladium metal adhering to the catalyst adhesion layer 20 as a catalyst.
  • nickel alloys such as Ni—P, Ni—B, and Ni—Cu—P are deposited.
  • the surface of the non-conductive substrate 10 can be discontinuously covered with an island-shaped metal film formed on the upper surface of the catalyst adhesion layer 20 according to the present invention by an electroless plating method.
  • the electromagnetic wave transmitting metal coating 100 according to the present invention described above can be suitably used as the metal coating 30 that covers the surface of the cover member of the millimeter wave radar device provided in an automobile or the like as described above.
  • the on-vehicle radar device and the cover member will be described.
  • the in-vehicle radar device includes a transmission unit that transmits a millimeter wave as a transmission wave, and a reception unit that receives a radio wave reflected by an object such as a preceding vehicle as a reception wave. Measuring means for measuring the time from when the transmitted wave is transmitted until the received wave is received, and calculating means for calculating the distance to the object, the relative speed with the object, etc. based on the time measured by the measuring means Etc.
  • Such an on-vehicle radar device is generally disposed on the back side of the exterior member of the vehicle, such as the back side of the front grille of the vehicle.
  • the exterior member of a vehicle is usually subjected to metal plating from the viewpoint of design. For this reason, the exterior member in which these in-vehicle radar devices are arranged is provided with an opening for emitting and receiving millimeter waves.
  • the on-vehicle radar device according to the present invention includes a cover member for covering such an opening.
  • an in-vehicle radar device is disposed behind an emblem 40 provided in the center of the front grill in the vehicle width direction, and an opening for entering and exiting millimeter waves is provided at the emblem 40 mounting position of the front grill. It will be described below as being formed.
  • FIG. 2A An emblem 40 as a cover member according to the present invention is shown in FIG.
  • the emblem 40 shown in FIG. 2A is a background touch coating that includes a masking portion (design portion 41) on the back side of a transparent non-conductive substrate 10 such as polycarbonate resin, as shown in FIG. 2B. It has a layer configuration in which the layer 42, the catalyst adhesion layer 20 formed using the above-described water-insoluble polyester resin, and the metal coating 30 layer according to the present invention are sequentially laminated.
  • the design portion 41 representing the emblem 40 shown in FIG. 2A is masked when the background color paint is applied, and the masked design portion 41 (masking portion) is masked.
  • the portion represented by the letter “K” is a design portion 41 representing the emblem 40.
  • the background color paint include a black paint that does not shield millimeter waves, but the background color is not limited to black. Since the non-conductive substrate 10 and the catalyst adhesion layer 20 constituting the emblem 40 shown in FIG. 2 are each transparent, the metal coating 30 provided on the masking portion is observed from the surface side of the non-conductive substrate 10. be able to. Therefore, when the emblem 40 is observed from the surface side of the non-conductive substrate 10, it appears that the metal film is provided only on the design portion 41 representing the letter "K” in the illustrated example.
  • ⁇ Formation of catalyst adhesion layer> Using a commercially available polycarbonate resin having a thickness of 1000 ⁇ m as a non-conductive substrate, spraying a coating solution obtained by diluting a water-insoluble polyester resin (Plus Coat Z-850: Mutual Chemical Co., Ltd.) with a solvent on one side, By drying, a catalyst adhesion layer having a thickness of 1 ⁇ m was formed.
  • Example 2 The electromagnetic wave-transmitting metal coating of Example 2 was prepared in the same manner as in Example 1 except that the water-insoluble polyester resin of Example 1 was changed to a water-insoluble polyester resin (Plus Coat Z-730: Mutsuga Chemical). Obtained.
  • a background color coating layer 42 including a masking portion shown in FIG. 2 is formed on one side (back side) using a black paint.
  • the catalyst adhesion layer 20 was formed on the coating layer 42 using the same water-insoluble polyester resin as in Example 1, and nickel was deposited on the upper surface of the catalyst adhesion layer 20 in the same manner as in Example 1. Then, the metal film for electromagnetic wave transmission of Example 3 was obtained.
  • Example 1 a metal film of a comparative example was obtained in the same manner as in Example 1 except that one surface of the non-conductive substrate was subjected to corona discharge treatment.
  • the metal coating provided in Examples 1 to 3 was deposited in an island shape on the surface of the catalyst adhesion layer as shown in FIG. 3, whereas the metal coating formed in the comparative example was in an island shape. A continuous film was formed without precipitation.
  • the metal coatings obtained in Examples 1 to 3 had electromagnetic wave permeability and exhibited excellent metallic luster in appearance.
  • the metal coatings of Examples 1 to 3 were excellent in adhesion to the nonconductive substrate.
  • the metal film formed in the comparative example did not have electromagnetic wave permeability and had low adhesion to the non-conductive substrate.
  • the metal coating formed in Example 3 decorates the emblem shown in FIG. 2 as a cover member of the on-vehicle radar device. In this evaluation, it was proved that the metal coating transmits electromagnetic waves entering and exiting the on-vehicle radar device.
  • the stereoscopic microscope photograph shown in FIG. 3 is a photograph of the surface of the metal coating obtained in Example 1.
  • a stereomicroscope SZX7: Olympus was used for the photographing, and the magnification was 25 times.
  • the white line is the gap between islands.
  • 150 to 800 gaps were formed in a unit area (1 mm 2 ).
  • the metal film for electromagnetic wave transmission according to the present invention is a cover for an in-vehicle radar device or the like using inexpensive nickel or a nickel alloy instead of the conventionally used vacuum deposition film of indium as a metal film for millimeter wave transmission. It can be used as an electromagnetic wave transmitting metal coating provided on the member. Moreover, the formation method of the metal film for electromagnetic wave transmission which concerns on this invention can be utilized as an inexpensive manufacturing method of the film for electromagnetic wave transmission.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Radar Systems Or Details Thereof (AREA)
  • Details Of Aerials (AREA)

Abstract

Cette invention concerne un film de revêtement métallique pour transmission d'ondes électromagnétiques qui peut être produit de manière peu coûteuse en utilisant un métal autre que l'indium. L'invention concerne en outre un procédé de formation d'un film de revêtement métallique pour transmission d'ondes électromagnétiques et un dispositif radar embarqué. Dans le procédé de formation du film de revêtement métallique pour transmission d'ondes électromagnétiques (100), une couche d'adhésion catalytique (20) contenant une résine polyester insoluble dans l'eau et disposée sur la surface d'une base non conductrice (10) est dotée d'un film de revêtement métallique (3). Ledit film (3) est déposé en forme d'îlot par dépôt autocatalytique. Entre les îlots (31), ledit film comprend de 1 à 5 000 interstices (32) par surface unitaire (1mm2). Lesdits interstices forment le chemin de transmission pour l'onde électromagnétique. Le film de l'invention présente un éclat métallique.
PCT/JP2011/052513 2010-02-09 2011-02-07 Film de revêtement métallique pour transmission d'ondes électromagnétiques, procédé de formation d'un film de revêtement métallique pour transmission d'ondes électromagnétiques et dispositif radar embarqué WO2011099444A1 (fr)

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JP2010-026635 2010-02-09
JP2010026635A JP5390427B2 (ja) 2010-02-09 2010-02-09 電磁波透過用金属被膜、電磁波透過用金属被膜の形成方法及び車載用レーダー装置

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JPWO2019230955A1 (ja) * 2018-06-01 2021-07-29 大日本印刷株式会社 金属調加飾用部材及びそれを用いた金属調加飾成形体

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JP5465030B2 (ja) * 2010-02-09 2014-04-09 関東化成工業株式会社 電磁波透過用金属被膜、電磁波透過用金属被膜の形成方法及び車載用レーダー装置
JP5665234B2 (ja) * 2011-11-04 2015-02-04 三恵技研工業株式会社 電磁波透過用金属被膜及び車載用レーダ装置用のレドーム
JP5993676B2 (ja) 2012-09-14 2016-09-14 三恵技研工業株式会社 表面光輝品の製造方法
JP2014145678A (ja) * 2013-01-29 2014-08-14 Toyota Motor Corp 装飾被膜
JP2016080479A (ja) * 2014-10-15 2016-05-16 豊田合成株式会社 電波透過性カバー
JP6141816B2 (ja) * 2014-11-10 2017-06-07 三恵技研工業株式会社 電磁波透過用金属被膜及び車載用レーダ装置用のレドーム
JP5892629B2 (ja) * 2014-11-10 2016-03-23 三恵技研工業株式会社 電磁波透過用金属被膜の製造方法
JP6400062B2 (ja) * 2016-10-24 2018-10-03 日東電工株式会社 電磁波透過性金属光沢部材、これを用いた物品、及び、金属薄膜

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