WO2008004558A1 - Procédé de production un objet ornemental plaqué en convertissant une résine en une résine conductrice par métallisation sous vide et gabarit suspendu pour la fixation du moulage de résine - Google Patents

Procédé de production un objet ornemental plaqué en convertissant une résine en une résine conductrice par métallisation sous vide et gabarit suspendu pour la fixation du moulage de résine Download PDF

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Publication number
WO2008004558A1
WO2008004558A1 PCT/JP2007/063324 JP2007063324W WO2008004558A1 WO 2008004558 A1 WO2008004558 A1 WO 2008004558A1 JP 2007063324 W JP2007063324 W JP 2007063324W WO 2008004558 A1 WO2008004558 A1 WO 2008004558A1
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WO
WIPO (PCT)
Prior art keywords
resin
sputtering
molded product
resin molded
plating
Prior art date
Application number
PCT/JP2007/063324
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English (en)
Japanese (ja)
Inventor
Kunihiro Kakihara
Yoshinori Noda
Takashi Ouro
Original Assignee
Kakihara Kogyo Co., Ltd.
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Filing date
Publication date
Application filed by Kakihara Kogyo Co., Ltd. filed Critical Kakihara Kogyo Co., Ltd.
Publication of WO2008004558A1 publication Critical patent/WO2008004558A1/fr

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Classifications

    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics

Definitions

  • the present invention relates to a resin plating technique for applying metal plating to a resin molded product, and in particular, before the resin plating until the surface adjustment process of the resin resin plating, the etching process power, and the conductive metal treatment process.
  • the present invention relates to a method for producing a decorative adhesive product using a resin conductive material by sputtering carried out by sputtering treatment without using hexavalent chromic acid and a hanging jig for fixing the resin molded product.
  • a conventional general resin plating film-forming method includes: an etching process for roughening the surface of the resin molded article to be plated, an etching neutralization process, Direct plating pre-treatment process such as catalyst application process, conductive process (or electroless plating), and metal plating process, and pre-treated resin moldings with bright copper plating, semi-bright nickel plating, gloss
  • each plating process is performed in the order of nickel plating and MP nickel plating (microporous nickel plating), and finally chrome plating is applied.
  • a conductive step direct plating pretreatment or electroless plating is required to impart conductivity to the resin as a pretreatment for electroplating.
  • the conductive process (or electroless plating) of a resin molded product that uses a general wet method for resin plating is performed with a high concentration of chromic acid (hexavalent chromium) and sulfuric acid.
  • a catalyst such as PdZSn
  • a pretreatment technique for plating when electroless plating is applied to a resin molded product for example, as disclosed in Japanese Patent Application Laid-Open No. 5-132785, “Electroless plating pretreatment method”, Fiber
  • the surface of the insulating material contains chromic anhydride and sulfuric acid in the etching process of the insulating material, which is performed as a pretreatment when the surface of the insulating material made of polyimide resin is subjected to electroless plating.
  • electroless plating pretreatment method in which a two-stage etching process is performed in which etching is performed using a solution and then etching is performed using a solution containing hydrazine.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-132785
  • the resin etching process that roughens the resin surface which is the basis of this resin plating, still uses a mixed acid of high-concentration chromic acid (hexavalent chromium) and sulfuric acid.
  • This etching process using chromic acid has the potential to adversely affect the human body even during work in the process that requires only waste liquid treatment.
  • various technologies have been proposed to eliminate the etching process using chromic acid.
  • a pretreatment has been proposed that satisfies the stringent adhesion standards that are the basic performance of resin plating, such as automotive parts standards! I did not hesitate.
  • a PA resin polyamide resin, 6-nylon
  • POM resin polyacetal
  • LC P resin liquid crystal polymer
  • some resin materials can be etched without using a chromic acid-based etching solution.
  • a resin molded product of a resin that is relatively weak in acidity such as PPE resin (polyphenyl ether) can be surface-roughened using a permanganic acid-based etching solution.
  • PPE resin polyphenyl ether
  • a resin molded product of a general-purpose resin such as ABS resin (acrylonitrile Z butadiene Z styrene resin) can be etched using a manganic acid-based etchant. Etching can be performed with a weak etchant such as permanganate etching by adding a solvent pre-etching process.
  • a weak etchant such as permanganate etching by adding a solvent pre-etching process.
  • a conductive treatment technology for the resin base material for example, as disclosed in Japanese Patent Application Laid-Open No. 6-212405 of "Patent Document 2," a method of attaching copper on a polyphenylene sulfide support, Polyphenylene sulfide support is etched with RF argon plasma under vacuum . Sputter a layer of titanium on the etched surface without breaking the vacuum, and sputter the first copper layer on the surface sputtered with titanium, and after the sputtering procedure, apply the second copper layer to the support as desired. A method of electroplating the thickness has been proposed.
  • Patent Document 2 JP-A-6-212405
  • Patent Document 2 provides a peel strength of 4.5 to 5.5 pounds Z inches. This method is said to be useful for making products for EMI shielding and printed circuit boards.
  • Patent Document 3 Apparatus for coating a substrate with material vapor in a negative pressure or vacuum
  • a material vapor source and an ionic device comprising a cold anode and a cold cathode to generate a plasma between the anode and cathode and ionize the material vapor in an arc discharge assisted by the material vapor
  • the material vapor source and the anode and cathode of the ionization apparatus are electrically separated from each other in a negative pressure or vacuum!
  • a coating device has been proposed.
  • Patent Document 3 Japanese Patent Publication No. 9 511792
  • the conventional sputtering apparatus causes atoms to be ejected from the metal target 52 by collision of argon or the like excited by plasma discharge in a vacuum chamber 51, and a resin molded product ( W).
  • a metal target 52 is formed on the resin molded product W by this sputtering treatment.
  • the resin molded product W is placed in the apparatus. It was enough to fix it. However, a uniform film could not be formed on the surface of the resin molded product W having an uneven surface.
  • conductive resin is used using various chemicals such as a mixed acid of high concentration chromic acid and sulfuric acid.
  • chemicals may remain on the surface of the resin molded product.
  • the lift film S is a metal film with a thickness of about 30 to 50 m.
  • PCZ polyester-based materials such as ZPBT and PCZPET are used. This is because PCZ polyester-based materials are more suitable as a resin material for door handles, but it is not possible to make resin-handled door handles that can meet automotive specifications that are difficult to plate.
  • the handling environment is bad and handling is also dangerous.
  • the work environment was bad because formalin and ammonia, which are carcinogenic substances, were used in the electroless plating process.
  • it requires a complexing agent, making it difficult to treat wastewater. Since a water washing step is required after each treatment step, the amount of water used has problems such as winter.
  • the suspension jig is rotated with respect to the resin molded product fixed to the hanging jig, so that the outer peripheral side of the resin molded product can approach the metal target.
  • the inner peripheral side of the resin molded product does not approach the metal target. Therefore, a thick metal film is always formed on the outer peripheral side of the resin molded product, and on the contrary, a thin metal film is formed on the inner peripheral side of the resin molded product. The problem was.
  • the present invention has been devised in order to solve the problem. That is, the object of the present invention is to provide a resin surface roughening to a resin molded product by a processing method that does not use chemicals such as a mixed acid of chromic acid and sulfuric acid in the conventional etching process and conductive process, that is, a dry method. By adding conductivity and imparting conductivity, the surface layer of the resin does not deteriorate due to such chemicals, and it is possible to prevent cracking due to peeling between the oils and prevent cracking, and the safety of the resin-plated product Is also to provide a method for producing a decorative garment that can be secured.
  • a processing method that does not use chemicals such as a mixed acid of chromic acid and sulfuric acid in the conventional etching process and conductive process, that is, a dry method.
  • Another object of the present invention is to maintain the durability-abrasion resistance of the metal film of the resin plating by the wet electroplating method, to invest a large amount of equipment such as a clean room for painting, This is to eliminate the need for a painting process that has a high yield reduction risk.
  • the deposited film of the present invention is a metal-plated film formed by sputtering and wet electric plating in a vacuum chamber, and the laminated films are all metal, so that they have wear resistance that can withstand automotive applications. Durability and the like can be imparted. In addition, since there is no painting process, it is possible to reduce trash defects. Accordingly, it is an object of the present invention to provide a method for manufacturing a decorative article that can simultaneously eliminate the disadvantages of a conventional wet plating method and a decorative chromium sputtering method.
  • the object of the present invention is to use a sputtering apparatus improved so as to suppress deformation of the resin molded product and to perform sputtering at a high rate at a low temperature.
  • a method for producing a decorative plated product that makes it possible to perform the pretreatment process of various types of resin moldings by enabling the plating of strong resin materials that are difficult to fit by the wet method. There is also to provide.
  • an object of the present invention is to rotate the entire surface of the resin molded product so as to face the metal target in the vacuum chamber, so that the surface of the resin molded product having unevenness can be obtained without overheating.
  • An object of the present invention is to provide a hanging jig for fixing a resin molded product capable of uniformly forming a metal film.
  • the surface of the resin molded article (W) is cleaned by plasma treatment in a vacuum atmosphere and activated by surface modification in a sputtering apparatus.
  • the resin molded product (W) on which a metal thin film is formed in the step (S2) is moved so as to revolve before another metal target (52), and a conductive film is formed by sputtering while rotating there.
  • a conductive film forming step (S4), and forming the conductive film An electric plated step of step (S4) ⁇ molded article has finished (W) to electrically plated, a method of manufacturing a decorative plated products made of.
  • a film surface activation treatment step (S3) is performed in which the metal thin film formed on the resin molded product (W) is activated by surface modification treatment by plasma treatment. It is preferable to further provide.
  • the resin molded product (W) is suspended from the hanging jig (11), and the hanging jig (11) is rotated around its rotation axis (L). While sputtering is preferred.
  • the resin molded product (W) is suspended from a plurality of hanging jigs (11), and each hanging jig (11) is rotated around its rotation axis (L). It is preferable to perform sputtering treatment by moving a plurality of hanging jigs (11) so that their rotational axes follow a circular trajectory and revolve.
  • the resin surface cleaning 'activation step (S1) is plasma-treated in a vacuum atmosphere with a small amount of air remaining on the surface of the resin molded product (W).
  • a surface modification treatment by plasma treatment may be performed by injecting argon and a trace amount of oxygen into the surface of the resin molding (W) in a vacuum atmosphere. preferable.
  • the surface of the resin molded product (W) has a strong single metal bond or strong bond strength with oxygen. Strong metal An alloy containing is formed by sputtering.
  • a metal ionized to 0.01 to 50% can be formed on the surface of the resin molded product (W) in a vacuum atmosphere.
  • the film is formed so that the film thickness is about 0.01 to 2.0 m.
  • nickel or copper can be formed.
  • the film thickness is about 0.1 to 5.0 m.
  • the electroplating process is performed in the order of bright copper sulfate plating (S6), semi-bright nickel plating (S7), Mitsuzawa-Neckel plating (S8), MP nickel plating (microporous nickel plating) (S9).
  • S6 bright copper sulfate plating
  • S7 semi-bright nickel plating
  • S8 Mitsuzawa-Neckel plating
  • S9 MP nickel plating (microporous nickel plating) (S9).
  • S9 decorative finish plating
  • a plating treatment such as trivalent chromium plating, chromium plating, tin Z nickel alloy plating, ruthenium or gold plating is performed.
  • the sputtering process is performed in which atoms are ejected from the metal target (52) by collision of argon or the like excited by plasma discharge, and a film is formed on the resin molded product (W).
  • a hanging jig configured to fix the resin molded product during the sputtering process, which is characterized in that it is configured to manage.
  • a plurality of hanging rods (12) that are detachably leaned at intervals in the circumferential direction, and a hook jig that detachably fixes the resin molded product (W) attached to each hanging rod (12) (13) or In the vacuum chamber, the upper and lower rotating plates (14) can be rotated, and at the same time, the hanging rods (12) can be sputtered while being sputtered.
  • a partition wall (15) is further provided between the adjacent hanging rods (12) which are erected between the rotating plates (14).
  • the surface of the resin molded product (W) is cleaned and treated by plasma treatment in the sputtering apparatus in the resin surface cleaning 'active process (S1). Activated surface modification, and then in the metal thin film deposition step (S2), also in the sputtering apparatus, the strength of the bond strength with oxygen, single metal or the strength of bond strength with oxygen, including the metal An alloy is formed, and then a conductive film is formed by sputtering a predetermined metal on the metal thin film formed on the resin molded product (W) in the conductive film formation step (S4).
  • a metal film can be uniformly formed on the surface of the resin molded article (W) having an uneven surface by performing sputtering treatment on the surface while rotating it.
  • a high addition / high function film transparent protective film, high hardness film, etc.
  • plating using a dry method is possible.
  • Application as surface treatment technology other than pretreatment technology is possible.
  • the conductive film deposition process (S4) By adding the film surface activation treatment process (S3) after the metal thin film deposition process (S2), which is processed for the purpose of obtaining adhesion to the resin, the conductive film deposition process (S4) The adhesion of the conductive film to be processed is strengthened.
  • the final resin-plated product can be produced simply by applying the same electrical plating as in normal resin-plating.
  • the pretreatment of the resin plating that is, the conductive treatment of the resin molded product (W), Wet process power using hexavalent chrome
  • the conductive treatment of the resin molded product (W) Wet process power using hexavalent chrome
  • the resin molded product (W) is fixed to the hanging jig (11) in the vacuum chamber, and sputtering is performed while rotating the hanging jig (11).
  • the uneven shaped resin molded product (W) maintains the same distance as the metal target (52) force, so of course both the front and back sides of the resin molded product (W)
  • the metal can be uniformly formed on the entire surface of the molded resin article (W) having an uneven surface.
  • the upper and lower rotating plates (14) are rotated, and at the same time, the individual suspension rods (12) are rotated while performing the sputtering treatment to obtain the resin molded product (W).
  • the resin molded product (W) can only be uniformly formed on the entire surface of the resin molded product (W) with an uneven surface.
  • the metal target (52) can also be cooled away from the metal force.
  • FIG. 1 is a process diagram showing a method for producing a decorative garnish using a resin conductive material obtained by sputtering in Example 1.
  • FIG. 2 A bright nickel plating method is shown, (a) is a process diagram of a resin conductive treatment, and (b) is a wet electroplating process diagram.
  • FIG. 3 is a perspective view showing an example of a hanging rod of a hanging jig for fixing a resin molded product during a sputtering process.
  • FIG. 4 is an explanatory plan sectional view showing a positional relationship between a hanging rod of a hanging jig and a metal target.
  • FIG. 5 is a perspective view showing a hanging jig placed in a vacuum chamber.
  • FIG. 6 is a cross-sectional view of a resin molded product that has been subjected to a resin conductive treatment by sputtering in Example 1.
  • FIG. 7 is a cross-sectional view of a plating film attached by the method for producing a decorative garment using the resin conductive material obtained by sputtering in Example 1.
  • FIG. 8 is a table showing “Table 1 Plate Adhesion Measurement Results”.
  • FIG. 9 is a table showing “Table 2 Sputtering Experiment Conditions”.
  • FIG. 10 This is a table showing “Table 3 Result of actual product adhesion measurement (Ni—Cr) No 1”.
  • FIG. 11 This is a table showing “Table 4 Actual Product Adhesion Measurement Results (Ni—Cr) No2”.
  • FIG. 12 is a table showing “Table 5 Result of actual product adhesion measurement (Cr)”.
  • FIG. 13 is a SEM observation photograph.
  • FIG. 15 is a table showing “Table 21 Experimental results of ion irradiation treatment”.
  • FIG. 16 This is a table showing “Table 22-1 Experimental results 1Z2 with M target”.
  • FIG. 17 is a table showing “Table 22-2 Experimental result 2Z2 with M target”.
  • FIG. 18 is a table showing “Table 23 Experimental Results with Cr Targets”.
  • FIG. 19 is a table showing “Table 24 Experimental Results with Cu Target”.
  • FIG. 20 is a process diagram showing a conventional bright nickel plating method.
  • FIG. 21 is a process diagram showing a conventional method for conducting a resin.
  • FIG. 22 is a conceptual diagram showing a sputtering apparatus.
  • the method for producing a decorative garnish using the resin conductive material by sputtering according to the present invention is a pretreatment method in which the wet conductive method of the resin plating is changed to the dry conductive method. After the electrification, wet electroplating is performed as usual.
  • FIG. 1 is a process diagram showing a method for producing a decorative garment using the resin conductive material by sputtering in Example 1.
  • FIG. 2 shows an example of the bright nickel plating method.
  • (A) is a process diagram of a resin conductive treatment
  • (b) is a wet electroplating process diagram.
  • the resin molded product W is set in a jig, and the resin surface cleaning 'active process step S1 is performed.
  • the surface of the resin molded product W is cleaned and activated by plasma treatment in a vacuum atmosphere.
  • the surface of the resin molded article W is also cleaned in the sputtering apparatus.
  • a single layer of a metal having a strong binding force to oxygen or an alloy containing a metal having a strong binding force to oxygen is formed on the surface of the molded fat W by sputtering.
  • the metal thin film formed on the resin molded product W is activated by surface modification treatment by plasma treatment, and finally in the conductive film formation step S4, the resin molded product is activated.
  • Sputtering a predetermined metal on a metal thin film deposited on W This is a method of forming a conductive film.
  • a sputtering apparatus used in magnetron sputtering is an apparatus that deposits atoms on a metal target W by depositing atoms from a metal target by collision of argon or the like excited by plasma discharge in a vacuum atmosphere. .
  • a metal film of the target is formed on the resin molded product W, or the resin molded product W is irradiated with plasma.
  • the resin molded product W which is a decorative garment according to the present invention, is a so-called "appearance product" such as a resin glazed part for automobiles, a housing-related mortar plated part such as a chassis or faucet part.
  • the plating film floats up due to the separation of the resin-molded product W between the oil and grease, which may cause personal injury such as cutting hands.
  • the finishing power of the appearance is important. Incidentally, if it is a “functional product” such as a printed circuit board, there is no need to apply such decoration.
  • a vacuum atmosphere such as a vacuum chamber one Activates cleaning and surface modification.
  • argon plasma treatment is performed with a small amount of air remaining.
  • plasma treatment is performed by injecting argon and trace oxygen.
  • This resin surface cleaning 'active step S1 can use a plasma treatment method by an arc plasma deposition method in addition to the magnetron' sputtering method.
  • the metal thin film forming step S2 is a step for securing the adhesion between the resin and the plating film by the magnetron-sutter method in a vacuum atmosphere such as a vacuum chamber.
  • Vacuum for example 10 _2 ⁇ 3 (10 - 2-3 square) pulled about Pa, chromium ionized to 0.01 to 50% by the plasma, molybdenum, tungsten, titanium, zirconium, aluminum - ⁇ beam, indium
  • a single metal of a metal having a strong binding force with oxygen, such as nickel, noradium (an oxygen-rich metal) or an alloy containing these metals is formed on the resin molded product W.
  • the metal thin film to ensure the adhesion between the resin and the plating film is not only the good adhesion with the resin, but also the adhesion with the conductive film to smoothly handle the subsequent electric mating. It is necessary to use a metal with good properties.
  • the alloy ratio is not specified. Adhesion depending on the type of resin and molding conditions Select a good deposition metal material. For example, metallic copper can be used.
  • the resin molded product W after the metal thin film forming step S2 is further subjected to the active surface treatment in the film formation surface active surface treatment step S3.
  • the active surface treatment in the film formation surface active surface treatment step S3 For example, in a resin molded product W, 0.01 ⁇ ! The metal thin film formed at ⁇ 2.0 ⁇ m is activated by surface modification treatment with argon plasma treatment. This increases the adhesion between the resin molded product W and the metal thin film.
  • Conductive film forming step S4 is a step of forming a conductive film on the resin molded product W for electroplating.
  • a conductive film for electroplating is a conductive film for electroplating treatment, but it provides adhesion between the plating film formed by the dry plating method and the film formed by the electroplating method. It must be a metal film that can withstand acid treatment, soft etching with a dilute oxidizing agent, or electrolytic activation treatment. Therefore, the appropriate film thickness by the conductive film forming step S4 is, for example, 0. force and 2. O / zm in the case of metallic copper.
  • This conductive film formation process S4 film formation is a pre-process (activation process) of wet electroplating (electrocopper plating and electronickel plating), which is a subsequent process that has good adhesion to the underlying metal.
  • a metal other than metallic copper can be deposited if S5 is simple and has high adhesion.
  • FIG. 3 is a perspective view showing an example of a hanging jig for fixing the resin molded product W during the sputtering process.
  • FIG. 4 is an explanatory plan sectional view showing the positional relationship between the hanging rod of the hanging jig and the metal target.
  • the hanging jig 11 for fixing the resin molded product during the sputtering process of the present invention includes a hanging rod 12 provided to rotate in a vacuum chamber (not shown), and the hanging jig 12.
  • a hook 13 for fixing the resin molded product W is attached to the rod 12.
  • the resin molded product W is attached to each hook 13.
  • the resin molded product W indicates a door handle of an automobile. This door handle is only an example, and a resin molded product W having an uneven shape is suitable for the hanging jig 11 of the present invention.
  • a resin molded product W is attached, and the hanging jig 11 is placed in a vacuum chamber of a sputtering apparatus, and a metal target is formed by collision of argon or the like excited by plasma discharge.
  • This jig is used when atoms are ejected from the base 52 to form a film on the resin molded product (W).
  • a metal film can be uniformly formed on the entire surface of the concavo-convex shaped resin molded product W. can do.
  • FIG. 5 is a perspective view showing a hanging jig placed in the vacuum chamber.
  • the hanging jig 11 is used in a vacuum chamber that is detachably stood between two rotating plates 14 arranged in the vertical direction and the vertical rotating plate 14 with an interval in the circumferential direction. It is like that.
  • a partition wall 15 is provided between the hanging jigs 11 between the upper and lower rotating plates 14. This partition wall 15 is for preventing the metal sputtered from the metal target 52 from being deposited on another resin molded product W adjacent to the intended resin molded product W.
  • the sputtering process can be performed while rotating the upper and lower rotating plates 14 and simultaneously rotating the individual hanging jigs 11 in the vacuum chamber.
  • each of the resin molded products W revolves while rotating, even if the resin molded product W has an uneven shape, it can have an uneven surface by maintaining an equal distance from the metal target 52.
  • a film can be uniformly formed on the surface of the fat molded product W. Further, the resin molded product W can be cooled away from the metal target 52.
  • the resin surface cleaning 'activation process S1 the resin molded product w attached to the hanging jig 11 in a vacuum atmosphere is rotated so as to rotate.
  • cleaning and surface modification activities were performed by plasma treatment
  • the metal thin film forming step S2 the resin molded product W attached to the hook 12 was moved so as to revolve in front of the metal target 52 and rotated there.
  • the adhesion of the metal to the resin is ensured by sputtering.
  • the resin molded product W formed with the metal thin film in the metal thin film forming step S2 is replaced with another metal.
  • the conductive film is moved to revolve before the target 52 and rotated there, and a conductive film is formed by sputtering to complete the resin conductive process.
  • the vacuum Take out the Yanbar force, replace it with a jig for electric fitting, and finish it with the usual electric fitting process.
  • a molded resin W which has been subjected to a resin conductive treatment by magnetron sputtering, is activated in step S5. I'll do it.
  • This activation process S5 is a process for ensuring close contact with the electric plating. For example, when copper was used as the final conductive metal for dry plating, it was performed in a soft etching process that was immersed in a 20 gZL sodium persulfate solution for 30 seconds.
  • this activation process S5 depending on the type of conductive metal used for dry plating. The method is not limited as long as the adhesion between the dry plating film and the electroplating film can be secured.
  • Electric plating processes S6 to S10 can be applied to normal plating such as bright copper sulfate plating or metal plating.
  • each plating process is performed in the order of bright copper sulfate plating S6, semi-bright nickel plating S7, bright nickel plating S8, MP nickel plating (microporous nickel plating) S9.
  • plating finish S10 with trivalent chromium plating, tin Z nickel alloy plating, ruthenium or gold plating, and finish the plating process.
  • the conventional chromium plating of hexavalent chromium can be used.
  • This electric plating process S6 to S10 is an example, and it is a matter of course that other metals can be plated.
  • FIG. 6 is a cross-sectional view of a resin molded article that has been subjected to a resin conductive treatment by sputtering in Example 1.
  • FIG. 7 is a cross-sectional view of the plating film attached by the method for manufacturing a decorative adhesive using the resin conductive material by sputtering in Example 1.
  • Fig. 8 is a table showing "Table 1 Plate adhesion measurement results”.
  • Fig. 9 shows ⁇ Table 2. It is a table
  • Figure 10 is a table showing “Table 3 Actual Product Adhesion Measurement Results (Ni—Cr) No 1”.
  • Fig. 11 is a table showing "Table 4 Actual Product Adhesion Measurement Results (Ni-Cr) No2”.
  • Figure 12 is a table showing “Table 5 Result of actual product adhesion measurement (Cr)”.
  • the conductive film used metal copper (99.9%) as a target.
  • Figures 10 to 12 show “Table 3 Actual product adhesion measurement results (Ni—Cr) Nol” and “Table 4 Actual product adhesion measurement results (Ni—Cr) No2”. Actual product adhesion measurement results (Cr) ”show the results for chromium.
  • PCZABS resin plating prototype product of NiZCr experimental condition 10
  • PA / ABS resin plating prototype standard condition with 30 ° C / 0.5Hr ⁇ 80 ° C / 0.5Hr as one cycle, 120 A cycle thermal shock test was conducted. Therefore, it has been proved that the use of the method of the present invention makes it possible to mass-produce safe resin-plated parts.
  • the method for producing a decorative messenger product using a resin conductive material by sputtering uses a dry stencil method of sputtering for pretreatment of the resin plating, so that the conventional chromic acid method is used. Unlike the conductive wrinkle treatment method, various types of resin can be targeted.
  • AB S resin acrylonitrile / butadiene / styrene
  • PCZABS resin polycarbonate Z acrylonitrile / butadiene / styrene
  • PC / PET resin polycarbonate / polyethylene terephthalate
  • PCZPBT resin polycarbonate Z polybutylene terephthalate
  • LCP resin liquid crystal polymer
  • PA resin polyamide
  • PA / ABS polyamide Z atari mouth-tolyl / butadiene / styrene
  • PPE resin polyphenylene ether
  • PP resin polypropylene
  • PPS resin polyphenylene sulfide
  • SPS resin crystalline polystyrene
  • PS resin polystyrene
  • MMA resin methyl methacrylate
  • epoxy resin urethane resin
  • PET resin polyethylene terephthalate
  • PBT resin polybutylene terephthalate
  • the adhesion between the nylon-based resin and the dry plating film is good.
  • Nylon-based resin is difficult to obtain a beautiful plating appearance due to etching treatment with hydrochloric acid or the like when wet-coated, and it is difficult to obtain a beautiful plating appearance. A beautiful appearance like a messy product was obtained.
  • Adhesion can be improved by performing oxygen plasma treatment (including plasma treatment with air) together with resin cleaning prior to dry staking.
  • oxygen plasma treatment including plasma treatment with air
  • the condition is ⁇ It is necessary to change according to fat and molding conditions.
  • the surface observation after the surface cleaning and activation step S 1 was performed using a scanning electron microscope SEM (scanning electron microscope and AFM (Atomic Force Microscope)). .
  • Fig. 13 shows the SEM observation results and Fig. 14 shows the AFM observation results.
  • This functional group chemically bonds with the sputtered metal in the metal thin film forming step S2, thereby generating adhesion with the resin.
  • Fig. 15 “Table 21 Experimental Results of Ion Irradiation Treatment” shows various plasma treatments for PAZABS (PA ratio 50%, 70%, with filler) and PCZABS, PCZPET automotive interior door handle products.
  • Fig. 3 shows the results of an experiment on the condition of the resin surface cleaning 'activation step S1).
  • the door handle RH (right side) and LH (left side) may differ greatly in adhesion, so the adhesion was different depending on the molding conditions.
  • a mold is used for a product having the same shape and using different resin raw material specifications such as plating (PCZABS) and Z coating (PCZPET).
  • PCZABS plating
  • PCZPET Z coating
  • Effort raw material change work The cost can be reduced such that the work and the die mounting work on the molding machine can be omitted.
  • the resin surface of the resin molded product W is treated by a treatment method that does not use chemicals such as a mixed acid of chromic acid and sulfuric acid in the conventional etching process and conductive process, that is, a dry process.
  • a treatment method that does not use chemicals such as a mixed acid of chromic acid and sulfuric acid in the conventional etching process and conductive process, that is, a dry process.
  • the method for producing a decorative garnish using a resin conductive material by sputtering includes a radiator grill, a door regulator handle, a knock door girsh, and a mall that require high corrosion resistance and heat cycle resistance.
  • Parts such as automotive parts with grease for automobiles, handles that do not require high corrosion resistance, parts with grease for household appliances such as knobs, notebook PC cases that require high corrosion resistance, camera cases, mobile phone cases, etc. It can be used for various applications such as products such as fat-plated rigid housings.
  • the method for producing a decorative article using a resin conductive material by sputtering includes an automobile resin such as an automobile interior door handle, an exterior door handle, and an exterior handle cover part.
  • an automobile resin such as an automobile interior door handle, an exterior door handle, and an exterior handle cover part.
  • Suitable for products such as metal parts, shower heads, faucet parts, etc. that are directly touched by humans, such as housing-related grease plated parts, and mobile phone parts.
  • the hanging jig of the present invention can be used as long as it is an apparatus for forming a film on a resin molded product W having an uneven shape.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physical Vapour Deposition (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention permet non seulement de façonner la surface de la résine, sans recourir à des produits chimiques classiques, par exemple l'acide chromique, mais aussi d'obtenir une conductivité pour le moulage de résine par un procédé à sec. On empêche ainsi la détérioration de la surface de résine du moulage de résine par ces produits chimiques. De plus, comme on n'utilise pas de produits chimiques polluants, on peut diminuer l'utilisation de substances polluantes. En outre, on évite le détachement de la couche de surface des objets plaqués de résine, ce qui permet d'assurer leur sécurité. L'invention concerne un procédé qui comprend une étape (S1) de nettoyage/activation de la surface de résine qui consiste à réaliser un traitement au plasma de la surface du moulage de résine pour obtenir un nettoyage et une activation du reformage de surface ; une étape (S2) de formation d'un film fin métallique pour former un film fin métallique sur la surface du moulage de résine par métallisation sous vide ; une étape (S4) de formation d'un film qui confère une conductivité, qui consiste à former par métallisation sous vide un film de nickel, de cuivre, entre autres, qui confère une conductivité sur le film fin métallique formé sur le moulage de résine et enfin une étape d'électroplacage qui consiste à électroplaquer le moulage de résine.
PCT/JP2007/063324 2006-07-05 2007-07-03 Procédé de production un objet ornemental plaqué en convertissant une résine en une résine conductrice par métallisation sous vide et gabarit suspendu pour la fixation du moulage de résine WO2008004558A1 (fr)

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PCT/JP2006/313968 WO2008004315A1 (fr) 2006-07-05 2006-07-13 procédé de production d'objets plaqués de manière décorative en communiquant une électroconductivité à la résine par pulvérisation cathodique
PCT/JP2007/063324 WO2008004558A1 (fr) 2006-07-05 2007-07-03 Procédé de production un objet ornemental plaqué en convertissant une résine en une résine conductrice par métallisation sous vide et gabarit suspendu pour la fixation du moulage de résine

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014229223A (ja) * 2013-05-27 2014-12-08 アルプス電気株式会社 入力装置
CN107326414A (zh) * 2017-05-11 2017-11-07 厦门建霖工业有限公司 一种塑料基材无铬金属化方法

Families Citing this family (2)

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US20100161359A1 (en) * 2008-12-18 2010-06-24 At&T Intellectual Property I, L.P. Risk Management for Cable Protection Via Dynamic Buffering
FR2977254B1 (fr) * 2011-06-29 2013-08-30 Valeo Securite Habitacle Piece plastique a metallisation selective et procede de fabrication correspondant

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JPH05311486A (ja) * 1982-12-27 1993-11-22 Tokyo Pureiteingu Kk アルミニウムを素材とするメッキにより鏡面を付与された製品
JPH06212405A (ja) * 1991-10-31 1994-08-02 Hoechst Celanese Corp ポリフェニレンサルファイド支持体上に銅をめっきする方法
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JPH11185308A (ja) * 1997-12-25 1999-07-09 Nikon Corp 光ディスク並びにその製造装置および製造方法
JP2001104875A (ja) * 1999-10-05 2001-04-17 Toyo Terumii Kk 自動車外装用樹脂メッキ部品及びその製造法
JP2002293967A (ja) * 2001-03-30 2002-10-09 Ichikoh Ind Ltd ウレタン樹脂メッキ製品の製造方法

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JPH05311486A (ja) * 1982-12-27 1993-11-22 Tokyo Pureiteingu Kk アルミニウムを素材とするメッキにより鏡面を付与された製品
JPH03229890A (ja) * 1990-08-31 1991-10-11 Tokyo Pureiteingu Kk アルミニウムを素材としメッキにより鏡面を付与された製品の製造法
JPH06212405A (ja) * 1991-10-31 1994-08-02 Hoechst Celanese Corp ポリフェニレンサルファイド支持体上に銅をめっきする方法
JPH07292471A (ja) * 1994-04-26 1995-11-07 Mitsubishi Chem Corp スパッタリング方法
JPH09157844A (ja) * 1995-11-30 1997-06-17 Nippon Piston Ring Co Ltd 回転式コンプレッサ用ベーンの物理蒸着膜形成方法および装置
JPH11185308A (ja) * 1997-12-25 1999-07-09 Nikon Corp 光ディスク並びにその製造装置および製造方法
JP2001104875A (ja) * 1999-10-05 2001-04-17 Toyo Terumii Kk 自動車外装用樹脂メッキ部品及びその製造法
JP2002293967A (ja) * 2001-03-30 2002-10-09 Ichikoh Ind Ltd ウレタン樹脂メッキ製品の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014229223A (ja) * 2013-05-27 2014-12-08 アルプス電気株式会社 入力装置
CN107326414A (zh) * 2017-05-11 2017-11-07 厦门建霖工业有限公司 一种塑料基材无铬金属化方法
CN107326414B (zh) * 2017-05-11 2020-05-15 厦门建霖健康家居股份有限公司 一种塑料基材无铬金属化方法

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