JP5131683B2 - Plating jig used for plating of resin moldings - Google Patents

Description

  The present invention relates to a plating jig used for plating a resin molded body.

  As a method of forming an electroplated film on a resin molded body, after degreasing and etching, neutralization and pre-dip are performed as necessary, and then a colloidal solution containing a tin compound and a palladium compound is used. A general method is to apply an electroless plating catalyst, perform an activation treatment (accelerator treatment) as necessary, and perform electroless plating and electroplating sequentially.

  In this case, a chromic acid mixed solution composed of a mixed solution of chromium trioxide and sulfuric acid is widely used as the etching treatment solution. However, the chromic acid mixture contains toxic hexavalent chromium, which has an adverse effect on the working environment. In addition, in order to treat wastewater safely, neutralization precipitation is performed after reducing hexavalent chromium to trivalent chromium ions. Therefore, complicated treatment is required for wastewater treatment. For this reason, in consideration of safety during work on site and the environmental impact of wastewater, it is desirable to use an etching treatment solution that does not contain chromic acid.

  As an etching solution that can replace the chromic acid mixed solution, an etching solution containing permanganate as an active ingredient is known. As such an etchant, an alkaline etchant containing a permanganate and an alkali metal hydroxide (see Non-patent Document 1 below), an acidic etchant containing a permanganate and an inorganic acid (the following non-patent patent) Document 2) is known. However, when an etching solution containing a permanganate is used, there is a problem that electroless plating is likely to deposit on a plating jig for fixing an object to be plated.

  When using a chromic acid mixture used in the past as an etching solution, a small amount of hexavalent chromium remains in the insulating coating portion of the plating jig in the etching process, which becomes a catalyst poison and is used for electroless plating. Even when the catalyst remains on the insulating coating portion of the plating jig, the deposition of electroless plating on the plating jig is prevented. For this reason, even when electroplating is subsequently performed, electroplating does not deposit on the plating jig, and electroless plating and electroplating can be performed continuously.

  On the other hand, when using an etching treatment liquid containing permanganate as an active ingredient, since the etching treatment liquid does not contain a component that becomes a catalyst poison, electroless plating is applied to the insulating coating portion of the plating jig. When the catalyst for use adheres, electroless plating is deposited on this portion. For this reason, when electroplating is continued, it is necessary to replace the plating jig, and the treatment process becomes very complicated.

For this reason, as a measure for preventing the deposition of electroless plating on the jig for plating, a jig on which a fluororesin coating is applied leaving an energized part (see Patent Document 1 below), and a part to be plated that is not in contact with the plating jig A jig (see Patent Document 2 below) having an insulating coating such as a fluororesin is proposed. However, these jigs are not practical because the entire surface of the plating jig needs to be coated with an expensive fluororesin or the like, and the cost is high.
Japanese Patent Laid-Open No. 5-1488692 JP-A-6-10197

  The present invention has been made in view of the above-mentioned problems of the prior art, and its main purpose is a jig for plating used in plating treatment of a resin molded body, which comprises permanganate as an active ingredient. An object of the present invention is to provide a new plating jig capable of preventing the deposition of electroless plating on the jig even when an etching process using an etching solution is performed.

  The present inventor has intensively studied to achieve the above-described object. As a result, in the case where a film containing at least one resin selected from the group consisting of silicone resin and olefin resin is formed on at least a part of the insulating coating portion of the plating jig, electroless is applied to these resin portions. It has been found that the plating hardly deposits, and when the electroplating is subsequently performed, these resin portions become insulating portions and the deposition of the plating film on the jig can be prevented. Moreover, both the silicone resin film and the olefin resin film are hardly attacked by the etching solution containing the permanganate, and are long-term in the plating process including the etching process using the etching solution containing the permanganate. The present inventors have found that it can be used stably and have completed the present invention.

That is, the present invention provides the following plating jig.
1. A plating jig for use in plating treatment of a resin molded body, wherein the entire insulating coating portion of the plating jig or at least a part of the surface portion of the insulating coating portion is selected from the group consisting of a silicone resin and an olefin resin. A plating jig characterized by being formed of a film containing at least one kind of resin.
2. The plating jig according to claim 1, wherein the entire insulating coating portion is formed of a film containing at least one resin selected from the group consisting of a silicone resin and an olefin resin.
3. Item 2. The plating jig according to Item 1, wherein in the insulating coating portion, another insulating film is formed under the film containing at least one resin selected from the group consisting of a silicone resin and an olefin resin.
4). Item 2. The plating jig according to Item 1, wherein in the insulating coating portion, another insulating film is formed on a film containing at least one resin selected from the group consisting of a silicone resin and an olefin resin.
5. A film containing at least one resin selected from the group consisting of silicone resin and olefin resin is (i) a single film of a silicone resin, (ii) a film made of a mixed resin of a silicone resin and another insulating resin, ( iii) Single film of olefin resin, (iv) Film made of mixed resin of olefin resin and other insulating resin, or (v) Film made of mixed resin of silicone resin, olefin resin and other insulating resin The plating jig according to any one of claims 1 to 4.
6). Item 6. The plating jig according to any one of Items 1 to 5, which is used in a plating treatment method including an etching treatment step using an etchant containing a permanganate.

  Hereinafter, the plating jig used for the plating treatment of the resin molded body of the present invention and the plating treatment step using the plating jig will be specifically described.

Plating Jig The plating jig of the present invention is a film containing at least one resin selected from the group consisting of a silicone resin and an olefin-based resin, wherein the entire insulating coating portion or at least a part of the surface portion of the insulating coating portion is formed. It is formed by. That is, in the plating jig of the present invention, the entire insulating coating portion or at least a part of the surface portion of the insulating coating portion is (i) a single coating of a silicone resin, and (ii) a silicone resin and other insulating resins. (Iii) A single film of olefin resin, (iv) A film of mixed resin of olefin resin and other insulating resin, or (v) Silicone resin, olefin resin and other insulation It is formed by the membrane | film | coat which consists of mixed resin of adhesive resin.

  The plating jig having such a structure can be effectively used when a resin molded body is an object to be plated, and in the electroless plating process, at least selected from the group consisting of a silicone resin and an olefin resin. It is possible to suppress the deposition of electroless plating on the film portion containing a kind of resin. As a result, even when electroplating is performed after the electroless plating process, the plating process can be continuously performed without replacing the jig.

  FIG. 1 is a drawing schematically showing a plating jig of the present invention. In FIG. 1, 1 is a jig | tool main body, 2 is a contact part with to-be-plated object, 3 is an insulation coating | coated part, 4 is an electric power feeding part.

  In the plating jig 1 shown in FIG. 1, the object to be plated is fixed to the jig at the contact portion 2 and is energized from this portion. The shape of the contact portion 2 can be determined as appropriate according to the shape of the object to be plated, and may be any shape as long as the object to be plated can be stably fixed and current can be secured to the object to be plated. The contact portion 2 is in a state where the conductive material is exposed so as to allow current to be applied to the object to be plated. The conductive material forms a skeleton of the plating jig of the present invention, and for example, stainless steel, copper, or the like can be used.

  The insulating coating portion 3 is formed on the surface of the jig 1 at a portion immersed in the plating solution. Thereby, when performing an electroplating process, corrosion of a jig | tool can be prevented and precipitation of plating to a jig | tool can be prevented.

  The plating jig of the present invention is formed by a film containing at least one resin selected from the group consisting of a silicone resin and an olefin-based resin, wherein the entire insulating coating portion 3 or at least a part of the surface portion of the insulating coating portion 3 is formed. It is necessary to be. The plating jig of the present invention is used when a plating film is formed on a resin molded body. In the plating process on the resin molded body, there is no surface on the surface of the resin molded body that is the object to be plated. An electroplating catalyst is provided, then an electroless plating film is formed to impart conductivity to the surface of the resin molded body, and then electroplating is performed. When using the plating jig of the present invention, the deposition of electroless plating is almost completely prevented at the portion where the film containing at least one resin selected from the group consisting of silicone resin and olefin resin is formed. can do. For this reason, when electroplating is performed subsequent to electroless plating, a film portion containing at least one resin selected from the group consisting of a silicone resin and an olefin resin serves as an insulating portion, and the entire jig surface It is possible to prevent the electroplating from being deposited.

  A film containing at least one resin selected from the group consisting of a silicone resin and an olefin-based resin may be formed on the entire insulating coating portion 3 of the plating jig 1, and a part of the surface of the insulating coating portion 3. You may form in. However, it is necessary that a film containing at least one resin selected from the group consisting of a silicone resin and an olefin resin is present between each contact portion 2 and the power feeding portion 4.

  2 (a) to 2 (e) are cross-sectional views showing a cut surface by the AA 'line in the contact portion 2 of the plating jig shown in FIG. 1, from a group consisting of a silicone resin and an olefin resin. An embodiment of a jig on which a film containing at least one selected resin is formed is shown.

  The jig shown in FIG. 2A is a jig having a structure in which the insulating coating portion 3 is formed of a film 5 containing at least one resin selected from the group consisting of a silicone resin and an olefin resin.

  In the jig shown in FIG. 2 (b), the insulating film used in the conventional plating jig is formed on the film 5 containing at least one resin selected from the group consisting of silicone resin and olefin resin. A resin layer 6 is formed. As the insulating resin layer, for example, coating with soft vinyl chloride sol can be used. The exposed portion 5 ′ of the film containing at least one resin selected from the group consisting of a silicone resin and an olefin resin preferably has a width of about 5 mm or more in order to ensure sufficient insulation.

  2 (c) and 2 (d) are formed with a conventional insulating resin layer 6 such as soft vinyl chloride and at least one resin selected from the group consisting of silicone resins and olefin resins. The film 5 containing it is formed. The plating jig of this aspect includes at least one resin selected from the group consisting of a silicone resin and an olefin resin on the surface using a plating jig having a conventionally used insulating coating. It can be produced by forming a film. In the jig of FIG. 2 (c), only a part of the insulating resin layer 6 is exposed, and most of the part is covered with a film containing at least one resin selected from the group consisting of a silicone resin and an olefin resin. ing. In the jig of FIG. 2D, a film containing at least one kind of resin selected from the group consisting of a silicone resin and an olefin resin is formed only on a part of the surface of the insulating resin layer 6. In this case, in order to ensure sufficient insulation, the width of the film containing at least one resin selected from the group consisting of a silicone resin and an olefin resin is preferably about 5 mm or more.

  In the jig shown in FIG. 2 (e), a mixed resin layer 7 composed of a silicone resin and / or an olefin resin and another insulating resin is formed. As the other insulating resin, conventionally used soft vinyl chloride sol or the like can be used. In this case, for example, if necessary, aromatic hydrocarbons such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), isopropyl alcohol (IPA), diacetone alcohol, etc. A silicone resin and / or an olefin resin and another insulating resin may be dissolved in an organic solvent such as an alcohol solvent and used as a coating agent. The mixing ratio may be determined as appropriate so that the effect of preventing the deposition of electroless plating is sufficiently exhibited. Usually, the total amount of the silicone resin and the olefin resin is preferably about 40% by weight or more, and 50% by weight. It is more preferable to set it to about or more.

  The silicone resin used in the plating jig of the present invention may be a polymer having a siloxane bond (-Si-O-) as the main skeleton, and the type thereof is not particularly limited. For example, any of heat vulcanized silicone rubber, room temperature curable silicone rubber, and the like can be used.

  As the heat vulcanization type silicone rubber, millable rubber, liquid rubber and the like can be used, which may be either one-pack type or two-pack type, and resin such as organic oxide crosslinking type and addition reaction crosslinking type is used. be able to. As the room temperature curable silicone rubber, a one-component or two-component liquid rubber can be used, and either a condensation type or an addition type may be used.

  Among the above-mentioned silicone rubbers, as the millable rubber, for example, a compound containing, as a main component, a linear organosilicon compound (diorganopolysiloxane) of about 5000 to 10,000 after polymerization and a silica-based reinforcing agent or the like is used. be able to.

  As the condensation-type liquid rubber, diorganopolysiloxane having a reactive group such as Si—OH, Si—O—R, or Si—H (for example, a degree of polymerization of about 100 to 2000) can be used. A silicone resin film can be formed by crosslinking siloxanes using platinum, platinum compounds, tin, tin compounds, hydroxylamine and the like as catalysts. As the condensation reaction, those using various condensation reactions such as deacetic acid condensation, dealcoholization condensation, deamination condensation, deamidation condensation, deaminoxy condensation, deacetone condensation, dehydrogenation condensation, dehydration condensation, deoxime condensation, etc. Can be used. Specific examples of such condensation type silicone resins include deoxime type one-part room temperature curing type liquid silicone rubber (trade name: KE45T) manufactured by Shin-Etsu Silicone, and dealcohol type two manufactured by GE Toshiba Silicone. A liquid room temperature curable liquid silicone rubber (trade name: TSE350) or the like can be used.

  Further, as the addition type liquid rubber, polysiloxane having a vinyl group at the terminal can be used, and a silicone resin film can be formed by utilizing an addition reaction with a siloxane having a silanol group.

  In the present invention, an appropriate one may be appropriately selected from the above-described various silicone resins according to the method for forming the silicone resin film. For example, in order to form a silicone resin film by the dipping method described later, one having an appropriate viscosity suitable for dipping may be used.

  As the olefin resin, single weight of α-olefin such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 3-methylbutene-1,4-methylpentene-1, etc. Copolymers or copolymers of these α-olefins such as random or blocks can be used.

  As the olefin-based resin, an amorphous or crystalline resin can be used, but a crystalline resin is preferable. Among these, polyethylene, polypropylene, poly (1-butene), ethylene-propylene copolymer, poly (3-methylbutene-1), poly (4-methylpentene-1) and the like are preferable, and particularly polyethylene (for example, polyethylene Homopolymers, copolymers of ethylene units and other olefin units of 5 mol% or less, copolymers of ethylene units and other copolymerizable monomer units excluding 1 mol% or less of olefin units) are preferred. The average molecular weight, density, molecular structure (straight chain structure or branched chain structure) and the like of polyethylene are not particularly limited, but it is preferable to use, for example, those capable of forming a film by applying a powder coating method.

  The method for forming a film containing at least one resin selected from the group consisting of a silicone resin and an olefin resin is not particularly limited, and the film may be formed by a known method according to the type of resin used. As a method for forming the film, for example, a dipping method, a coating method, a spray method, or the like can be applied as appropriate, and a treatment such as vulcanization or baking may be performed as necessary. About these process conditions, what is necessary is just to determine suitably so that the film | membrane which has sufficient durability in a plating solution can be formed according to the kind of resin to be used. In the case of forming a film containing an olefin resin, it is particularly preferable to use a powdery olefin resin having a particle size of 1 to 10,000 μm and coat it by a powder coating method according to a known method.

  In addition, when using a mixture of a silicone resin and an olefin resin, for example, immerse the workpiece in a mixture of the silicone resin and the olefin resin, and then perform a treatment such as heating or baking as necessary. Just do it.

  The thickness of the resin film to be formed is not particularly limited, and may be a thickness that can ensure sufficient insulation and does not cause damage in the plating process. Usually, in the case of a film containing a silicone resin, it may be about 0.05 mm or more, and preferably about 0.05 to 5 mm. Moreover, in the case of the film | membrane containing an olefin resin, what is necessary is just to be about 0.1 mm or more, and it is preferable to set it as about 0.5-10 mm.

The plating jig of the present invention is used for the plating treatment of a resin molded body.
The type of the resin is not particularly limited, and in particular, a molded body made of various resins that have been subjected to electroless plating treatment can be used as an object to be plated. For example, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), a resin in which the butadiene rubber component of the ABS resin is replaced with an acrylic rubber component (AAS resin), and a butadiene rubber component in the ABS resin is replaced with an ethylene-propylene rubber component A styrene resin such as a resin (AES resin), an acrylonitrile-styrene copolymer resin (AS), or a polystyrene resin (PS) can be used as an object to be treated. In addition, an alloyed resin of the styrene resin and polycarbonate (PC) resin (for example, an alloy resin having a PC resin mixing ratio of about 30 to 70% by weight) can be used. Furthermore, polyacrylonitrile resin (PAN), polycarbonate resin (PC), polyamide resin (PA), nonyl, polyphenylene ether resin, polyphenylene oxide resin and the like having excellent heat resistance and physical properties can be used as well.
There is no limitation in particular about the shape of a resin molding, a magnitude | size, etc.

Plating treatment method The plating treatment method in the case of using the plating jig of the present invention is not particularly limited, and can be effectively used in a plating treatment method including a step of performing electroless plating treatment and electroplating treatment. This treatment method usually includes steps of etching treatment, catalyst application treatment, electroless plating treatment, and electroplating treatment, and neutralization treatment, conditioning treatment, etc. are performed as necessary. Hereinafter, although each process process is demonstrated easily, the jig | tool for plating of this invention is not limited to the use in the following process process.

(1) Etching process As an etching process, a well-known method is applicable as an etching process method with respect to a resin molding.

  In particular, the plating jig of the present invention can be effectively used in a plating method including an etching process using an etching solution containing permanganate as an active ingredient. The etching treatment liquid containing permanganate as an active ingredient does not contain harmful hexavalent chromium and is a highly safe treatment liquid, but does not contain a component that becomes a catalyst poison for electroless plating. There is a problem that electroless plating tends to be deposited on the insulating coating portion of the plating jig. When the plating jig of the present invention is used, even when etching is performed using an etching treatment liquid containing permanganate as an active ingredient, the electroless plating is hardly deposited on the jig surface. Can be completely prevented. As a result, it is possible to continuously perform electroless plating and electroplating without exchanging jigs in a plating process using a highly safe etching process solution containing permanganate. Moreover, the silicone resin film formed on the jig surface is hardly attacked by the etching treatment liquid containing permanganate as an active ingredient and can be used stably for a long period of time.

  Etching liquid containing permanganate as an active ingredient includes alkaline etching liquid containing permanganate and alkali metal hydroxide as active ingredients, and acidic etching liquid containing permanganate and inorganic acid as active ingredients. Etc. are known, and any of these etching solutions can be used.

  For example, as the alkaline etching solution, an aqueous solution containing about 40 to 70 g / L permanganate such as potassium permanganate and sodium permanganate and about 10 to 30 g / L sodium hydroxide can be used. It is not limited to this.

  Examples of the acidic etching solution include about 0.1 to 50 g / L permanganate such as potassium permanganate and sodium permanganate, and 100 to 100 inorganic acids such as sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid. An aqueous solution containing about 600 g / L can be used, but is not limited thereto.

  Etching using these etching solutions may follow a known method.

  Furthermore, as the etching treatment liquid containing permanganate, for example, about 20 to 1200 g / L of inorganic acid, about 0.01 to 40 g / L of permanganate, and halogen oxoacid, halogen oxoacid salt, An etching solution comprising an aqueous solution containing about 1 to 200 g / L of at least one component selected from the group consisting of persulfates and bismuth salts can be used. After performing an etching process on the resin molded body using this etching solution, a good electroless plating film having high adhesion is formed by applying a catalyst for electroless plating and then performing electroless plating. It becomes possible.

  Among the active ingredients in the etching solution described above, inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, carbonic acid, sulfurous acid, nitrous acid, phosphorous acid, boric acid, hydrogen peroxide, perchloric acid. Etc. can be used. Of these, sulfuric acid, hydrochloric acid and the like are particularly preferable. These inorganic acids can be used singly or in combination of two or more. The content of the inorganic acid needs to be about 20 to 1200 g / L, and preferably about 300 to 1000 g / L.

  Among the effective components in the etching solution, the permanganate may be a salt of an aqueous solution, and specific examples thereof include sodium permanganate and potassium permanganate. Permanganates can be used singly or in combination of two or more. The permanganate content needs to be about 0.01 to 40 g / L, and preferably about 0.1 to 10 g / L.

  Among the active ingredients in the etching solution, specific examples of halogen oxoacids include hypohalous acid, halous acid, halogen acid, perhalogen acid and the like. As the halogen oxoacid salt, the above-mentioned water-soluble salts of halogen oxoacids can be used. For example, sodium halogen oxoacid, potassium halogen oxoacid, etc. can be used. As the persulfate, water-soluble persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate can be used. Moreover, as bismuth acid salt, water-soluble bismuth acid salt, such as sodium bismuth acid and potassium bismuth acid, can be used. The halogen oxoacid, halogen oxoacid salt, persulfate and bismuth acid salt can be used singly or in combination of two or more. In particular, it is preferable to use at least one component selected from the group consisting of perhalogen acids such as perchloric acid, perbromic acid, and periodic acid, salts of the perhalogen acid, persulfates, and bismuth salts.

  In the etching solution described above, the content of at least one component selected from the group consisting of halogen oxoacids, halogen oxoacid salts, persulfate salts, and bismuth acid salts needs to be about 1 to 200 g / L. Yes, preferably about 10 to 100 g / L.

  Preferable specific examples of the etching solution include at least one inorganic acid selected from the group consisting of sulfuric acid and hydrochloric acid, permanganate, and a group consisting of perchloric acid, perbromic acid, periodic acid, and salts thereof. Mention may be made of aqueous solutions containing at least one selected halogenoxoacid.

  In order to perform an etching process using the above-described etching solution, a surface to be processed of a resin molded body that is a processing target may be brought into contact with the etching solution. The specific method is not particularly limited, and any method that can sufficiently bring the surface of the surface to be processed into contact with the etching solution may be used. For example, a method of spraying the etching solution onto the object to be processed can be applied, but normally, a method of immersing the object to be processed in the etching solution enables efficient processing.

  The etching process conditions are not particularly limited, and may be determined appropriately according to the degree of the target etching process. For example, when performing an etching process by immersing an object to be processed in an etching solution, the temperature of the etching solution may be about 30 ° C. to 70 ° C., and the immersion time may be about 3 to 30 minutes.

  If the surface of the resin molded body, which is the object to be processed, is severely soiled, the degreasing process may be performed according to a conventional method prior to the etching process.

(2) Neutralization process and conditioning After performing an etching process, a neutralization process can be performed as needed. By this treatment, components remaining after the etching treatment can be removed and unnecessary components can be prevented from being brought into the catalyst solution.

  As the treatment liquid used for the neutralization treatment, a reducing compound or the like can be used, but an inorganic acid or the like may be further contained. There is no particular limitation on the method of the neutralization treatment, and a conventional method may be followed.

  The conditioning process may be performed according to a conventional method. By performing the conditioning treatment, the amount of catalyst adhesion can be increased.

(3) Catalyst application process There are no particular limitations on the method for applying the electroless plating catalyst, and a catalyst for electroless plating such as palladium, silver, ruthenium, etc. may be applied according to a known method. As a method for applying the palladium catalyst, for example, a known method such as a so-called catalyst-accelerator method, a sensitizer-activating method, or an alkali catalyst method can be employed.

(4) Electroless plating step After applying the catalyst by the above-described method, an electroless plating film is formed on the surface of the resin molded body by performing electroless plating. When the plating jig of the present invention is used, an electroless plating film is almost deposited on the film containing at least one resin selected from the group consisting of a silicone resin and an olefin resin formed on the jig surface. There is nothing to do. For this reason, it is possible to continue electroplating without replacing the jig.

  As the electroless plating solution, any known self-catalyzed electroless plating solution can be used. Examples of the electroless plating solution include an electroless nickel plating solution, an electroless copper plating solution, an electroless cobalt plating solution, an electroless nickel-cobalt alloy plating solution, and an electroless gold plating solution.

  The conditions for electroless plating may be the same as known methods. Further, if necessary, two or more electroless plating films may be formed.

(5) Electroplating step After electroless plating, if necessary, activation treatment is performed with an aqueous solution of acid, alkali, etc., and then electroplating is performed. By using the plating jig of the present invention, it is possible to prevent deposition of electroless plating on the coating portion of at least one resin selected from the group consisting of a silicone resin and an olefin resin. The electroplating process can be performed continuously without changing the tool.

  The type of electroplating solution is not particularly limited, and may be appropriately selected from known electroplating according to the purpose.

  According to the plating jig of the present invention, the electroless plating hardly deposits on the film portion containing at least one resin selected from the group consisting of a silicone resin and an olefin resin, and the electroplating is performed subsequently. In this case, it is possible to prevent the plating film from being deposited on the jig. For this reason, it is possible to continuously perform the processes up to electroplating without exchanging the jig, and the plating process is greatly improved in efficiency.

  In particular, according to the plating jig of the present invention, when an etching solution containing a permanganate is used, it can be used stably for a long period of time without damaging the insulating coating. For this reason, a good plating film can be efficiently formed on the resin molded body by a plating method using a highly safe etching solution containing permanganate as an active ingredient.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 (silicone resin coating)
A plating jig was prepared by the following method.

(1) Jig for plating 1
A plating jig having the shape shown in FIG. 1 was prepared using a stainless steel wire having a diameter of 3 mm as a conductive material. The jig for plating is made of a stainless steel wire into a predetermined shape, applied with a commercially available primer for liquid silicone resin (trade name: ME121, manufactured by GE Toshiba Silicone), dried, and then condensed, two-component liquid Type liquid silicone resin (trade name: TSE350, manufactured by GE Toshiba Silicone) for 5 seconds, baked at 180 ° C. for 5 minutes, and then immersed again in the same liquid silicone resin for 5 seconds and at 180 ° C. for 7 minutes. A silicone resin film having a thickness of about 0.1 to 5 mm is formed by baking. In the obtained plating jig, as shown in FIG. 2A, the entire insulating coating portion is formed of the silicone resin film 5, and the contact portion 2 with the object to be plated has a length of about 15 mm. The stainless steel wire is exposed. This is referred to as a plating jig 1.

(2) Jig for plating 2
A silicone resin film 5 having a thickness of about 0.1 to 5 mm was formed on a plating jig made of stainless steel wire in the same manner as the plating jig 1. Thereafter, it is immersed in a soft vinyl chloride coating sol (trade name: PG2401, manufactured by Alpha Kasei Co., Ltd.) for 5 seconds, baked at 180 ° C. for 5 minutes, and again immersed in the same soft vinyl chloride coating sol for 5 seconds. A soft vinyl chloride film 6 having a thickness of about 0.1 to 5 mm was formed by baking at a temperature of 7 ° C. for 7 minutes.

  The contact portion 2 with the object to be plated is in a state where the stainless wire is exposed with a length of about 15 mm, and the silicone resin is exposed about 5 mm in width in the insulating coating portion 5 ′ adjacent to this portion. Soft vinyl chloride sol was applied.

  In the plating jig obtained by the above method, as shown in FIG. 2 (b), the insulating coating portion is a state in which the soft vinyl chloride film 6 is laminated on the silicone resin film 5, and the object to be plated As for the contact portion 2 with a length of about 15 mm, the stainless steel wire is exposed, and the insulating coating portion 5 ′ having a width of about 5 mm near the contact portion with the object to be plated is in a state where the silicone resin is exposed. This is referred to as a plating jig 2.

(3) Jig 3 for plating
Using a stainless steel wire with a diameter of 3 mm as a conductive material, a plating jig having the shape shown in FIG. 1 was prepared, and then a commercially available primer for soft vinyl chloride coating sol (trade name: MP-3000, manufactured by Alpha Kasei Co., Ltd.) After being coated and dried, it was immersed in a soft vinyl chloride coating sol (trade name: PG2401, manufactured by Alpha Kasei Co., Ltd.) for 5 seconds and baked at 180 ° C. for 5 minutes. Then, the soft vinyl chloride film 6 having a thickness of about 0.1 to 5 mm was formed by immersing again in the same soft vinyl chloride coating sol for 5 seconds and baking at 180 ° C. for 7 minutes.

  Next, the jig on which the soft vinyl chloride film 6 is formed by the above-described method is immersed in a liquid silicone resin (trade name: TSE350, manufactured by GE Toshiba Silicone) for 5 seconds, baked at 180 ° C. for 5 minutes, and then again. The silicon resin film 5 having a thickness of about 0.1 to 5 mm was formed by immersing in the same liquid silicone resin for 5 seconds and baking at 180 ° C. for 7 minutes.

  In the plating jig obtained by the above method, as shown in FIG. 2 (c), the insulating coating portion is formed by laminating the silicone resin film 5 on the soft vinyl chloride film 6, and with the object to be plated. The contact portion 2 is in a state where the stainless wire is exposed with a length of about 15 mm. This is referred to as a plating jig 3.

(4) Jig for plating 4
In the same manner as the plating jig 3, a hard vinyl chloride film 6 having a thickness of about 0.1 to 5 mm was formed on a plating jig made of stainless steel wire. Next, the jig on which the soft vinyl chloride film 6 is formed by the above-described method is immersed in a liquid silicone resin (trade name: TSE350, manufactured by GE Toshiba Silicone) for 5 seconds, baked at 180 ° C. for 5 minutes, and then again. The silicon resin film 5 having a thickness of about 0.1 to 5 mm was formed by immersing in the same liquid silicone resin for 5 seconds and baking at 180 ° C. for 7 minutes. The silicone resin film 5 was not formed on the entire surface of the hard vinyl chloride film, but only about 10 mm in width in the vicinity of the contact portion 2 with the object to be plated.

  In the plating jig obtained by the above method, as shown in FIG. 2 (d), the insulating coating portion is formed of the soft vinyl chloride film 6, and only in the vicinity of the contact portion 2 with the object to be plated. The silicone resin film 5 having a width of about 10 mm is formed, and the stainless steel wire is exposed at a length of about 15 mm at the contact portion 2 with the object to be plated. This is referred to as a plating jig 4.

(5) Jig for plating 5
Using a stainless steel wire with a diameter of 3 mm as a conductive material, a plating jig having the shape shown in FIG. 1 was prepared, and then a commercially available primer for soft vinyl chloride coating sol (trade name: MP-3000, manufactured by Alpha Kasei Co., Ltd.) Was applied and dried. After that, a soft vinyl chloride coating sol (trade name: PG2401, manufactured by Alpha Kasei Co., Ltd.) and a liquid silicone resin (trade name: TSE350, manufactured by GE Toshiba Silicone) at a 1: 1 weight ratio for 5 seconds. After immersing and baking at 180 ° C. for 5 minutes, it is immersed again in the same solution for 5 seconds and baked at 180 ° C. for 7 minutes, so that the thickness of the mixed resin 7 of soft vinyl chloride and silicone resin is about 0.1 to 5 mm. Insulation coating was formed. In the obtained plating jig, as shown in FIG. 2 (e), the insulating coating portion is formed of a mixed resin 7 of soft vinyl chloride and silicone resin, and the contact portion 2 with the object to be plated is about 15 mm. The length of the stainless steel wire is exposed. This is referred to as a plating jig 5.

(6) Jig for plating 6
Using a stainless steel wire with a diameter of 3 mm as a conductive material, a plating jig having the shape shown in FIG. 1 was prepared, and then a commercially available primer for soft vinyl chloride coating sol (trade name: MP-3000, manufactured by Alpha Kasei Co., Ltd.) Was applied and dried. After that, it is immersed in a soft vinyl chloride coating sol (trade name: PG2401, manufactured by Alpha Kasei Co., Ltd.) for 5 seconds, baked at 180 ° C. for 5 minutes, and then again immersed in the same soft vinyl chloride coating sol for 5 seconds. The film was baked at 180 ° C. for 7 minutes to form a soft vinyl chloride film having a thickness of about 0.1 to 5 mm.

  In the obtained plating jig, the insulating coating part is formed of a soft vinyl chloride film, and the stainless steel wire is exposed with a length of about 15 mm at the contact part with the object to be plated. This is referred to as a plating jig 6.

As a plating test result, a flat plate (10 cm × 5 cm × 0.3 cm, surface area of about 1 dm ² ) of ABS resin (manufactured by UMG ABS Co., Ltd., trade name: Psycolac 3001M) is used. An object to be plated was fixed to -6, and electroless copper plating (Okuno Pharmaceutical Co., Ltd. CRP selector) and electrolytic copper plating were performed according to the processing steps described in Table 1 below. In addition, between each process, it washed with water.

  According to the above-described processing steps, electrolytic copper plating was performed for a maximum of 5 minutes, and the state of electrolytic copper plating in the insulating coating part of each plating jig and the state of electrolytic copper plating film deposition on the object to be plated were visually observed. The case where a uniform copper plating film was formed on the entire surface of the object to be plated was evaluated as ○. The results are shown in Table 2.

  As is clear from the above results, when using the plating jigs 1, 2, and 5 in which the surface of the insulating coating portion of the plating jig is formed of a silicone resin or a mixed resin containing a silicone resin, Even when electroplating was subsequently performed after electroless plating, the deposition of electroplating on the jig could be prevented. In addition, in the plating jigs 3 and 4 in which the silicone film is exposed only on a part of the surface of the insulating coating portion, although electroplating is deposited from the electrical contact of the object to be plated to the portion where the silicone resin film is exposed, It was possible to prevent the electroplating deposition from spreading on the insulation coating part beyond that. In the plating jig 4, the electroless plating deposited on the soft vinyl chloride film with the progress of electroplating was dissolved in the electroplating solution.

  In contrast, in the plating jig 6 in which the insulating coating portion is formed of a soft vinyl chloride resin, when electroplating is subsequently performed after electroless plating, electroplating is deposited on the insulating stomach portion. Moreover, since the electroplating was deposited on the insulating coating portion, the electric supply to the object to be plated was insufficient, and an undeposited part of the electroplating was generated on the surface of the object to be plated.

  As is clear from the above results, by using a plating jig in which a silicone resin film is formed on the entire insulating coating part or a part of the surface, electroless plating can be performed without replacing the plating jig. It can be seen that electroplating can be performed continuously, and the plating process is greatly improved in efficiency.

Example 2 (polyethylene resin film)
A plating jig having the same structure as the plating jigs 1 to 4 was produced in the same manner as in Example 1 except that a polyethylene resin was used instead of the silicone resin used in Example 1.

  The film made of polyethylene resin was heated in a 180 ° C oven, then immersed in powdered polyethylene with an average particle size of 1,000 µm and allowed to stand for 1 minute, then taken out and again in an oven at 180 ° C. It was formed by a method in which the surface was melted and smoothed by heating for 5 minutes, and finally immersed in water and cooled. The thickness of the polyethylene film formed was in the range of about 1-2 mm.

  Further, with respect to the plating jig 5, instead of a film made of a mixed resin of soft vinyl chloride and silicone resin, an insulating coating having a thickness of about 1 to 5 mm made of a mixed resin of soft vinyl chloride and polyethylene is formed. This was produced by the same method as in Example 1. A film made of a mixed resin of soft vinyl chloride and polyethylene is a solution in which a vinyl chloride coating sol (trade name: PG2401, manufactured by Alpha Kasei Co., Ltd.) and powdered polyethylene resin are mixed at a weight ratio of 1: 1. After immersing for 5 seconds and baking at 180 ° C. for 5 minutes, it was again immersed in the same solution for 5 seconds and baked at 180 ° C. for 7 minutes.

  Using the plating jigs (polyethylene resin coated products) 1 to 5 obtained by the above method, electroless copper plating and electrolytic copper plating were performed in the same process as in Example 1.

  As a result, the result is almost the same as when using a plating jig formed with a film made of silicone resin. When using the plating jigs 1, 2, and 5, electroplating is continued after electroless plating. Even in this case, the deposition of electroplating on the jig could be prevented. Further, when the plating jigs 3 and 4 with the polyethylene film exposed on only a part of the surface of the insulating coating portion are used, electroplating is performed from the electrical contact of the object to be plated to the portion where the polyethylene resin film is exposed. Although it was deposited, it was possible to prevent the spread of electroplating deposition on the insulation coating portion beyond that. In the plating jig 4, the electroless plating deposited on the soft vinyl chloride film with the progress of electroplating was dissolved in the electroplating solution.

  As is clear from the above results, even when using a plating jig in which a polyethylene resin film is formed on the entire insulation coating part or a part of the surface, electroless plating is performed without replacing the plating jig. It can be seen that electroplating can be performed continuously, and the plating process is greatly improved in efficiency.

Example 3 (mixed resin film of silicone resin and polyethylene resin)
Instead of the silicone resin used in the plating jig 1 of Example 1, a structure similar to that of the plating jig 1 is obtained in the same manner as in Example 1 except that a mixed resin of silicone resin and polyethylene resin is used. A plating jig was produced.

  The film made of a mixed resin of silicone resin and polyethylene resin is immersed for 5 seconds in a solution in which a liquid silicone resin (trade name: TSE350, manufactured by GE Toshiba Silicone) and polyethylene resin are mixed at a weight ratio of 1: 1. After baking at 180 ° C. for 5 minutes, it was again immersed in the same solution for 5 seconds and baked at 180 ° C. for 7 minutes. The thickness of the formed film was in the range of about 0.1-5 mm.

  Using the obtained plating jig, electroless copper plating and electrolytic copper plating were performed in the same steps as in Example 1. As a result, the result is almost the same as when using a plating jig formed with a film made of silicone resin. Even when electroplating is subsequently performed after electroless plating, electroplating is deposited on the jig. We were able to prevent.

Example 4 (mixed resin film of liquid silicone resin, polyethylene resin, and vinyl chloride sol)
Example except that a film made of a mixed resin of soft vinyl chloride, silicone resin and polyethylene resin was formed instead of the film made of a mixed resin of soft vinyl chloride and silicone resin used in the plating jig 5 of Example 1. The plating jig was prepared in the same manner as the plating jig 5 in FIG.

  The film made of a mixed resin of soft vinyl chloride, silicone resin and polyethylene resin is made of soft vinyl chloride coating sol (trade name: PG2401, manufactured by Alpha Kasei Co., Ltd.), liquid silicone resin (trade name: TSE350, GE Toshiba Silicone Co., Ltd.) Manufactured) and polyethylene resin is immersed in a 1: 1 weight ratio solution for 5 seconds, baked at 180 ° C. for 5 minutes, then again immersed in the same solution for 5 seconds and baked at 180 ° C. for 7 minutes. Formed by. The thickness of the formed film was in the range of about 0.1-3 mm.

  Using the obtained plating jig, electroless copper plating and electrolytic copper plating were performed in the same steps as in Example 1. As a result, the result is almost the same as when using a plating jig formed with a film made of silicone resin. Even when electroplating is subsequently performed after electroless plating, electroplating is deposited on the jig. We were able to prevent.

Schematic which shows typically the jig | tool for plating of this invention. The fragmentary sectional view of the jig | tool for plating of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Jig body 2 Contact part with to-be-plated object 3 Insulation coating | cover part 4 Electric power feeding part 5 Film | membrane 6 which contains at least 1 type of resin chosen from the group which consists of silicone resin and olefin resin 6 Insulating resin layer 7 Mixed resin layer

Claims (5)

A plating jig for use in plating treatment of a resin molded body, wherein the entire insulating coating portion of the plating jig or at least a part of the surface portion of the insulating coating portion is selected from the group consisting of a silicone resin and an olefin resin. A plating jig characterized by being formed of a film containing at least one kind of resin ,
A plating jig used in a plating method including an etching process step using an etchant containing a permanganate . The plating jig according to claim 1, wherein the entire insulating coating portion is formed of a film containing at least one resin selected from the group consisting of a silicone resin and an olefin resin. The plating jig according to claim 1, wherein in the insulating coating portion, another insulating film is formed under the film containing at least one resin selected from the group consisting of a silicone resin and an olefin resin. The plating jig according to claim 1, wherein in the insulating coating portion, another insulating film is formed on a film containing at least one resin selected from the group consisting of a silicone resin and an olefin resin. Coating film containing at least one resin selected from the group consisting of silicone resins and olefin resin consists of (i) alone coating of silicone resin, (ii) a silicone resin and a mixed resin of other insulating resin, (iii) Single film of olefin resin, (iv) Film made of mixed resin of olefin resin and other insulating resin, or (v) Made of mixed resin of silicone resin, olefin resin and other insulating resin It is a film | membrane, The jig | tool for plating in any one of Claims 1-4.

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