JP4275157B2 - Metallization method for plastic surfaces - Google Patents

Description

  The present invention relates to a method for metallizing a plastic surface, and more specifically, a plating film having high adhesion is formed only on a plastic surface without depositing on the surface of a jig for holding a product to be plated during the plating operation. On how to do.

  Conventionally, when metallization treatment is applied to plastic surfaces such as acrylonitrile butadiene styrene (ABS) resin and polycarbonate / acrylonitrile butadiene styrene (PC / ABS), the adhesion between the plastic surface and the plating film is improved. Therefore, it is known to perform an etching process for roughening the plastic surface with a mixed solution of chromic acid and sulfuric acid before the plating process.

  However, in the above etching process, there is a problem that the working environment is deteriorated because the work is performed at a high temperature of 60 ° C. or more using harmful hexavalent chromium, and the waste water treatment needs attention. In addition, when plating on the plastic surface where plating such as PC / ABS is difficult to deposit in the plating process performed after the etching process, or when directly plating on an adsorbing metal catalyst called direct plating, adsorption of the catalytic metal In some cases, a conditioning process for increasing the thickness of the jig may be required. However, the plating may be deposited on the surface of the jig. Therefore, it is necessary to replace the jig when moving from the conditioning process to electroplating, and there is a problem that workability is very poor.

  Because of these problems, it is desired to provide an etching agent in place of a mixed solution of chromic acid and sulfuric acid. For example, instead of these etching agents, etching treatment is performed with a mixed solution of permanganate and phosphoric acid, and then ionicity is provided. A chromium-free plating process has been reported in which a treatment or the like is performed with the above catalyst solution, followed by plating (Patent Document 1).

However, in the above process, the amount of catalyst metal adsorbed on the plastic surface is increased by treatment with an ionic catalyst solution, but the catalyst metal is also adsorbed on the coating surface of the jig. There was a problem that plating was deposited on the surface of the jig together with the plastic surface depending on the process. In addition, this process has a problem that the reducing agent for reducing the catalyst metal is naturally decomposed and thus is not practical.
WO2005 / 094394 pamphlet

  Accordingly, an object of the present invention is to provide a metal having a highly practical plastic surface that can be plated with sufficient adhesion to the plastic surface in the metallization process of the chromium-free plastic surface and that does not deposit on the jig. Is to provide a method.

  As a result of intensive studies to solve the above problems, the present inventors have treated a plastic surface with an etching treatment solution containing a permanganate or the like, and then added a catalyst imparting enhancement solution containing a specific compound. By the treatment, it was found that the catalyst metal can be selectively adsorbed on the plastic surface in the subsequent catalyst application treatment, and the amount of adsorption is also increased. Furthermore, it was found that even if the plating treatment was performed following the catalyst application treatment, the plating could be sufficiently adhered to the plastic surface, and the plating was not deposited on the jig coating surface, and the present invention was completed. .

  That is, in the present invention, a plastic is treated with an etching treatment solution containing a permanganate and an inorganic acid, and then the treated plastic contains a compound having a selective adsorption property to a functional group exposed on the surface thereof. Treating with the catalyst imparting enhancing liquid, and further applying a catalyst to the plastic treated with the catalyst imparting enhancing liquid with the catalyst imparting treating liquid, and then performing metal plating on the plastic imparted with the catalyst. A method for metallizing a plastic surface.

  According to the method for metallizing a plastic surface according to the present invention, it is possible to perform plating with sufficient adhesion to the plastic surface, and it is a highly practical method in which plating does not deposit on a jig. Also, according to the metallization method of the plastic surface of the present invention, the amount of catalyst metal adsorbed on the plastic surface can be increased, so that it is possible to plate plastic that is difficult to adsorb catalyst metal in the conventional method as well. it can.

  Therefore, the method for metallizing a plastic surface according to the present invention is an excellent method for metallizing a chromium-free plastic surface.

  In the method for metallizing a plastic surface of the present invention (hereinafter referred to as “method of the present invention”), the plastic to be metallized is not particularly limited. For example, acrylonitrile butadiene styrene (ABS), polycarbonate / acrylonitrile Butadiene styrene (PC / ABS), acrylonitrile styrene acrylate (ASA), silicon-based composite rubber-acrylonitrile-styrene (SAS), noryl, polypropylene, polycarbonate (PC), acrylonitrile styrene, polyacetate, polystyrene, polyamide, Aromatic polyamide, polyethylene, polyether ketone, polyethylene terephthalate, polybutylene terephthalate, polysulfone, polyether ether sulfone, polyether imide, modified Polyphenylene ether, polyphenylene sulfide, polyamide, polyimide, epoxy resin, copolymer of a liquid crystal polymer or the like and the above polymers. In the method of the present invention, it is particularly preferable to metallize the surfaces of ABS and PC / ABS.

  In the method of the present invention, first, the plastic surface is treated with an etching treatment solution containing a permanganate and an inorganic acid. The permanganate contained in the etching treatment liquid is not particularly limited, and for example, metal salts of permanganate such as potassium permanganate and sodium permanganate can be used. The concentration of the permanganate in the etching treatment solution is 0.0005 mol / L or more, preferably 0.005 to 0.5 mol / L. On the other hand, the inorganic acid contained in the etching treatment solution is not particularly limited, and examples thereof include at least one inorganic acid selected from the group consisting of phosphoric acid, sulfuric acid, and nitric acid, and phosphoric acid is preferable. The concentration of these inorganic acids in the etching treatment solution is 2 mol / L or more, preferably 6 to 12 mol / L. In order to treat the plastic surface with the above etching treatment liquid, the liquid temperature is 0 to 50 ° C., preferably 25 to 40 ° C., and the plastic is immersed in the solution for 1 to 30 minutes, preferably 5 to 15 minutes. Good. By the treatment with the etching treatment solution, a functional group, specifically, a hydrophilic functional group such as a hydroxyl group or a carboxyl group is exposed on the surface of the plastic.

  Next, the plastic surface subjected to the etching treatment contains a compound having a selective adsorption property to the functional group exposed on the plastic surface by the treatment (hereinafter referred to as “selective adsorption compound”). Process. The selective adsorptive compound contained in the catalyst imparting enhancement liquid is not particularly limited as long as it is a compound having selective adsorptivity to the functional group as described above. For example, a compound containing a nitrogen atom, Compounds having a molecular weight of 100 or more, preferably compounds having 3 or more nitrogen atoms and a molecular weight of 100 or more. Specific examples of the selective adsorptive compound include ethylenediamine-based compounds such as ethylenetriamine and triethylenetetramine (excluding ethylenediamine); Epomin SP-003, Epomin SP-012, and Epomin SP-200 (all of which are Japan) Ethyleneimine polymer compounds such as PAA-03 and PAA-D41-HCl (both manufactured by Nitto Boseki Co., Ltd.); PAS-92 and PAS-M-1 And dialsylamine polymer compounds such as PAS-880 (all manufactured by Nitto Boseki Co., Ltd.); vinylamine polymer compounds such as PVAM-0570-B (manufactured by Mitsubishi Chemical Corporation). Among these selective adsorptive compounds, ethyleneimine polymer compounds, allylamine polymer compounds, and diallylamine polymer compounds are particularly preferable. The concentration of these selective adsorptive compounds in the catalyst application enhancing liquid is 10 mg / L or more, preferably 100 to 1000 mg / L. Moreover, it is preferable to adjust the pH of this catalyst provision enhancing liquid to 5 to 12, preferably 8 to 10, for example, with sodium hydroxide, sulfuric acid or the like. In order to treat the plastic surface with this catalyst application enhancing liquid, the liquid temperature is set to 0 to 70 ° C., preferably 25 to 35 ° C., and the plastic is immersed in the solution for 1 to 20 minutes, preferably 2 to 3 minutes. That's fine.

  Next, the plastic surface subjected to the catalyst application enhancing treatment is applied with a catalyst in a catalyst application treatment liquid. The catalyst application treatment liquid is not particularly limited as long as it is generally used for catalyst application in the plating step, but preferably contains a noble metal, more preferably contains palladium, and particularly preferably a palladium / tin mixed colloid catalyst solution. . In order to apply these catalysts to the plastic surface, the temperature of the catalyst application treatment solution is 10 to 60 ° C., preferably 20 to 50 ° C., and the plastic is immersed in the solution for 1 to 20 minutes, preferably 2 to 5 minutes. That's fine.

  The plastic surface thus provided with the catalyst is then metallized by metal plating such as electroless metal plating or electrometal plating (direct plating).

  When electroless metal plating is used for metallization of the plastic surface, the catalyst may be applied with a catalyst application treatment solution and then further treated with an activation treatment solution containing hydrochloric acid or sulfuric acid. The concentration of hydrochloric acid or sulfuric acid in this activation treatment liquid is 0.5 mol / L or more, preferably 1 to 4 mol / L. In order to treat the plastic surface with these activation treatment liquids, the liquid temperature of the activation treatment liquid is set to 0 to 60 ° C., preferably 30 to 45 ° C., and the plastic is added to the plastic for 1 to 20 minutes, preferably 2 to 5 minutes. What is necessary is just to immerse and process.

  The plastic subjected to the catalyst application and activation treatment as described above is then subjected to an electroless metal plating treatment. The electroless metal plating treatment can be performed according to a conventional method using electroless metal plating such as a known electroless nickel plating solution, electroless copper plating solution, and electroless cobalt plating solution. Specifically, when a plastic surface is plated with an electroless nickel plating solution, the plastic is immersed in an electroless nickel plating solution having a pH of 8 to 10 and a temperature of 30 to 50 ° C. for 5 to 15 minutes. Good.

  In addition, when electrometal plating (direct plating) is used for metallization of the plastic surface, after applying the catalyst with the catalyst applying treatment liquid, the activity further containing copper ions is pH 7 or more, preferably pH 12 or more. The treatment may be performed with a chemical treatment solution. The origin of the copper ions contained in this activation treatment liquid is not particularly limited, and examples thereof include copper sulfate. In order to treat the plastic surface with the activation treatment liquid, the liquid temperature of the activation treatment liquid is 0 to 60 ° C., preferably 30 to 50 ° C., and the plastic is immersed in it for 1 to 20 minutes, preferably 2 to 50 minutes. Process.

The plastic subjected to the application of the catalyst and the activation treatment as described above is then immersed in a general-purpose electrolytic copper plating bath such as a copper sulfate bath, and 2-10 in normal conditions, for example, 1-5 A / dm ² . What is necessary is just to process for one minute.

  In addition, metal plating such as electroless plating or electrometal plating may be performed on the plastic surface as described above, and various types of copper electroplating or nickel electroplating may be further applied to the metalized plastic surface according to the purpose. Is possible.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited by these descriptions.

Reference example 1
Surface modification treatment of plastic surface:
A 50 × 100 × 3 mm ABS resin (manufactured by UMGABS) was used as a sample, and this was used as an etching treatment solution at 35 ° C. containing 0.01 mol / L potassium permanganate and 7.5 mol / L phosphoric acid. Soaked for 10 minutes. For comparison, the sample was immersed in an etching treatment solution at 65 ° C. containing 3.5 mol / L chromic anhydride and 3.6 mol / L sulfuric acid for 10 minutes. The surface of each ABS resin after immersion was analyzed by a single reflection ATR method using a Fourier transform infrared spectrophotometer (FT / IR6100FV type (manufactured by JASCO Corporation)). The results are shown in FIG.

On the surface of the ABS resin treated with an etching treatment solution containing permanganic acid, peaks derived from hydroxyl groups and carboxyl groups were observed in the vicinity of 3340 cm ⁻¹ . On the other hand, no peaks derived from hydroxyl groups or carboxyl groups were observed on the surface of the ABS resin that was not etched. Moreover, almost no peaks derived from hydroxyl groups or carboxyl groups were observed on the surface of the ABS resin treated with the etching treatment solution containing chromic acid.

Example 1
Production of electroless plating film:
A 50 × 100 × 3 mm ABS resin (manufactured by UMGABS) was used as a sample, and this was used as an etching treatment solution at 35 ° C. containing 0.01 mol / l potassium permanganate and 7.5 mol / l phosphoric acid. Soaked for 10 minutes. Next, 200 mg / l PAA-03 (polyallylamine: manufactured by Nitto Boseki Co., Ltd.) was immersed in a catalyst application enhancing liquid at 30 ° C. adjusted to pH 10 with sodium hydroxide for 2 minutes. Further, after being immersed in 1.2 mol / l hydrochloric acid at room temperature for 1 minute, 35 ° C. palladium containing 10 ml / l CT-580 (manufactured by Ebara Eugleite Co., Ltd.) and 2.5 mol / l hydrochloric acid. / Soaking in tin mixed colloidal catalyst solution for 4 minutes, the catalyst was applied on the ABS resin. Next, this was immersed in an activation treatment liquid at 35 ° C. composed of 1.2 mol / l hydrochloric acid for 4 minutes to activate the catalyst. Thereafter, it is immersed in an electroless nickel plating solution ENILEX NI-5 (manufactured by Ebara Eugilite Co., Ltd.) at pH 8.8 and 35 ° C. for 10 minutes, and electroless nickel is formed on the ABS resin so that the film thickness becomes 0.5 μm. Plating was applied. Then, it was immersed for 1 minute at room temperature in the acid active solution containing 150-g / l V-345 (made by Ebara Eugene Corporation). Next, it was immersed in a 45 ° C. watt bath containing 0.75 mol / l nickel sulfate, 0.4 mol / l nickel chloride and 0.55 mol / l boric acid at 2 V / dm ² for 3 minutes. Further, this was dipped in a room temperature copper replacement solution containing 10 ml / l PDC (manufactured by Ebara Eugilite Co., Ltd.) and 0.5 mol / l sulfuric acid for 1 minute to replace the copper. Next, this was treated with a copper sulfate plating solution EP-30 containing 25 mol / l copper sulfate, 0.55 mol / l sulfuric acid and 0.0019 mol / l chlorine at 25 ° C. (manufactured by Ebara Eugene Corporation). Was immersed in 3 A / dm ² for 40 minutes, and electrolytic copper plating was performed on the ABS resin so that the film thickness was 20 μm. Thereafter, this was annealed at 70 ° C. for 1 hour.

Comparative Example 1
Preparation of electroless plating film (1):
In the process of Example 1, electroless nickel plating was performed on the ABS resin in the same manner except that the treatment for immersing in the catalyst application enhancing liquid for 2 minutes was not performed.

Comparative Example 2
Preparation of electroless plating film (2):
A 50 × 100 × 3 mm ABS resin (manufactured by UMGABS) was used as a sample, and this was used as an etching treatment solution at 35 ° C. containing 0.01 mol / l potassium permanganate and 7.5 mol / l phosphoric acid. Soaked for 10 minutes. Next, this was immersed in a catalyst solution at 50 ° C. containing 0.0024 mol / l palladium chloride for 4 minutes to give the catalyst onto the ABS resin. Next, the catalyst was activated by immersing in an activation treatment solution at 35 ° C. containing 10 ml / l of PC-66H (manufactured by Sugawara Eugleite Co., Ltd.) for 4 minutes. Thereafter, the same treatment as in Example 1 after electroless nickel plating was performed.

Comparative Example 3
Preparation of electroless plating film (3):
In the process of Comparative Example 2 , a 50 ° C. catalyst solution containing 0.0019 mol / l 2-aminopyridine and 0.00094 mol / l palladium sulfate instead of the 50 ° C. catalyst solution containing 0.0024 mol / l palladium chloride. Electroless nickel plating was performed on the ABS resin in the same manner except that it was immersed in 4 minutes.

Test example 1
The deposition property in the ABS resin of the electroless nickel plating film obtained in Example 1 and Comparative Examples 1 to 3 and the deposition on the jig coating were visually evaluated. Moreover, the palladium adsorption amount and adhesion strength on the ABS resin were measured as follows. These results are shown in Table 1.

<Measurement method>
Adsorption amount of palladium catalyst:
By reducing palladium ion adsorbed on the surface of the ABS resin, dissolving palladium with aqua regia and measuring the absorbance of the solution using a high-frequency plasma emission analyzer ICPS-7510 (manufactured by Shimadzu Corporation) The amount of palladium adsorbed was measured.
Adhesion strength measurement:
In accordance with JIS H8630 Annex 6, after forming an electrolytic copper plating film of about 20 μm on the surface of ABS resin, it is annealed at 70 ° C. for 1 hour, and then tensile strength tester AGS
-Adhesion strength was measured with H500N (manufactured by Shimadzu Corporation).

  In Example 1, the adsorption amount of the palladium catalyst was increased, and the depositability and adhesion strength of the electroless plating film were good. Moreover, no plating was deposited on the jig coating in this step. On the other hand, in Comparative Example 1, although the plating was not deposited on the jig, the amount of palladium adsorbed on the ABS resin was small, and an undeposited portion of the plating was generated. In Comparative Example 2 and Comparative Example 3, a sufficient amount of palladium adsorbed on the ABS resin was obtained, but plating was deposited on the jig coating.

Example 2
Direct plating on ABS resin:
A 50 × 100 × 3 mm ABS resin (manufactured by UMGABS) was used as a sample, and this was used as an etching treatment solution at 35 ° C. containing 0.01 mol / l potassium permanganate and 7.5 mol / l phosphoric acid. Soaked for 10 minutes. Next, after immersing 200 mg / l of PAA-03 (polyamylamine: manufactured by Nitto Boseki Co., Ltd.) for 2 minutes in a catalyst application enhancing liquid at 30 ° C. adjusted to pH 10 with sodium hydroxide, This was immersed in 1.2 mol / l hydrochloric acid for 1 minute at room temperature. Next, this was immersed for 4 minutes in an activator at 35 ° C. containing 25 ml / l D-POPACT (manufactured by Sugawara Eugilite), 1.2 mol / l hydrochloric acid and 1.7 mol / l sodium chloride. . Next, it was immersed for 3 minutes in a 45 ° C. metallizer containing 100 ml / l D-POPMEA (manufactured by Sakakibara Eugelite Co., Ltd.) and 100 ml / l D-POPMEB (manufactured by Sakakibara Eugelite Co., Ltd.). Finally, it is 10 to 25 ° C. EP-30 (copper sulfate plating solution: manufactured by Sugawara Eugleite Co., Ltd.) containing 0.9 mol / l copper sulfate, 0.55 mol / l sulfuric acid and 0.017 mol / l hydrochloric acid. Immerse for a minute and set the initial energization to a soft start (the first 30 seconds at 0.5 V, the next 30 seconds at 1.0 V, and finally 1.5 V), and direct plating on the ABS resin. gave.

  As a result of direct plating on the ABS resin, plating was able to be applied to the entire sample without energizing the plating on the jig coating within 5 minutes of energization. Further, the adhesion strength of the plating film measured in the same manner as in Test Example 1 was 0.8 kgf / cm.

Example 3
Preparation of electroless plating film on various resins:
Except for using various resins (ABS, PC / ABS (containing 65% PC), ASA, SAS, PC (manufactured by UMGABS), Noryl (manufactured by General Electric), polypropylene (manufactured by Nippon Polychem)) as samples. In the same manner as in Example 1, electroless nickel plating was applied on each resin.

Comparative Example 4
Preparation of electroless plating film on various resins:
Various resins (ABS, PC / ABS (containing 65% PC), ASA, SAS, PC (manufactured by UMGABS), Noryl (manufactured by General Electric), polypropylene (manufactured by Nippon Polychem)) were used as samples. Was immersed in an etching solution at 65 ° C. containing 3.5 mol / l chromic anhydride and 3.6 mol / l sulfuric acid for 10 minutes. Next, this was immersed in a reducing solution at 25 ° C. containing 0.5 mol / l hydrochloric acid and 10 ml / l Enirex RD (manufactured by Sugawara Eugleite Co., Ltd.) for 2 minutes. Further, it was subjected to the same treatment as in Example 1 after 1.2 mol / l hydrochloric acid immersion (pre-dip).

Test example 2
The depositability in various resins of the electroless plating film obtained in Example 3 and Comparative Example 4 and the deposition on the jig coating were evaluated visually. Further, the adhesion strength of the electroless plating film obtained on various resins was measured in the same manner as in Test Example 1. These results are shown in Table 2.

  The electroless plating film obtained in Example 3 was completely attached on any resin, and an adhesion strength equal to or higher than that of Comparative Example 4 (chromic acid etching process) could be obtained. Further, in Example 3, no plating was deposited on the jig coating even when any of the resins was subjected to electroless plating. On the other hand, in Comparative Example 4 (chromic acid etching process), an undeposited portion was generated in noryl and polypropylene resins, and no plating was deposited in the PC resin.

Example 4
Effect of catalyst application enhancing liquid:
In the process of Example 1, the active ingredient of the catalyst imparting enhancing liquid is PAA-03 (polyallylamine: manufactured by Nitto Boseki Co., Ltd.) as shown in Table 4 below, or Adeka Hope, Adekator, Adeka Bururonic (all Asahi Denka) The electroless nickel plating was performed on the ABS resin in the same manner except that it was changed to Industrial Co., Ltd. and Energy Coal (Lion Co., Ltd.). The depositability of the obtained electroless nickel coating on the ABS resin and the deposition on the jig coating were evaluated in the same manner as in Test Example 1. Further, the amount of palladium adsorbed on the ABS resin was measured in the same manner as in Test Example 1. These results are shown in Table 3.

  When an ethylenediamine compound, an ethyleneimine polymer compound, an allylamine polymer compound, a diallylamine polymer compound, or a vinylamine polymer compound is used as an active ingredient of the catalyst imparting enhancement liquid, the amount of palladium adsorption increases. Good plating depositability was obtained without depositing the jig. In contrast, compounds such as monoethanolamine, ethylenediamine, glycine, taurine, and aminoethanethiol, which are compounds having 2 or less nitrogen atoms in one molecule, did not show an increase in palladium adsorption. In addition, the effect of increasing the amount of adsorbed palladium was not observed even with anionic surfactants such as Adeka Hope and Energy Coal. In addition, the adsorbing amount of palladium did not increase with nonionic surfactants, such as adekatol and adekabururonic, and further caused deposition to the jig coating.

Example 5
Effect of inorganic acid in etching solution:
In the process of Example 1, electroless nickel plating was performed on the ABS resin in the same manner except that the composition of the etching treatment liquid was changed to that shown in Table 5 below. The depositability of the obtained electroless nickel coating on the ABS resin was evaluated in the same manner as in Test Example 1. These results are shown in Table 5. Moreover, the adhesive strength of the obtained electroless nickel plating film | membrane was done in the following tape peeling tests.

<Measurement method>
A cellophane tape (CT24: manufactured by Nichiban Co., Ltd.) was brought into close contact with the surface of the sample after electroless nickel plating, and the tape was peeled upward 90 °. After peeling the cellophane tape, it was confirmed by visual observation that the plating film was not peeled off together with the tape.

  All the mixed solutions of potassium permanganate and inorganic acid had good plating depositability and high adhesion strength, which cleared the tape peeling test. On the other hand, since the plastic surface was hardly modified in the liquids having a single composition of potassium permanganate and phosphoric acid, undeposited portions were generated in the subsequent electroless nickel plating. Moreover, the adhesion strength of the plated part was low and it was easily peeled off with tape.

Example 6
Effect of pH of aqueous solution containing catalyst application enhancing liquid:
In the process of Example 1, electroless nickel plating was performed on the ABS resin in the same manner except that the pH of the catalyst application enhancing solution was adjusted to the values shown in Table 6 below using sodium hydroxide and sulfuric acid. The depositability of the obtained electroless nickel coating on the ABS resin and the deposition on the jig coating were evaluated in the same manner as in Test Example 1. Further, the amount of palladium adsorbed on the ABS resin was measured in the same manner as in Test Example 1. These results are also shown in Table 6.

  When the pH of the catalyst application enhancing liquid was 5.0 to 12.0, the effect of increasing the amount of palladium adsorbed was observed without plating being deposited on the jig.

Example 7
Effect of concentration of catalyst application enhancing liquid:
In the process of Example 1, except that the concentration of polyallylamine (PAA-03: manufactured by Nitto Boseki Co., Ltd.), which is an active ingredient in the catalyst application enhancing liquid, is adjusted to the values shown in Table 7, all on the ABS resin. Was subjected to electroless nickel plating. Precipitation of the obtained electroless nickel coating on the jig coating in the ABS resin was evaluated in the same manner as in Test Example 1. Further, the amount of palladium adsorbed on the ABS resin was measured in the same manner as in Test Example 1. These results are also shown in Table 7.

  Regardless of the polyallylamine concentration, the effect of suppressing the precipitation on the jig coating and increasing the amount of palladium adsorbed was observed.

  The method for metallizing a plastic surface according to the present invention is a highly practical method that can perform plating with sufficient adhesion to the plastic surface and that does not deposit on the jig. In addition, according to the method of the present invention, the amount of catalyst metal adsorbed on the plastic surface can be increased, and therefore, it is possible to similarly plate plastic that is difficult to adsorb catalyst metal by the conventional method.

  Therefore, the method of the present invention can be used as a metallization process for a chromium-free plastic surface.

FIG. 1 shows the result of measuring the surface of an ABS resin with a Fourier transform infrared spectrophotometer (1: ABS resin surface without etching treatment, 2: ABS resin surface after treatment with an etching treatment solution containing chromic acid) 3: ABS resin surface after treatment with an etching treatment solution containing permanganic acid).

Claims (17)

Plastic, treated with etching solution containing permanganate and inorganic acids, then said treated plastic, Ri selective adsorptive functional groups exposed on the surface Oh, three or more nitrogen atoms And a catalyst imparting enhancing liquid containing a compound having a molecular weight of 100 or more , and further, a catalyst is imparted to the plastic treated with the catalyst imparting enhancing liquid with the catalyst imparting treating liquid, and then the catalyst is added. A method for metallizing a plastic surface, comprising applying metal plating to the applied plastic.   The method for metallizing a plastic surface according to claim 1, wherein the inorganic acid contained in the etching treatment solution is at least one inorganic acid selected from the group consisting of phosphoric acid, sulfuric acid and nitric acid.   The method for metallizing a plastic surface according to claim 1 or 2, wherein the etching treatment is performed using an etching treatment solution at 0 ° C to 50 ° C.   The method for metallizing a plastic surface according to any one of claims 1 to 3, wherein the concentration of permanganate in the etching solution is 0.0005 mol / L or more.   The method for metallizing a plastic surface according to any one of claims 1 to 4, wherein the concentration of the inorganic acid in the etching solution is 2 mol / L or more. Is contained in the catalyst imparting amplifier solution, Ri selective adsorptive functional groups exposed on the plastic surface is Oh, the nitrogen atom contains three or more compounds having a molecular weight of 100 or higher, ethylene diamine based compounds, ethyleneimine polymers The method for metallizing a plastic surface according to any one of claims 1 to 5, which is a compound, an allylamine polymer compound, a diallylamine polymer compound or a vinylamine polymer compound . The method for metallizing a plastic surface according to any one of claims 1 to 6 , wherein the concentration of the compound having selective adsorptivity to the functional group exposed on the plastic surface in the catalyst application enhancing liquid is 10 mg / L or more. The method of metallizing a plastic surface according to any one of claims 1 to 7 , wherein the pH of the catalyst application enhancing liquid is 5 to 12. The method for metallizing a plastic surface according to any one of claims 1 to 8 , wherein the metal plating is electroless plating. The method for metallizing a plastic surface according to claim 9 , wherein the catalyst application treatment liquid contains a noble metal. The method for metallizing a plastic surface according to claim 9 or 10 , wherein the catalyst application treatment liquid is a solution containing palladium. The method for metallizing a plastic surface according to any one of claims 9 to 11 , wherein the catalyst application treatment liquid is a palladium / tin mixed colloid catalyst solution. The method for metallizing a plastic surface according to any one of claims 1 to 12 , further comprising a step of treating with an activation treatment liquid containing hydrochloric acid or sulfuric acid after applying the catalyst with the catalyst application treatment liquid. The method for metallizing a plastic surface according to claim 13 , wherein the concentration of hydrochloric acid or sulfuric acid in the activation treatment liquid is 0.5 mol / L or more. The method for metallizing a plastic surface according to any one of claims 1 to 8 , wherein the metal plating is electroplating. The method for metallizing a plastic surface according to claim 15 , wherein the catalyst application treatment solution is a palladium / tin mixed colloid catalyst solution. The method for metallizing a plastic surface according to claim 16 , further comprising treating with an activation treatment liquid containing copper ions and having a pH of 7 or higher after the catalyst is imparted with the catalyst provision treatment liquid.

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