WO2008012984A1

WO2008012984A1 - Process for metallization of plastic surfaces

Info

Publication number: WO2008012984A1
Application number: PCT/JP2007/060332
Authority: WO
Inventors: Yasuyuki Kuramochi; Kaori Nakayama
Original assignee: Ebara-Udylite Co., Ltd.
Priority date: 2006-07-27
Filing date: 2007-05-21
Publication date: 2008-01-31
Also published as: JP4275157B2; TW200811311A; CN101490310B; JP2008031513A; KR101365970B1; CN101490310A; KR20090036123A

Abstract

The invention aims at providing a practical process for chrome-free metallization of plastic surfaces by which a plating film adhering tightly to the surface of a plastics part can be formed and which is free from the deposition on a jig. A process for the metallization of plastic surfaces which is characterized by treating a plastics part with an etching fluid containing both a permanganate and an inorganic acid, treating the resulting plastics part with a potentiator fluid for the impartment of a catalyst which contains a compound exhibiting selective adsorption to functional groups exposed on the surface of the plastics part, imparting a catalyst to the treated plastics part with a catalyst imparting fluid, and then subjecting the resulting plastics part to metal plating.

Description

Specification

Metallization method for plastic surfaces

Technical field

[0001] The present invention relates to a method for metallizing a plastic surface. More specifically, the present invention provides high adhesion only to a plastic surface without plating and depositing on the surface of a jig for holding the product to be stuck. The present invention relates to a method for forming a plating film.

Background art

[0002] Conventionally, when metallization treatment is performed on a plastic surface such as acrylonitrile butadiene styrene (ABS) resin, polycarbonate Z atari mouth-tolyl butadiene styrene (PCZABS), the plastic surface and plating film In order to improve the adhesion to the substrate, it is known to perform an etching process in which the plastic surface is roughened with a mixed solution of chromic acid and sulfuric acid before the plating process.

[0003] However, in the etching process described above, work is performed at a high temperature of 60 ° C or higher using harmful hexavalent chromium, so that the working environment is deteriorated, and the wastewater treatment needs attention. There was a problem. Also, in the plating process performed after the above etching process, when plating on a plastic surface where plating such as PCZABS is difficult to deposit, or when plating directly on an adsorbing metal catalyst called direct plating, adsorption of the catalyst metal Force that may require a conditioning treatment to increase the amount of treatment This treatment sometimes causes tangling to deposit on the surface of the jig. For this reason, it was necessary to replace the jig when moving to the conditioning process force electric mating, and there was a problem that workability was very poor.

[0004] 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, an etching treatment is performed with a mixed solution of permanganate and phosphoric acid, Next, a chromium-free plating process in which treatment is performed with an ionic catalyst solution and then plating is reported (Patent Document 1).

[0005] 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 surface of the jig is also touched. Since the medium metal was adsorbed, there was a problem that the metal plating was deposited on the surface of the jig together with the plastic surface in the subsequent plating process. In addition, this process has a problem that it is not practical because the reducing agent for reducing the catalytic metal decomposes spontaneously. Patent Document 1: WO2005Z094394 pamphlet

Disclosure of the invention

Problems to be solved by the invention

[0006] Therefore, the object of the present invention is that the metallization process of the chromium-free plastic surface can be performed with sufficient adhesion to the plastic surface, and the force does not deposit on the jig! It is highly practical! To provide a metallization method for plastic surfaces. Means for solving the problem

[0007] As a result of intensive studies to solve the above problems, the present inventors have determined that a catalyst containing a specific compound after treating a plastic surface with an etching treatment solution containing a permanganate or the like. It has been found that the treatment with the application-enhancing liquid allows the catalyst metal to be selectively adsorbed on the plastic surface in the subsequent application of the catalyst, and also increases the amount of adsorption. Furthermore, even if a plating process is performed subsequent to the catalyst application process, it is possible to perform plating with sufficient adhesion to the plastic surface, and it has been found that plating does not deposit on the jig coating surface. Completed.

That is, the present invention treats a plastic with an etching treatment solution containing a permanganate and an inorganic acid, and then selectively treats the treated plastic with a functional group exposed on the surface thereof. In addition, a catalyst is applied to the plastic treated with the catalyst application-enhancing liquid, and a catalyst is applied to the plastic applied with the catalyst application-enhancing liquid. It is a metallization method for a plastic surface characterized by applying a metal plating.

The invention's effect

[0009] According to the method for metallizing a plastic surface of the present invention, it is a highly practical method that can sufficiently adhere to and squeeze the plastic surface and does not deposit plating on the jig. Moreover, according to the metallization method of the plastic surface of the present invention, the plastic surface Since the amount of catalyst metal adsorbed can be increased, it can be applied to plastics that are difficult to adsorb catalyst metal by conventional methods.

[0010] Therefore, the method for metallizing a plastic surface of the present invention is an excellent method as a metallizing process for a chromium-free plastic surface.

BEST MODE FOR CARRYING OUT THE INVENTION

[0011] 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.

'Butadiene styrene (ABS), polycarbonate Z acrylonitrile' Butadiene 'styrene (PCZABS), acrylonitrile styrene acrylate (ASA), silicon composite rubber —acrylonitrile monostyrene (SAS), noryl, polypropylene, polycarbonate (PC) , Acrylonitrile, Styrene, Polyacetate, Polystyrene, Polyamide, Aromatic polyamide, Polyethylene, Polyetherol ketone, Polyethylene terephthalate, Polybutylene terephthalate, Polysulfone, Polyetherethersulfone, Polyetherimide, Modified polyphenylene ether Polyphenylene sulfide, polyamide, polyimide, epoxy resin, liquid crystal polymer, and copolymers of the above polymers. In the method of the present invention, it is particularly preferable to metallize the surfaces of ABS and PCZABS.

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 solution is not particularly limited, and for example, metal salts of permanganate such as potassium permanganate and sodium permanganate can be used. The concentration of this permanganate in the etching solution is 0.0005 molZL or more, preferably 0.005 to 0.5 molZL. On the other hand, the inorganic acid contained in the etching solution is not particularly limited, and examples thereof include at least one selected from the group of inorganic acids selected from phosphoric acid, sulfuric acid, and nitric acid, preferably phosphoric acid. is there. The concentration of these inorganic acids in the etching treatment solution is 2 molZL or more, preferably 6 to 12 molZL. In order to treat the plastic surface with the above etching treatment liquid, the liquid temperature is set to 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. do it. The surface of the plastic is treated with functional groups, specifically hydroxyl groups, A hydrophilic functional group such as a xyl group is exposed.

[0013] The plastic surface subjected to the above etching treatment is then subjected to a compound having a selective adsorption property to the functional group exposed on the plastic surface by the above treatment (hereinafter referred to as "selective adsorption compound" t, And a catalyst application enhancing solution containing The selective adsorption compound contained in the catalyst imparting enhancement liquid is not particularly limited as long as it is a compound having selective adsorption on the functional group as described above. For example, a compound containing a nitrogen atom, a nitrogen atom, etc. Or a compound having a molecular weight of 100 or more, preferably a compound having 3 or more nitrogen atoms and a molecular weight of 100 or more. Specific examples of the selective adsorptive compound include ethylenediamine compounds such as ethylenetriamine and triethylenetetramine (excluding ethylenediamine); Epomin SP-003, Epomin SP-012, Epomin SP-200 ( Ethyleneimine polymer compounds such as Nippon Shokubai Co., Ltd .; arylamine polymer compounds such as PAA-03, PAA-D41-HC1 (both manufactured by Nitto Boseki Co., Ltd.); PAS-92, PAS — Diallylamine polymer compounds such as M-1, PAS-880 (all manufactured by Nitto Boseki Co., Ltd.); vinylamine polymer compounds such as PVAM-0570-B (manufactured by Mitsubishi Chemical Corporation). Among these selectively adsorbing compounds, ethyleneimine polymer compounds, arylamine polymer compounds and diallylamine polymer compounds are particularly preferred. The concentration of these selective adsorptive compounds in the catalyst application enhancing liquid is 10 mgZL or more, preferably 100 to 1000 mgZL. Further, it is preferable to adjust the pH of the catalyst application enhancing liquid to 5 to 12, preferably 8 to 10, with, for example, sodium hydroxide or sulfuric acid. In order to treat the plastic surface with the 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. What is necessary is to process.

[0014] Next, a catalyst is applied to the plastic surface subjected to the above-described catalyst application enhancing treatment with a catalyst application treatment liquid. The catalyst application treatment liquid is not particularly limited as long as it is generally used for the catalyst application in the plating process, but the one containing noble metal is preferred, and the one containing palladium is more preferred, especially palladium Z tin mixed colloidal catalyst. A solution is preferred. 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. The Processing.

[0015] The plastic surface thus provided with the catalyst is then metallized by metal plating such as electroless metal plating (direct plating).

[0016] 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. Good. The concentration of hydrochloric acid or sulfuric acid in this active liquid treatment solution is 0.5 molZL or more, preferably 1 to 4 molZL. In order to treat the plastic surface with these active liquid treatment liquids, the liquid temperature of the active liquid treatment liquid is set to 0 to 60 ° C, preferably 30 to 45 ° C, and the plastic is preferably used for 1 to 20 minutes. Can be soaked for 2-5 minutes.

[0017] Next, the plastic subjected to the application of the catalyst and subjected to the activity treatment as described above is subjected to an electroless metal plating treatment. The electroless metal plating treatment can be carried out in accordance with a conventional method using an electroless metal plating such as a known electroless nickel plating solution, electroless copper plating solution, or electroless cobalt plating solution. Specifically, when the surface of a plastic is treated with an electroless nickel plating solution, the plastic is immersed in an electroless nickel plating solution at a pH of 8 to 10 and a temperature of 30 to 50 ° C for 5 to 15 minutes. What is necessary is to process.

[0018] Also, in the case where electrometal plating (direct plating) is used for metallization of the plastic surface, after applying the catalyst with the catalyst applying treatment liquid, the pH further containing copper ions is 7 or more. The treatment may preferably be performed with an active soot treatment solution having a pH of 2 or more. 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 active liquid treatment solution, the temperature of the activation treatment solution is set to 0 to 60 ° C, preferably 30 to 50 ° C, and the plastic is added to the plastic for 1 to 20 minutes, preferably 2 to Soak and treat for 50 minutes.

[0019] The plastic that has been subjected to the application of the catalyst and treated with the activity as described above is then immersed in a general-purpose electric copper plating bath such as a copper sulfate bath, under normal conditions, for example, 1 to 5 AZdm ² . 2 ~: Process for LO minutes.

[0020] Further, metal plating such as electroless plating or electrometal plating is applied to the plastic surface as described above, and various types of electrolytic copper are further applied to the metalized plastic surface according to the purpose. Plating or electro nickel plating can also be applied.

Example

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

[0022] Reference Example 1

Surface modification treatment of plastic surface:

Using 50 x 100 x 3 mm ABS resin (UMGABS Co., Ltd.) as a sample, immerse it in an etching solution at 35 ° C containing O. OlmolZL potassium permanganate and 7.5 molZL phosphoric acid for 10 minutes. did. For comparison, the sample was immersed in an etching solution at 65 ° C. containing 3.5 mol / L of anhydrous chromic acid and 3.6 mol ZL of 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 (FTZIR61 OOFV type (manufactured by JASCO Corporation)). The results are shown in Fig. 1.

[0023] On the surface of 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, after the etching treatment, no peaks derived from hydroxyl groups or carboxyl groups were observed on the surface of the ABS resin. Moreover, almost no peaks derived from hydroxyl groups or carboxyl groups were observed on the surface of ABS resin treated with an etching solution containing chromic acid.

[0024] Example 1

Production of electroless plating film:

A 50 x 100 x 3 mm ABS resin (UMGABS Co., Ltd.) was used as a sample, and this was placed in a 35 ° C etching solution containing O. OlmolZl potassium permanganate and 7.5 molZl phosphoric acid for 10 minutes. Soaked. Next, 200 mg / l PAA-03 (polyallylamine: manufactured by Nitto Boseki Co., Ltd.) was soaked in a 30 ° C catalyzing enhancement solution adjusted to pH 10 with sodium hydroxide for 2 minutes. . Further, after immersing this in 1.2molZl hydrochloric acid at room temperature for 1 minute, 35 ° C palladium Z tin mixed colloidal catalyst solution containing lOmlZl CT-580 (manufactured by Ebara Eugilite Co., Ltd.) and 2.5molZl hydrochloric acid. Soak for 4 minutes in AB A catalyst was applied on S resin. Next, this was immersed for 4 minutes in a 35 ° C. active water treatment solution having a hydrochloric acid power of 1.2 mol Zl to activate the catalyst. After that, immerse it for 10 minutes in electroless nickel plating solution ENILEX NI-5 (made by EBARA Eugleite Co., Ltd.) at pH 8.8 and 35 ° C, so that the film thickness is 0.5 m on the ABS resin. Electrolytic nickel plating was applied. Thereafter, it was immersed in an acid active solution containing 150 g / l of V-345 (manufactured by Ebara Eugleite Co., Ltd.) at room temperature for 1 minute. Next, it was immersed in a 45 ° C. watt bath containing 0.75 molZl nickel sulfate, 0.4 molZl nickel chloride nickel and O.55 mol / 1 boric acid at 2 V / dm ² for 3 minutes. Further, this was immersed for 1 minute in a room temperature copper replacement solution containing lOmlZl PDC (manufactured by Ebara Eugilite Co., Ltd.) and 0.5 molZl sulfuric acid to perform copper replacement. Next, this was added to a 25 ° C copper sulfate plating solution EP-30 (manufactured by EBARA Eugleite Co., Ltd.) containing 0.9 mol / 1 copper sulfate, 0.55 mol / l sulfuric acid and 0.0017 mol / l chlorine. It was immersed in 3AZdm ² for 40 minutes, and copper electroplating was applied on the ABS resin so that the film thickness was 20 m. This was then annealed at 70 ° C for 1 hour.

[0025] 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.

[0026] Comparative Example 2

Preparation of electroless plating film (2):

A 50 x 100 x 3 mm ABS resin (UMGABS Co., Ltd.) was used as a sample, and this was placed in a 35 ° C etching solution containing O. OlmolZl potassium permanganate and 7.5 molZl phosphoric acid for 10 minutes. Soaked. Next, this was immersed in a catalyst solution at 50 ° C. containing 0.0024 mol / l of sodium chloride palladium for 4 minutes to give the catalyst onto the ABS resin. Next, the catalyst was activated by immersing in PC-66H (manufactured by Sakakibara Eugelite Co., Ltd.) for 4 minutes in a 35 ° C. active soot treatment solution containing 10 ml / l. Thereafter, the same treatment as in Example 1 after electroless nickel plating was performed.

[0027] Comparative Example 3

Production of electroless plating film (3): In the process of Comparative Example 1, instead of a 50 ° C catalyst solution containing 0.0024 mol / l palladium chloride, a 50 ° C catalyst solution containing 0.0019 molZl 2-aminoviridine and 0.00094 molZl palladium sulfate was added. The electroless nickel plating was applied to the ABS resin in the same manner except for immersion for 4 minutes.

[0028] Test Example 1

The depositability 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. In addition, the amount of palladium adsorbed and adhesion strength on ABS resin was measured as follows. These results are shown in Table 1.

[0029] <Measurement method>

Adsorption amount of palladium catalyst:

By reducing the palladium ions adsorbed on the surface of the ABS resin with aqua regia, dissolving the palladium with aqua regia, and measuring the absorbance of the solution using a high-frequency plasma emission spectrometer 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, annealing is performed at 70 ° C for 1 hour, and then tensile strength tester AGS—H5 OON (Shimadzu Corporation) Adhesion strength was measured by a manufacturer.

[0030] [Table 1]

-: Measurement not possible

[0031] In Example 1, the adsorption amount of the palladium catalyst increased, and the depositability and adhesion strength of the electroless plating film were good. In this process, plating did not deposit on the jig coating. On the other hand, in Comparative Example 1, although there was no plating deposition on the jig, there was an undeposited portion of plating where the amount of palladium adsorbed on the ABS resin was small. Comparative Example 2 and Comparative Example 3 In this case, a sufficient amount of palladium was adsorbed on ABS resin, but plating was deposited on the jig coating.

[0032] Example 2

Direct plating on ABS resin:

A 50 x 100 x 3 mm ABS resin (UMGABS Co., Ltd.) was used as a sample, and this was placed in a 35 ° C etching solution containing O. OlmolZl potassium permanganate and 7.5 molZl phosphoric acid for 10 minutes. Soaked. Next, 200 mg / l PAA-03 (Polyamylamine: manufactured by Nitto Boseki Co., Ltd.) was immersed in a 30 ° C. catalyzing solution for 2 minutes adjusted to pH 10 with sodium hydroxide. Thereafter, it was further immersed in 1.2 mol Zl hydrochloric acid for 1 minute at room temperature. Next, this was immersed for 4 minutes in an activator at 35 ° C. containing 25 ml Zl D-POPACT (manufactured by Sugawara Eugene Corporation), 1.2 mol Zl hydrochloric acid and 1.7 mol Zl sodium chloride. Next, it was immersed in a metallizer at 45 ° C. containing lOOmlZl D-POPMEA (manufactured by Sugawara Eugleite Co., Ltd.) and lOOmlZl D-POPMEB (manufactured by Sugawara Eugilite Co. Ltd.) for 3 minutes. Finally, immerse in 25 ° C EP-30 containing copper sulfate 0.9molZl, 0.55molZl sulfuric acid and 0.017molZl hydrochloric acid (copper sulfate plating solution: manufactured by Ebara Eulite Co., Ltd.) for 10 minutes. A soft start was performed (0.5 V for the first 30 seconds, 1.0 V for the next 30 seconds, and finally 1.5 V), and direct plating was performed on the ABS resin.

[0033] As a result of direct plating on the ABS resin, it was possible to squeeze the entire sample without plating depositing on the jig coating within 5 minutes of energization. The adhesion strength of the adhesive film was 0.8 kgfZcm as measured in the same manner as in Test Example 1.

[0034] Example 3

Preparation of electroless plating film on various types of resin:

Various types of resin (ABS, PC / ABS (containing 65% PC), ASA, SAS PC (manufactured by UM GABS), Noryl (manufactured by General Electric), polypropylene (manufactured by Nippon Polychem Co., Ltd.)) An electroless nickel plating was applied on each resin in the same manner as in Example 1 except that it was used.

[0035] Comparative Example 4 Preparation of electroless plating film on various types of resin:

Various types of resin (ABS, PC / ABS (containing 65% PC), ASA, SAS PC (manufactured by UM GABS), Noryl (manufactured by General Electric), polypropylene (manufactured by Nippon Polychem Co., Ltd.)) This was immersed in an etching solution at 65 ° C. containing 3.5 mol Zl chromic anhydride and 3.6 mol Zl sulfuric acid for 10 minutes. Next, this was immersed in a reducing solution at 25 ° C. containing O.5 mol / 1 hydrochloric acid and 10 ml / l Erex RD (manufactured by Ebara Eugelite Co., Ltd.) for 2 minutes. Further, it was subjected to the same treatment as in Example 1 after the 1.2 mol Zl hydrochloric acid immersion (pre-dip).

[0036] Test Example 2

The depositability of the electroless plating film obtained in Example 3 and Comparative Example 4 in various types of grease and deposition on the jig coating were evaluated visually. In addition, the adhesion strength of the electroless plating film obtained on each type of resin was measured in the same manner as in Test Example 1. These results are shown in Table 2.

[0037] [Table 2]

-: Measurement not possible

The electroless plating film obtained in Example 3 was completely applied on all the resins, and an adhesion strength equal to or higher than that of Comparative Example 4 (chromic acid etching process) was obtained. Further, in Example 3, no plating was deposited on the jig cover even when electroless plating was applied to any of the resins. On the other hand, Comparative Example 4 (chromic acid etching process) In this case, unprecipitated parts were generated in noryl and polypropylene resin, and in the case of PC resin, plating did not precipitate.

[0039] Example 4

Effect of catalyst application enhancing liquid:

In the process of Example 1, the active ingredient of the catalyst imparting enhancement liquid is PAA-03 (polyallylamine: manufactured by Nitto Boseki Co., Ltd.) as shown in Table 4 below, or Ade force hope, Ade force tall, Ade force bull mouth Electroless nickel plating was applied on the ABS resin in the same way except that it was changed to Nick (all manufactured by Asahi Denki Kogyo Co., Ltd.) and Energy Coal (manufactured by Lion Co., Ltd.). The depositability of the obtained electroless nickel film on ABS resin and the deposit on the jig coating were evaluated in the same manner as in Test Example 1. Further, the amount of palladium adsorbed on ABS resin was measured in the same manner as in Test Example 1. These results are shown in Table 3.

[0040] [Table 3-1]

[Table 3-2]

3) Manufactured by Pingtung Spinning Co., Ltd. 4) Manufactured by Mitsubishi Chemical Corporation

Active component of catalyst application enhancement liquid Electroless plating film Jig coating of palladium catalyst Precipitation of adsorbed amount (mg / dm ² ) Molybdenol 7 Min 6

I Trenchy "Amin Unprecipitated portion Not present 0. 0 2 2

I Chirenshi '7-min compound Good 0.0 4 5

(Shii I Chileen Min)

I Tiren ”Amine compound Good None 0. 0 5 0

(卜 I I Tylenetetramine)

I Tirens' amine compounds Good None 0. 0 6 1

(Henta I Tylene Hexamine)

I Tylene imine polymer compound Good None 0. 0 7 4

(SP-003)

Ethyleneimine polymer compound Good None 0.1 2

(SP0-01 2)

I Tylene imine polymer compound Good None 0. 1 0 7

(SP200)

Aryl amine polymer compound Good None 0. 1 0 8

(PAA-03)

Aryl 7-min polymer compound Good None 0. 0 7 9

(PAA-D41 -HCL)

Cialyl 7-min polymer compound Good None 0. 0 4 9

(PAS-92)

Cialyl 7-Mine polymer compound Good None 0. 0 6 8

(PAS-M- 1)

'N' arylamine-based polymer compound Good None 0. 0 4 8

(PAS-880)

Vinylamine polymer compound Good None 0 0 8 2

(PVAM-0570-B)

Crisin unprecipitated part not present 0 .0 2 9

Taurine Unprecipitated portion None 0. 0 2 3

Amitanchi Without undeposited part 0. 0 3 3 Fat "Force hough" Without undeposited part 0. 0 2 4

Key "Force" Unprecipitated portion Yes 0. 0 3 1

0 "Cuff" mouth nick Unprecedented part Yes Yes 0 0 9

Energize "Cole Unprecipitated portion None 0. 0 2 9

No treatment with catalyst imparting enhancement liquid Unprecipitated part present None 0.0 2 5 As active ingredients of catalyst imparting enhancement liquid, ethylenediamine compound, ethyleneimine polymer compound, arylamine polymer compound, diallylamine polymer compound, vinyl When amine-based polymer compounds were used, the palladium adsorption amount increased, and good plating deposition properties were obtained without jig deposition. In contrast, compounds such as monoethanolamine, ethylenediamine, glycine, taurine, and aminoethanethiol, which are compounds with less than nitrogen atoms in one molecule, did not increase the amount of palladium adsorbed. In addition, the effects of increasing the amount of palladium adsorbed were also observed with the Ade-powered Hope and Energy Coal, which are surfactants. Adekato, a non-ionic surfactant The amount of palladium adsorbed did not increase at the Able Bull nick, and even caused deposition on the jig coating.

[0043] 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 solution was changed to that shown in Table 5 below. The depositability of the obtained electroless nickel coating on ABS resin was evaluated in the same manner as in Test Example 1. These results are shown in Table 5. Further, the adhesion strength of the obtained electroless nickel plating film was measured by the following tape peeling test.

[0044] <Measurement method>

Cellophane tape (CT24: manufactured by Chiban Co., Ltd.) was brought into close contact with the sample surface after electroless nickel plating, and the tape was peeled upward 90 °. After the cellophane tape was peeled off, it was confirmed by visual inspection that the clinging film was not peeled off together with the tape.

[0045] [Table 5]

[0046] All the mixed solutions of potassium permanganate and inorganic acid had good precipitation and high adhesion strength, and cleared the tape peeling test. On the other hand, in the case of potassium permanganate and phosphoric acid having a single composition, the surface of the plastic was almost modified. Therefore, non-deposited portions were generated in the subsequent electroless nickel plating. Also, the adhesion strength of the plated part was low and it was easily peeled off with tape.

[0047] Example 6

Effect of ρΗ of aqueous solution containing catalyst application enhancing liquid:

In the process of Example 1, all except that the ρΗ of the catalyst imparting enhancement liquid was adjusted to the values listed in Table 6 below using sodium hydroxide and sulfuric acid, the same was applied to the electroless gasket on the ABS resin. Was plated. Precipitation properties of the obtained electroless nickel coating on ABS Precipitation on the jig coating was evaluated in the same manner as in Test Example 1. Further, the amount of palladium adsorbed on ABS resin was measured in the same manner as in Test Example 1. These results are also shown in Table 6.

[0048] [Table 6]

[0049] When the pH of the catalyst application enhancing solution was 5.0 to 12.0, plating was not deposited on the jig, and an effect of increasing the amount of palladium adsorbed was observed.

[0050] 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 the same Electroless nickel plating was performed on the resin. The deposition of the obtained electroless nickel coating on the jig coating with 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 were also set to 7.

[0051] [Table 7]

[0052] Suppression of precipitation on the jig coating related to the concentration of polyallylamine was suppressed, and the amount of palladium adsorbed The effect which increases is seen.

Industrial applicability

[0053] The method for metallizing a plastic surface according to the present invention is a highly practical method that can sufficiently adhere to the surface of the plastic and cause a stagnation, and that plating 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, so that the conventional method can be applied to plastics that are difficult to adsorb catalyst metal.

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

Brief Description of Drawings

[0055] [Fig. 1] Fig. 1 shows the result of measuring the surface of the ABS resin surface with a Fourier transform infrared spectrophotometer (1: ABS resin surface without etching treatment, 2: Etching containing chromic acid) ABS resin surface after treatment with treatment liquid, 3: ABS resin surface after treatment with etchant containing permanganic acid).

Claims

The scope of the claims

[1] The plastic is treated with an etching treatment solution containing a permanganate and an inorganic acid, and then the treated plastic is a catalyst containing a compound having a selective adsorption property to a functional group exposed on the surface thereof. Treating with an application enhancing liquid, and further applying a catalyst to the plastic treated with the catalyst application enhancing liquid with the catalyst application processing liquid, and then applying metal plating to the plastic with the catalyst applied. Metallization method for plastic surface.

[2] The method for metallizing a plastic surface according to [1], wherein the inorganic acid contained in the etching solution is at least one inorganic acid selected from the group consisting of phosphoric acid, sulfuric acid and nitric acid.

[3] 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.

[4] The method for metallizing a plastic surface according to any one of [1] to [3], wherein the concentration power of permanganate in the etching solution is 0.0005 molZL or more.

5. The method for metallizing a plastic surface according to any one of claims 1 to 4, wherein the concentration power of the inorganic acid in the etching treatment solution is 2 molZL or more.

[6] The plastic surface according to any one of claims 1 to 5, wherein the compound that is selectively adsorbed on the functional group exposed on the plastic surface and contained in the catalyst imparting enhancement liquid is a compound containing a nitrogen atom. Metallization method.

[7] The compound according to any one of claims 1 to 5, wherein the compound that is selectively adsorbed on the functional group exposed on the plastic surface and contained in the catalyst imparting enhancement liquid is a compound containing three or more nitrogen atoms. Metallization method for plastic surfaces.

[8] The metal on the plastic surface according to any one of [1] to [5], which is a compound having a selective adsorption property to a functional group exposed on the plastic surface and contained in the catalyst imparting enhancement liquid, and having a molecular weight of 100 or more. Method.

[9] The metal on the plastic surface according to any one of [1] to [8], wherein the concentration of the compound having a selective adsorption property to the functional group exposed on the plastic surface in the catalyst imparting enhancement liquid is lOmgZL or more. Method.

[10] The method for metallizing a plastic surface according to any one of [1] to [9], wherein the catalyst imparting enhancing liquid has a pH force of 5 to 12.

[11] The method for metallizing a plastic surface according to any one of [1] to [10], wherein the metal plating is an electroless plating.

12. The method for metallizing a plastic surface according to claim 11, wherein the catalyst application treatment liquid contains a noble metal.

13. The method for metallizing a plastic surface according to claim 11 or 12, wherein the catalyst application treatment liquid is a solution containing palladium.

14. The method for metallizing a plastic surface according to any one of claims 11 to 13, wherein the catalyst application treatment liquid is a palladium Z tin mixed colloid catalyst solution.

[15] The method for metallizing a plastic surface according to any one of [1] to [14], further comprising the step of treating with an activation treatment solution containing hydrochloric acid or sulfuric acid after applying the catalyst with the catalyst application treatment solution. .

16. The method for metallizing a plastic surface according to claim 15, wherein the concentration of hydrochloric acid or sulfuric acid in the active liquor treatment solution is 0.5 molZL or more.

17. The method for metallizing a plastic surface according to any one of claims 1 to 10, wherein the metal plating is electric plating.

18. The method for metallizing a plastic surface according to claim 17, wherein the catalyst application treatment solution is a palladium Z tin mixed colloid catalyst solution.

[19] The method for metallizing a plastic surface according to [18], wherein after the catalyst is imparted with the catalyst imparting treatment liquid, the catalyst is further treated with an active soot treatment liquid containing copper ions and having a pH of 7 or higher.