TW200811311A - Method for metallizing plastic surface - Google Patents

Abstract

A chromium-free, highly-practical method for metallizing a plastic surface which can provide the plastic surface having sufficient adhesiveness thereto without depositing the plating on the jig is provided. The method comprises treating a plastic with an etching treatment solution containing a permanganate ad an inorganic acid, treating the thus-treated plastic with a catalyst-loading enhancing solution containing a compound having selective adsorption properties to a functional group or functional groups exposed on the surface of the treated plastic, applying a catalyst to the plastic treated with the catalyst-loading enhancing solution, and carrying out metal plating of the plastic loaded with the catalyst.

Description

200811311 IX. INSTRUCTIONS OF THE INVENTION [Technical Fields of the Invention] The present invention relates to a metallization method for a plastic surface, and more particularly to the fact that the surface of the frame in the operation of maintaining the plated product to be plated is not plated and precipitated. A method of forming a coated film having high adhesion on a plastic surface. [Prior Art] In the prior art, the surface of plastics such as acrylonitrile butadiene styrene (ABS) resin, polycarbonate/acrylonitrile butadiene styrene (PC/ABS) was plated. In the metallization treatment, in order to improve the adhesion between the surface of the plastic and the plating film, the plastic surface is etched by roughening the mixture of chromic acid and sulfuric acid before the plating treatment. However, in the engraving treatment, the use of harmful hexavalent chromium is carried out at a high temperature of 60 ° C or higher, which results in a deterioration of the working environment, and the treatment of the degree of water must not be an issue. Further, in the plating step performed after the etching treatment, when plating such as PC/ABS is applied to the surface of the plastic which is hard to be deposited, the plating is directly applied to the so-called direct plating adsorption metal catalyst. It is necessary to carry out the adjustment treatment for increasing the adsorption of the catalytic metal, but after the treatment, the plating of the surface of the frame is also precipitated. Therefore, it is necessary to change the process from the adjustment process to the plating, which results in a problem that the system is extremely poor. > With respect to such problems, it is expected to provide a etchant for replacing a mixture of chromic acid and sulfuric acid, such as: after replacing these etchants, etching treatment is carried out by a mixture of permanganate and phosphoric acid. Sexual contact liquid treatment, etc., -4- 200811311, the chrome-free plating process for plating is disclosed (Patent Document 1). In this step, after the ionic catalyst liquid is treated, the plastic is applied. Although the adsorption amount of the catalyst metal on the surface is increased, the catalyst metal is also adsorbed on the coating surface of the frame, so that the subsequent plating process and the plastic surface also cause plating precipitation on the surface of the frame. Further, in this process, there is a problem that the reducing agent for reducing the catalytic metal is decomposed due to natural decomposition. Patent Document 1: WO 2005/094394 Manual [Summary of the Invention] Accordingly, the object of the present invention is to provide a surface that can be sufficiently adhered to a plastic surface during metallization of a chrome-free plastic surface. The metallization method of the plastic surface with high practicability of the precipitation is not plated. The inventors of the present invention have found that the surface of the plastic is treated with a uranium engraving treatment solution containing permanganate or the like, and then treated with a catalyst-enhancing liquid containing a specific compound. After the catalyst treatment, the catalyst metal can be selectively adsorbed on the plastic surface, and the adsorption amount is also increased. Further, after the catalyst treatment is carried out and the plating treatment is performed, the plating can be sufficiently adhered to the surface of the plastic, and the surface of the frame coating layer is not plated and precipitated, thereby completing the present invention. That is, the present invention treats the plastic with a uranium engraving treatment solution containing perrhenate and a mineral acid, and then imparts a selective adsorption property to the functional group on which the treated plastic is exposed on the surface. After the treatment of the catalyst-enhancing liquid 5-200811311, the catalyst is applied to the plastic treated with the catalyst-enhancing liquid, and then the metal is applied to the plastic to which the catalyst is applied. A metallization method for a plastic surface characterized by it. The metallization method of the plastic surface of the invention can be made to be fully adhered and plated on the surface of the plastic, and is not plated and precipitated in the frame, which is a highly practical method. The metallization method of the plastic surface of the present invention can increase the adsorption amount of the catalyst metal on the plastic surface. Therefore, in the prior art method, the same plating can be performed on the plastic which is not easy to adsorb the catalyst metal. Therefore, the metallization process of the plastic surface of the present invention is a good method for the metallization process of the chrome-free plastic surface. [Embodiment] [Best Mode for Carrying Out the Invention]

The metal which is the object of metallization in the metallization method of the plastic surface of the present invention (hereinafter referred to as "the method of the present invention") is not particularly limited, and generally, for example, acrylonitrile butadiene styrene (ABS), polycarbonate Ester/acrylonitrile butadiene styrene (PC/ABS), acrylonitrile styrene acrylate (ASA), polyoxymethylene composite rubber-acrylonitrile-styrene (SAS), no ril, polypropylene , polycarbonate (PC), acrylonitrile, styrene, polyacetate, polystyrene, polyamine, aromatic polyamine, polyethylene, polyether ketone, polyethylene terephthalate, Polybutylene terephthalate, polyfluorene, polyetheretherether, polyetherimine, modified polyphenylene ether, polyphenylene sulfide, polyamine, polyimine, epoxy resin, liquid crystal polymerization Examples of the copolymers of the above polymers, and the like. In the method of the present invention, it is preferred to carry out metallization on the surface of ABS and PC/ABS 200811311. In the present invention, first, the plastic surface is treated by an etching treatment liquid containing permanganate and a mineral acid. The permanganate contained in the uranium engraving treatment liquid is not particularly limited, and a metal salt of permanganic acid such as potassium permanganate or sodium permanganate can be generally used. The concentration in the permanganate etching treatment liquid is preferably 0.0005 mol/L or more, preferably 0.005 to 0.5 mol/L. Further, the inorganic acid contained in the etching treatment liquid is not particularly limited, and is generally, for example, an inorganic acid selected from the group consisting of phosphoric acid, sulfuric acid and nitric acid, and preferably a phosphoric acid. The concentration in the etching solution of the inorganic acid is preferably 2 mol/L or more, preferably 6 to 12 mol/L. When the surface of the plastic is treated with the uranium engraving treatment liquid, the liquid temperature is 〇50 ° C, preferably 25 to 40 ° C, and the plastic is immersed for 1 to 30 minutes, preferably 5 to 15 minutes. After processing. After the treatment of the etching treatment liquid, the functional group is exposed on the surface of the plastic, and for example, a hydrophilic functional group such as a hydroxyl group or a carboxyl group is exposed. The plastic surface subjected to the engraving treatment is then treated with a catalyst-enhancing liquid containing a selective adsorbing compound (hereinafter referred to as "selective adsorbing compound") on a functional group exposed through the surface of the above-mentioned treated plastic. The selective adsorbing compound contained in the catalyst-enhancing liquid is not particularly limited as long as it has a selective adsorption property on the functional group as described above, and is generally, for example, a compound containing a nitrogen atom, and contains three The compound of the above nitrogen atom or the compound having a molecular weight of 100 or more is preferably a compound having three or more nitrogen atoms and a molecular weight of 100 or more. Specific examples of the adsorbent compound selected for this purpose include ethylene diamine compounds such as ethylene triamine and triethylenetetramine (in which ethylene diamine is removed); epomin 200811311 SP-003, epomin SP-012, epomin SP- Ethylene imine polymer compound such as 200 (both manufactured by Nippon Shokubai Co., Ltd.); allylamine polymer compound such as PAA-03, PAA-D41-HC1 (both manufactured by Nitto Spinning Co., Ltd.) ; PAS-92, PAS-M-1, PAS-880 C are all diallylamine-based polymer compounds such as Nitto Spinning Co., Ltd.; PVAM-0570-B (manufactured by Mitsubishi Chemical Corporation) An example of a vinylamine polymer compound. Among these selective adsorbing compounds, an ethyleneimine-based polymer compound, an allylamine-based polymer compound, and a diallylamine-based polymer compound are particularly preferable. The concentration of the selective adsorbing compound in the catalyst-enhancing liquid is preferably the above, preferably 100 to 1 000 mg/L. Further, the catalyst-improving liquid is adjusted to have a pH of 5 to 12, preferably 8 to 10, by, for example, sodium hydroxide or sulfuric acid. When the surface of the plastic is treated with the catalyst-enhancing liquid, the liquid temperature is preferably 0 to 70 ° C, preferably 25 to 35 ° C, and the plastic is immersed for 1 to 20 minutes, preferably impregnated. 2 to 3 minutes to process. The plastic surface to which the catalyst-enhancing treatment is applied is then applied to the catalyst by the application of the catalyst treatment liquid. The catalyst treatment is generally not limited as long as it is used for the plating step, and is usually limited to a noble metal, and more preferably a palladium-containing, especially palladium/ruthenium mixed colloid catalyst solution. For the best. When the catalyst is applied to the surface of the plastic, the temperature of the liquid to which the catalyst treatment liquid is applied is preferably 10 to 60 ° C, preferably 20 to 50 ° C, and the plastic is immersed therein for 1 to 20 minutes. The best one can be treated by dipping for 2 to 5 minutes. The plastic surface thus imparted to the catalyst is then metallized on the surface of the plastic by electroless metal plating, metal ore (direct electric ore), and metallization. When the metallization of the plastic surface is carried out by electroless metal plating, the catalyst may be added to the catalyst treatment liquid, and further treated with an active treatment liquid containing hydrochloric acid or sulfuric acid. The concentration of hydrochloric acid or sulfuric acid in the activation treatment liquid is preferably 0.5 mol/L or more, preferably 1 to 4 mol/L. When treating the plastic surface with the activation treatment liquid, the liquid temperature of the activation treatment liquid is preferably 〇60 ° C, preferably 30 to 45 ° C, and the plastic is immersed therein for 1 to 20 minutes, preferably Dip for 2 to 5 minutes. The plastic which is subjected to the catalyst and the activation treatment as described above is then subjected to an electroless gold plating treatment. The electroless metal plating treatment can be carried out by a conventional method using electroless mineral plating such as a known electroless nickel plating solution, an electroless copper plating solution, or an electroless cobalt plating solution. Specifically, when the electroless nickel plating solution is applied to the surface of the plastic, the plastic is immersed in an electroless nickel plating solution at a liquid temperature of pH 8 to 10 and 30 to 50 ° C for 5 to 15 minutes. . Further, when metal plating (direct plating) is used for metallization of the plastic surface, after the catalyst is supplied to the catalyst treatment liquid, the copper ion may further contain a copper ion at a pH of 7 or higher, preferably an activation treatment liquid having a pH of 12 or higher. . The source of the copper ion contained in the activation treatment liquid is not particularly limited, and is generally exemplified by copper sulfate. When the plastic surface is treated by the activation treatment liquid, the liquid temperature of the activation treatment liquid is preferably 0 to 60 ° C, more preferably 30 to 5 (TC, and the plastic is impregnated for 1 to 20 minutes, preferably 2 to 2). The treatment can be carried out for 50 minutes. The plastic which is given the catalyst and activated treatment is then immersed in a copper sulphate bath for general use, such as: 1~5 A / d m2, 2~10 minutes. -9- 200811311 In addition, after the metal plating such as electroless plating or metal plating is applied to the surface of the plastic, various kinds of electroplated copper or nickel plating may be performed on the surface of the metallized plastic according to the purpose. EXAMPLES Hereinafter, the present invention will be described more specifically by way of examples and comparative examples. However, the present invention is not limited thereto. [Reference Example 1] ABS resin (UMGABS shares) of 50 x 1 00 x 3 mm used as a sample was used. The company's sample was immersed in a 35 ° C etching treatment solution containing 0.5 mol/L of potassium permanganate and 7.5 mol/L of phosphoric acid for 10 minutes. In addition, the above sample was contained in 3.5 mol/L of chromium. The acid anhydride and 3.6 m〇l/L of sulfuric acid were immersed in a 65 °C contact solution for 10 minutes. The surface of each of the impregnated ABS resins was analyzed by a single-reflection ATR method using a Fourier transform infrared spectrophotometer (FT/IR 6100 FV type (manufactured by JASCO Corporation)). The results are shown in Fig. i. • The surface of the AB S resin treated with an etching solution containing permanganic acid appears to be a peak derived from a hydroxyl group or a carboxyl group in the vicinity of .334001^1. Further, the surface of the ABS resin which has not been subjected to etching treatment does not appear to be derived from a hydroxyl group. The peak of the carboxyl group. Further, the surface of the ABS resin treated with the uranium etching solution containing chromic acid hardly appeared from the peak of the hydroxyl group and the carboxyl group. [Example 1] -10- 200811311 (Production of electroless plating film) :

The 50% 1 00 x 3 mm ABS resin (manufactured by UMGABS Co., Ltd.) was used as a sample, and this was immersed in a 35 ° C uranium engraving treatment solution containing 0.5 mol of potassium permanganate and 7.5 mol/l of phosphoric acid. Minutes. Then, the pH of PAA-〇3 (poly-propylamine: manufactured by Nitto Spinning Co., Ltd.) adjusted to 200 mg/l with sodium hydroxide was changed to 10%. (: immersion in the catalyst-enhancing liquid for 2 minutes. Further immersing in 1.2 mol/l hydrochloric acid at room temperature for 1 minute, and then in CT-580 containing l〇ml/l (Sudi Udilyt Co., Ltd.) And 3·5πιο1/1 hydrochloric acid 35. After immersing for 4 minutes in the sputum/钖 mixed colloidal catalyst solution, the catalyst was added to the ABS resin, and this was made up of 1.2 mol/l hydrochloric acid. After immersing in the activation treatment liquid for 4 minutes, the catalyst was activated, and then immersed in an electroless nickel plating solution ENILEX Nb 5 (manufactured by Udilyt Co., Ltd.) at pH 8.8 and 35 ° C for 10 minutes. An electroless nickel plating having a film thickness of 0.5 μm was carried out on the ABS resin, and then immersed in an acid activation solution containing 150 g/l of ν-345 (manufactured by Udilyt Co., Ltd.) for 1 minute at room temperature. This was immersed in a 45 ° C Watt bath containing 0.75 m·l/l of nickel sulfate, 0.4 mol/l of nickel chloride and 0.55 mol/l of boric acid for 2 minutes at 2 V/dm 2 . Mol/l PDC (manufactured by Ubilyt Co., Ltd.) and a room temperature copper substitution solution of 0.5 mol/1 sulfuric acid for 1 minute to carry out copper substitution. This is further included in 3A/dm2. After immersing in a 25 ° C sulfuric acid copper plating solution EP-30 (manufactured by Udilyt Co., Ltd.) of 0.9 mol/l of copper sulfate, 0.55 mol/l and 0.0017 mol/l of chlorine for 40 minutes, the film thickness on the ABS resin was Electroplating copper of 20 μm. After that, the steel was dehydrated at 70 ° C for 1 hour. [Comparative Example 1] (Production of electroless plating film (1)): In the step of Example 1, Electroless nickel plating was performed on the ABS resin in the same manner as in the catalyst-enhancing liquid for 2 minutes. [Comparative Example 2] (Preparation of electroless plating film (2)): Use as a sample 50xlO〇x3mm of ABS resin (manufactured by UMGABS Co., Ltd.), immersed in a 35t etching treatment solution containing 0.5 mol/l of potassium permanganate and 7.5 mol/i of phosphoric acid for 10 minutes.浸渍. After immersing in a catalyst solution of 50 mol/l of palladium chloride at 50 ° C for 4 minutes, a catalyst was added to the ABS resin, and then PC-66H (manufactured by Udilyt Co., Ltd.) was contained at 10 ml/l. The catalyst was immersed in the activation treatment liquid at 35 ° C for 4 minutes to activate the catalyst. Subsequently, it was treated in the same manner as the electroless nickel plating of Example 1. [Comparative Example 3] (Preparation of electroless plating film (3)): In the step of Comparative Example 2, it was carried out by containing 19 mol/l of 2-aminopyridine and 0.00094 mol/l of palladium sulfate. The electroless nickel plating was carried out on the ABS resin in the same manner as the 50 ° C catalyst solution was immersed in a 50 ° C catalyst solution containing palladium chloride of 〇·〇〇 24 〇η〇 1/1 for 4 minutes. -12-200811311 [Testing Example 1] The precipitation property in the ABS resin of the electroless nickel-plated film obtained in Example 1 and Comparative Examples 1 to 3 and the precipitation on the frame were evaluated by visual observation. Further, the amount of palladium adsorbed on the ABS resin and the adhesion strength were measured as follows. These results are shown in Table 1. <Measurement method> (Adsorption amount of palladium catalyst) After the palladium ion adsorbed on the surface of the AB S resin was subjected to reduction treatment, the palladium was dissolved in aqua regia, and the high-frequency plasma luminescence analyzer ICPS-7510 (manufactured by Shimadzu Corporation) was used. After measuring the absorbance of the solution, the amount of adsorption of palladium was measured. (Measurement of adhesion strength): According to JIS H8630 Attachment 6, an electroplated copper film of about 20 μm was formed on the surface of the ABS resin, and then annealed at 70 ° C for 1 hour, after which the tensile strength tester AGS-H50 0N (Joint Company) The contact strength was measured by Shimadzu Corporation. [Table 1] Adsorption amount of electroless plating film deposition property on the palladium catalyst deposited on the frame (mg/dm2) Adhesion strength (kgf/cm) Example 1 Good y y\\\ 0.108 1.4 Comparative Example 1 There is unprecipitated portion Μ j\\\ 0.025 - Comparative Example 2 Good 0.063 1.4 Comparative Example 3 Good 0.082 1.4 -: Unmeasured -13 - 200811311 The adsorption amount of the palladium catalyst in Example 1 is increased, and the electroless plating film is formed. The precipitation and adhesion strength are good. Moreover, no plating deposition occurred in the rack coating in this step. On the other hand, in Comparative Example 1, although no plating was deposited on the frame, the amount of palladium adsorbed on the ABS resin was decreased, and the unexposed portion of the plating occurred. Further, in Comparative Example 2 and Comparative Example 3, the amount of adsorption of palladium was sufficiently obtained for the ABS resin, but plating was deposited on the frame. 10 [Example 2] (For direct plating on ABS resin) A 50% 00 x 3 mm ABS resin (manufactured by UMGABS Co., Ltd.) was used as a sample, and this was contained in potassium permanganate containing 0.001 mol/l and 7.5 mol/ l Immersion in the 35 ° C uranium engraving treatment solution for 1 minute. Then, the PAA-03 (polyamylamine: manufactured by Nitto Spinning Co., Ltd.) adjusted to 200 mg/l of sodium hydroxide was added to the catalyst-enhanced liquid for 30 minutes at pH °C for 2 minutes, and then further 1.2 mol/l hydrochloric acid, immersed for 1 minute at room temperature. Further, this was immersed in a solution containing 25 ml/l of D-POPACT (manufactured by Udilyt Co., Ltd.), 1.2 mol/l hydrochloric acid, and 1.7 mol/l of sodium chloride at 35 ° C for 4 minutes. Then, it was immersed for 3 minutes in a metallization of 45 ° C of D-POPMEA (manufactured by Ebara Udilyt Co., Ltd.) and l〇〇ml/l D-POPMEB (manufactured by Ebara Udilyt Co., Ltd.). . Finally, it was immersed in 25 °C EP-3 0 (copper sulfate plating solution: manufactured by Ubilyt Co., Ltd.) containing copper sulfate 〇.9 mol/l, 0.55 mol/l sulfuric acid and 〇.〇17 mol/l hydrochloric acid. In the first minute, the initial stage of energization was soft start (first 30 seconds -14 - 200811311 at 0.5V 'the next 30 seconds at 1.0V, and finally 1.5V), and direct plating was performed on the AB S resin. As a result of direct electroporation on the AB S resin, after 5 minutes of energization, the rack coating did not appear to be plated, and the sample was plated on the whole. Further, the plating film adhesion strength measured by the same method as in Test Example 1 was 〇8 kgf/cm. [Example 3] (Production of electroless plating film on various resins): Except for various resins (ABS, PC/ABS (including 65% PC), ASA, SAS, PC (UMGABS shares) used as samples Electroless nickel plating was performed on each of the resins in the same manner as in Example 1 except that the company (manufactured by Nippon Co., Ltd.) and polypropylene (manufactured by Nippon Chemical Co., Ltd.). [Comparative Example 4] (Production of electroless plating film on various resins): Various resins were used as samples (eight 88, ? (: / eight 88 (including 65% PC), ASA, SAS, PC) (manufactured by UMGABS Co., Ltd.), η ori 1 (manufactured by General Electric Co., Ltd.), and polypropylene (manufactured by Polychem Co., Ltd., Japan), in an etching solution containing 65 mol/l of chromic anhydride and 3.6 mol/l of sulfuric acid at 65 °C After immersing for 1 minute, the mixture was immersed in a 25 ° C reducing solution containing 0. 5 mο 1 /1 hydrochloric acid and 10 m 1 /1 of enil eX RD (manufactured by Udi 1 yt Co., Ltd.) for 2 minutes. Further, this was treated in the same manner as the 1.2 m〇l/l hydrochloric acid of Example 1 after the immersion (spray plating). -15-200811311 [Test Example 2] The electrolessness obtained in the above Example 3 and Comparative Example 4 was visually evaluated. The precipitation property in the various resins of the plating film and the precipitation on the frame were measured. The adhesion strength of the electroless plating film was measured in the same manner as in Test Example 1. The results are shown in Table 2.

〔Table 2〕

Electroless plating film deposition property Precipitation adhesion strength (kgf/cm) for rack coating Example 3 ABS Good Ant ΠΤΓ j\\\ 1.4 PC/ABS Good 4rrr πιι: /\\\ 0.8 ASA Good I111I J\ \\ 0.8 SAS Good 4nr mr y\\\ 1.1 noril Good 4fTT Μι II: J vw 1.0 Polypropylene good inL· jim y\\\ 1.2 PC good ^frrr nn: /\ \\ 0.1 Comparative example 4 ABS Good 4nr itTr j\\\ 1.2 PC/ABS Good&gt;frrf: ΊΠΓ /\\\ 0.8 ASA Good 4rvf 111ΙΓ J\\\ 0.7 SAS Good yvw 0.9 noril There are unprecipitated parts AnL· Till j\\\ 丨Polypropylene has not Precipitated portion M j \ \\ PC is not precipitated 4 nr liir - Unmeasured The electroless plating film obtained in Example 3 is completely applied to any resin, and Comparative Example 4 (chromic acid etching process) can be obtained in an equivalent or more. strength. Further, in Example 3, when electroless plating was carried out in any of the resins, the coating of -16 - 200811311 on the frame was not plated. Further, in Comparative Example 4 (chromic acid etching process), unprecipitated portions appeared in nor il and polypropylene resin, and no plating was deposited on PC resin. [Example 4] (Effect of imparting a catalyst reinforcing liquid): In the step of Example 1, the active ingredient to the catalyst-enhancing liquid was changed to PAA-03 (polyallylamine: manufactured by Nitto Spinning Co., Ltd.) In addition to those contained in Table 4 below, or Adecahorp, Adecatol, Adecablulonic (all manufactured by Asahi Denki Kogyo Co., Ltd.) and enadicol (manufactured by Lion Co., Ltd.), electroless nickel plating is performed on the AB S resin. In the AB S resin obtained by obtaining an electroless plating film, the precipitation property was evaluated in the same manner as in Test Example 1, and precipitation on the frame was evaluated. Further, the amount of palladium adsorbed on the A B S resin was measured in the same manner as in Test Example 1. These results are shown in Table 3 °

-17- 200811311 [Table 3-1]

The active ingredient of the catalyst-enhancing liquid, the molecular weight, the number of nitrogen atoms, the structural monoethanolamine 1] 61.08 1 ΗΟ~called ethylene diamine υ 60.11 2 η2ν^/ΝΗ2 ethylene diamine compound (diethylenetriamine) 1) 103.17 3 Η ethylene Diamine compound (triethylenetetramine) 1> 146.3 4 1 乙烯 Ethylene diamine compound (pentaethylene hexamine) 232 232.44 6 Ethylene imine polymer compound (SP-003) 2) 300 &gt; 5 Ethylene Amine-based polymer compound (SP0-012) 2) 1,200 &gt; 10 ethyleneimine-based polymer compound (SP200) 2) 20,000 &gt; 10 allylamine-based polymer compound (ΡΑΑ-03) 3) 3,000 &gt; 10 H —cc — H2 lH 〒h2 nh2 n Allylamine-based polymer compound (PAA-D41-HCL) 3) 20,000 &gt; 10 - Π n n-diallyl-based polymer compound (PAS-92 3) 5,000 &gt;10 if-η λ h2c ch2 八C" HH n -18- 200811311 [Table 3-2]

Diallylamine-based polymer compound (PAS-M-1)3) 20,000 &gt;10 Η H _ _c a c--c-c- H2 丫| h2 h2C\,h2 八cr h3c hn diallyl Amine-based polymer compound (PAS-880) 3) 40,000 &gt; 10 Ilc Η H c\. Ic p __\ 1 M f 1 ^ \ \ ch&gt; / hn Vinylamine-based polymer compound (PVAM-0570-B) 4) 400,000 &gt;10 h42 — —π-glycine” 75.7 1 HjN^^COOH Taurine” 125.15 1 〇V0 h2n^^ soh Amine ethanethiol hydrazine 157.2 1 h2h~sh 1 ) : Heguang Pure Pharmaceutical Co., Ltd. 2 ) : Sakamoto Catalyst Co., Ltd. 3) : Mindong Spinning Co., Ltd. 4): Mitsubishi Chemical Corporation -19- 200811311

[Table 4] The precipitation of the electroless plating film which is an effective component of the catalyst-enhancing liquid, and the adsorption amount of the palladium catalyst deposited on the rack coating (mg/dm2), the unprecipitated portion of the monoethanolamine, Ant τΤΓΓ j\\\ 0.026 ethylene diamine has unprecipitated portion 4τττ. ΊΠ1 /ν\\ 0.022 ethylene diamine compound (diethylenetriamine) good 4ητ ίΠΓ J 1 \\ 0.045 ethylene diamine compound (triethylenetetramine) good 4nr ΤίΤΠ /\\\ 0.050 Ethylene diamine compound (pentaethylene hexamine) Good &gt;frrr ΝΙΓ j\\\ 0.061 Ethylene imine polymer compound (SP-003) Good ΙΠΓ J\\\ 0.074 Ethylene imide high Molecular compound (SP0-012) Good 4πΐ ΊΠΓ j\\\ 0.122 Ethyleneimine polymer compound (SP200) Good ιΓΤΤ: j\\\ 0.107 Allylamine polymer compound (PAA-03) Good &gt;fr |T 111 ι: 0.108 Allylamine-based polymer compound (PAA-D41-HCL) cake ^fnrr ill Γ J\\\ 0.079 Diallylamine-based polymer compound (PAS-92) Good &gt; frrT llil J\\\ 0.049 Diallylamine-based polymer compound (PAS-M-1) Good 4mi Τ1Π: j \ w 0.068 Diallylamine-based polymer compound (PAS-880) Good ^111 J\ \\ 0.048 Vinylamine-based polymer compound (PVAM-0570-B) Good M y\\\ 0.082 Glycine Unprecipitated part &gt;fnr IMr /\\\ 0.029 Taurine has unprecipitated part Arvt. illl 0.023 Amine ethanethiol has unprecipitated part &gt;frrr ΊΙΙΙ: J\\\ 0.033 Adecahorp has unprecipitated part 4rrC JOlt \ 0.024 Adecatol has unprecipitated portion 0.031 Adecablulonic with unprecipitated portion 0.029 enadicol with unprecipitated portion 4ττΐ zleC jw\ 0.029 No catalyst-enhancing liquid treatment with unprecipitated portion ^frrr. ΠΙΙΓ 0.025 - 20 - 200811311 As a compound for imparting an effective component of a catalyst-enhancing liquid, a palladium is used as a compound, an ethyleneimine-based polymer compound, an allylamine compound, a diallylamine-based polymer compound, or a vinylamine system. As the amount of adsorption increases, the rack does not precipitate for decomposability. In this case, there is no increase in the amount of palladium adsorption in the presence of two or less nitrogen original monoethanolamine, ethylene diamine, glycine, taurine or amine compound in one molecule. In addition, the Adecahorp and enadicol of the anion agent did not particularly appear. Further, in the Adecablulonic of the nonionic surfactant, no increase in the amount of palladium adsorption occurred, and the precipitate was precipitated. [Example 5] (Inorganic acid effect in etching treatment liquid): In Example 1, except that the composition of the uranium engraving treatment liquid was changed, the same method as in the electroless example 1 was performed on the AB S resin. The results of the obtained electroless nickel film ABS resin and the like are shown in Table 5. Further, the adhesion strength of the nickel plating film was solved by the following tape peeling test. <Measurement Method> On the surface of the sample for electroless nickel plating, it was passed through a fingertip: Nichivan Co., Ltd.), and it was placed at 90°. After the scotch tape was peeled off, it was confirmed by visual observation that the amount of interfacial activity adsorption amount of the sub-ethyl thiol or the like of the compound having a plated ethylene diamine-based polymer compound compound having a good plating property was increased. A decat ο 1 More appears for the machine to be replaced by the following table 5 nickel plating. And the precipitation of the test. The electroless gelatin tape obtained by this evaluation ( whether the tape peeled off by the CT24 side is peeled off from the tape - 21 - 200811311. [Table 5] The composition of the etching treatment liquid The precipitation of the electroless plating film The tape peeling test has not precipitated potassium citrate Partially peeled off phosphoric acid has not precipitated part, peeled potassium permanganate + phosphoric acid &gt; frrf YlUZ /\\\ No peeling of potassium permanganate decahydrate y\\\ No peeling of potassium permanganate + nitric acid Frrr. 1 III, yv\n No peeling test was carried out in which the mixed solution of potassium permanganate and inorganic acid showed good plating precipitation and the strength of the combination was also good. In addition, potassium permanate and phosphoric acid were single. In the liquid of the composition, the surface of the plastic is hardly modified, so that undecomposed portions appear in the subsequent electroless nickel plating. Moreover, the adhesion strength of the plated portion is also low, and the tape is easily peeled off. Example 6] (pH effect containing an aqueous solution to which a catalyst-enhancing liquid is added) In the step of Example 1, except that the pH of the catalyst-enhancing liquid is adjusted using sodium hydroxide and sulfuric acid as described in the following Table 6, the same method is used. ABS resin Electroless nickel plating was carried out, and the precipitation property in the AB S resin of the obtained electroless nickel film and the precipitation on the frame coating were evaluated in the same manner as in Test Example 1. Further, the palladium adsorption amount on the ABS resin was measured in the same manner as in Test Example 1. The results are shown in Table 6. -22- 200811311 [Table 6] PH to the catalyst-enhanced liquid Electroless plating film deposition property The adsorption amount of the palladium catalyst precipitated on the rack (mg/dm2) 5.0 Good yfrrC Μ 0.045 6.0 Good Μ 0.061 7.0 Good Μ 0.063 8.0 Good Difficulty 0.073 9.0 Good yfTTt Μ 0.094 100 Good &gt;frrp Μ 0.108 11.0 Good AvaL Μ 0.116 12.0 Good 4rcL No 0.102 No Catalyst Enhancer Treatment - No Precipitation Part of Μ 0.025 gives an effect of increasing the amount of adsorption of the catalyst in the case where the pH of the catalyst-enhancing liquid is 5 · 0 to 1 2 · 0 °, and no increase in the amount of adsorption occurs. [Example 7] (Protection of catalyst-enhancing liquid The effect of the concentration) In the step of the first embodiment, the concentration of the polyallylamine (PAA-03: manufactured by Nitto Spinning Co., Ltd.) which is an active ingredient in the catalyst-enhancing liquid is adjusted to be as shown in Table 7, Same law Electroless nickel plating was carried out on the AB S resin, and the precipitate of the ABS resin of the obtained electroless nickel film was evaluated in the same manner as in Test Example 1. Further, the adsorption amount of palladium on the ABS resin was measured in the same manner as in Test Example 1. The results are shown in Table 7. -23- 200811311 [Table η The concentration of polyallylamine in the catalyst-enhanced liquid is adsorbed to the catalyst of the rack-coated precipitation pin (mg/dm2) 10 mg/l 4nL· Ι1ΤΓ j\ w 0.066 lOOmg/1 4ττΤ ι ΙΤΓ J\\\ 0.098 lg/1 None 0.119 10g/l 4rrr nil y\\\ 0.098 No treatment with catalyst-enhanced liquid M y\\\ 0.025 φ Irrelevant polyallyl The concentration of the amine 'suppresses the precipitation of the rack coating' and the effect of increasing the amount of palladium adsorption occurs. [Industrial Applicability] The metallization method of the plastic surface of the present invention can be formed into a method of sufficiently adhering and plating on a plastic surface, and which is not practically plated and deposited in a frame. Further, the method of the present invention can increase the amount of adsorption of the catalytic metal to the surface of the plastic. Therefore, the plastic which is less likely to adsorb the catalytic metal in the prior art method can also be plated. Therefore, the present invention is applicable to the metallization process of a chrome-free plastic surface [Simplified description of the drawing] [Fig. 1] Fig. 1 shows the result of measuring the surface of the ABS resin surface by a Fourier transform infrared spectrophotometer (1) : surface of ABS resin without etching treatment, 2: surface of AB S resin treated with etching solution containing chromic acid, surface of -24-200811311 ABS resin) 3 : treated with a contact treatment liquid containing permanganic acid

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Claims (1)

200811311 X. Patent Application Scope 1 A metallization method for plastic surface, characterized in that the plastic is treated with an engraving treatment liquid containing permanganate and a mineral acid, and then the functional group exposed on the surface thereof is provided with selective adsorption. The addition of the compound to the catalyst, the treatment of the plastic treated as described above, and the application of the catalyst-treated liquid to the plastic treated with the catalyst-enhancing liquid, followed by the application of the catalyst Metal plating on the plastic. 2. The metallization method of the plastic surface according to the first aspect of the invention, wherein the inorganic acid contained in the etching treatment liquid is at least one selected from the group consisting of phosphoric acid, sulfuric acid and nitric acid. 3. For the metallization method of the plastic surface according to item 1 or item 2 of the patent application, it is etched by using an etching solution of 0 ° C to 50 ° C. 如 4 The metallization method of the plastic surface according to any one of the items 3, wherein the permanganate concentration in the etching treatment liquid is 0.0005 mol/L or more. 5. A plastic material according to any one of claims 1 to 4, wherein the concentration of the inorganic acid in the etching treatment liquid is 2 mol/L or more. 6. The metallization method of a plastic surface according to any one of claims 1 to 5, which comprises a compound which selectively adsorbs a functional group exposed to a surface of the plastic to which the catalyst-enhancing liquid is provided. A compound of a nitrogen atom. 7. A method of metallizing a surface of a plastic -26-200811311 according to any one of claims 1 to 5, which comprises selectively adsorbing a functional group exposed to the surface of the plastic to which the catalyst-enhancing liquid is added. The compound is a compound containing three or more nitrogen atoms. 8. A method of metallizing a surface of a plastic* according to any one of claims 1 to 5, which comprises a compound which is selectively adsorbed to a functional group which is provided to the surface of the plastic to which the catalyst-enhancing liquid is exposed. A compound having a molecular weight of 100 or more. 9. The method of metallizing a plastic surface according to any one of claims 1 to 8, wherein the concentration of the compound which imparts selective adsorption to the functional group exposed on the surface of the plastic in the catalyst-enhancing liquid is 1 Omg / L or more. The metallization method of the plastic surface according to any one of claims 1 to 9, wherein the pH of the catalyst-enhancing liquid is 5 to 12. 1 1 The method of metallizing a plastic surface according to any one of claims 1 to 10, wherein the metal plating is electroless plating. ® 12. A metallization method for a plastic surface as claimed in claim 1 wherein the catalyst treatment liquid is a precious metal containing material. 1 3 · As in the case of the plastic surface of claim 11 or item 12, the metallization method' wherein the catalyst treatment liquid is a solution of palladium. The metallization method of the surface of the plastic material according to any one of the items 11 to 13 wherein the catalyst treatment liquid is a palladium/ruthenium mixed colloidal catalyst solution. 1 5 . The metallization method of the surface of the plastic® according to any one of the first to the fourteenth aspects of the patent application, which contains the catalyst of the -27-200811311 by using the catalyst-imparting treatment liquid, and contains hydrochloric acid or sulfuric acid. The step of treating the activated treatment liquid. 1 6. The metallization method of the plastic surface according to claim 15 wherein the concentration of hydrochloric acid or sulfuric acid in the activation treatment liquid is 0.5 mol/L or more. A metallization method for a plastic surface according to any one of claims 1 to 10, wherein the metal plating is electroplating. • 1 8. A metallization method for a plastic surface as claimed in claim 17 wherein the catalyst treatment solution is a palladium/ruthenium mixed colloidal catalyst solution. 1 . The metallizing method of the plastic surface according to claim 18, wherein the catalyst is applied to the catalyst treatment liquid, and further treated with an activation treatment liquid having a pH of 7 or more containing copper ions.