JP2009228083A - Metal plating method on plastic surface - Google Patents
Metal plating method on plastic surface Download PDFInfo
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- JP2009228083A JP2009228083A JP2008076995A JP2008076995A JP2009228083A JP 2009228083 A JP2009228083 A JP 2009228083A JP 2008076995 A JP2008076995 A JP 2008076995A JP 2008076995 A JP2008076995 A JP 2008076995A JP 2009228083 A JP2009228083 A JP 2009228083A
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- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 230000003213 activating effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 78
- 229910052759 nickel Inorganic materials 0.000 description 39
- 238000001994 activation Methods 0.000 description 25
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 23
- 229910000365 copper sulfate Inorganic materials 0.000 description 18
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 18
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- 229910052804 chromium Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 8
- 238000007772 electroless plating Methods 0.000 description 8
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 8
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
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- 239000012286 potassium permanganate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
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- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
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- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- QMRNDFMLWNAFQR-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid;styrene Chemical compound C=CC#N.OC(=O)C=C.C=CC1=CC=CC=C1 QMRNDFMLWNAFQR-UHFFFAOYSA-N 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
本発明は、プラスチック表面への金属めっき方法に関し、更に詳細には、プラスチック表面と金属めっき皮膜の密着性が向上する金属めっき方法に関する。 The present invention relates to a metal plating method on a plastic surface, and more particularly to a metal plating method in which adhesion between a plastic surface and a metal plating film is improved.
これまで種々のプラスチック表面にめっき皮膜が形成され、半導体、自動車等の部品等として利用されている。このような部品等に用いられるプラスチック表面とめっき皮膜との密着性はあまり高くないので、めっき前にプラスチック表面のエッチング処理が行われている。しかし、このエッチング処理でよく用いられているクロム酸エッチング液には有害な６価クロムが多量に含まれており、環境対応等の面からその代替品が望まれていた。 Until now, plating films have been formed on various plastic surfaces and used as parts for semiconductors, automobiles and the like. Since the adhesion between the plastic surface used for such parts and the like and the plating film is not so high, the plastic surface is etched before plating. However, the chromic acid etching solution often used in this etching process contains a large amount of harmful hexavalent chromium, and an alternative is desired in terms of environmental friendliness.
現在では、クロム酸エッチング液の代替品として、過マンガン酸を含む酸性のエッチング液について多数の報告がされている（特許文献１等）。一般的に過マンガン酸を含む酸性のエッチング液はプラスチック表面の強い改質効果が得られるものの、めっき処理中は密着性が弱く、各処理液や水洗水の温度差、めっき皮膜の応力などにより密着不良（めっき皮膜の膨れ）を引き起こすことがあり、特にこの不良は銅めっき後に、最終的なニッケル、クロム等の電気めっきを行った場合には顕著であったため実用化には至っていなかった。 At present, as an alternative to the chromic acid etching solution, many reports have been made on acidic etching solutions containing permanganic acid (Patent Document 1, etc.). In general, an acidic etching solution containing permanganic acid can provide a strong modification effect on the plastic surface, but it has poor adhesion during the plating process, depending on the temperature difference of each processing solution and washing water, the stress of the plating film, etc. Insufficient adhesion (swelling of the plating film) may occur, and this defect was particularly noticeable when the final electroplating of nickel, chromium, etc. was performed after copper plating, so it was not put into practical use. .
密着不良対策としては、無電解めっき上がりにて加工部品を乾燥（アニール）させることも有効な手段と考えられるが、その場合、その後のめっき工程において析出不良や外観不良、金属の不導体化による密着不良など新たな問題が発生し、また生産性が著しく低下するという問題もあった。
従って、本発明は、めっき工程に過マンガン酸を含む酸性のエッチング液で処理する工程がある場合であっても、従来のクロム酸エッチング液による処理の場合と同等なめっき皮膜とプラスチック表面の良好な密着性や生産性が得られるプラスチック表面への金属めっき方法を提供することを課題とした。 Therefore, even when the plating process includes a process of treating with an acidic etchant containing permanganic acid, the plating film and the plastic surface are as good as those of the conventional chromic acid etchant. An object of the present invention is to provide a method of metal plating on a plastic surface that can provide excellent adhesion and productivity.
本発明者らは、上記課題を解決するために鋭意研究した結果、従来の過マンガン酸を含む酸性のエッチング液で処理する工程を含むプラスチック表面への金属めっき方法において、エッチング後、最終的な電気金属めっきを行うまでにプラスチック表面を温水溶液で処理することにより、上記課題を解決可能なことを見出し、本発明を完成させた。 As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention, in a conventional method for plating a metal surface on a plastic surface including a step of treating with an acidic etchant containing permanganic acid, after etching, finally The present inventors have found that the above problems can be solved by treating the plastic surface with a warm aqueous solution before performing electrometal plating, and have completed the present invention.
すなわち、本発明はプラスチック表面を過マンガン酸を含む酸性のエッチング液でエッチング処理した後、プラスチック表面に触媒付与処理および触媒活性化処理し、最終的に電気金属めっきを行うプラスチック表面への金属めっき方法であって、何れかの処理の後にプラスチック表面を温水溶液で処理することを特徴とするプラスチック表面への金属めっき方法およびこの方法により得られるめっき製品である。 That is, in the present invention, after the plastic surface is etched with an acidic etchant containing permanganic acid, the plastic surface is subjected to a catalyst imparting treatment and a catalyst activation treatment, and finally the metal plating is performed on the plastic surface for electrometal plating. A metal plating method on a plastic surface, characterized in that the plastic surface is treated with a warm aqueous solution after any treatment, and a plated product obtained by this method.
本発明によれば、プラスチック表面に金属めっきする際に、過マンガン酸を含む酸性のエッチング液を用いた場合であっても、プラスチック表面を温水溶液で処理するだけの簡単な方法により、密着性や生産性が従来のクロム酸を含むエッチング液を用いた場合と同様なものとなり、実用的である。 According to the present invention, when metal plating is performed on a plastic surface, even if an acidic etching solution containing permanganic acid is used, adhesion can be achieved by a simple method of treating the plastic surface with a warm aqueous solution. Further, the productivity is the same as that in the case of using a conventional etching solution containing chromic acid, which is practical.
本発明のプラスチック表面への金属めっき方法（以下、「本発明方法」という）は、プラスチック表面を過マンガン酸を含む酸性のエッチング液でエッチング処理し、次いで、プラスチック表面に触媒付与処理および触媒活性化処理し、最終的に電気金属めっきを行うプラスチック表面への金属めっき方法であって、何れかの処理の後にプラスチック表面を温水溶液で処理する方法である。なお、本明細書において、上記「何れかの処理」には、最終的な電気金属めっきは含まれない。 In the metal plating method on the plastic surface of the present invention (hereinafter referred to as “method of the present invention”), the plastic surface is etched with an acidic etching solution containing permanganic acid, and then the catalyst is applied to the plastic surface and the catalytic activity is applied. This is a method of metal plating on a plastic surface that is subjected to a chemical treatment and is finally subjected to electrometal plating, in which the plastic surface is treated with a warm aqueous solution after any treatment. In the present specification, the “any process” does not include final electrometal plating.
本発明方法で金属めっきされるプラスチックとしては、特に制限されないが、例えば、アクリロニトリル・ブタジエン・スチレン（ＡＢＳ）、ポリカーボネート／アクリロニトリル・ブタジエン・スチレン（ＰＣ／ＡＢＳ）、アクリロニトリル・スチレン・アクリレート（ＡＳＡ）、シリコン系複合ゴム−アクリロニトリル−スチレン（ＳＡＳ）、ノリル、ポリプロピレン、ポリカーボネート（ＰＣ）、アクリロニトリル・スチレン、ポリアセテート、ポリスチレン、ポリアミド、芳香族ポリアミド、ポリエチレン、ポリエーテルケトン、ポリエチレンテフタレート、ポリブチレンテフタレート、ポリスルホン、ポリエーテルエーテルスルホン、ポリエーテルイミド、変性ポリフェニレンエーテル、ポリフェニレンスルフィド、ポリアミド、ポリイミド、エポキシ樹脂、液晶ポリマー等や上記各ポリマーのコポリマー等が挙げられる。これらプラスチックの中でも、特にＡＢＳおよびＰＣ／ＡＢＳが好ましい。 The plastic to be metal-plated by the method of the present invention is not particularly limited. For example, acrylonitrile butadiene styrene (ABS), polycarbonate / acrylonitrile butadiene styrene (PC / ABS), acrylonitrile styrene acrylate (ASA), Silicone composite rubber-acrylonitrile-styrene (SAS), noryl, polypropylene, polycarbonate (PC), acrylonitrile styrene, polyacetate, polystyrene, polyamide, aromatic polyamide, polyethylene, polyetherketone, polyethylene terephthalate, polybutylene terephthalate , Polysulfone, polyetherethersulfone, polyetherimide, modified polyphenylene ether, polyphenylene sulfide, polyamide, Polyimide, epoxy resin, copolymer of a liquid crystal polymer or the like and the above polymers. Among these plastics, ABS and PC / ABS are particularly preferable.
本発明方法においてエッチング処理は、過マンガン酸を含む酸性のエッチング液を用いて行われる。このエッチング液を用いたエッチング処理は、特に限定されないが、例えば、上記エッチング液の液温を０〜１００℃、好ましくは３５〜７０℃とし、それにプラスチックを１〜３０分間、好ましくは５〜１５分間浸漬することにより行われる。 In the method of the present invention, the etching treatment is performed using an acidic etching solution containing permanganic acid. Although the etching process using this etching liquid is not specifically limited, For example, the liquid temperature of the said etching liquid shall be 0-100 degreeC, Preferably it is 35-70 degreeC, and also plastics for 1 to 30 minutes, Preferably it is 5-15. It is performed by soaking for a minute.
上記エッチング液に含有される過マンガン酸塩としては、特に限定されないが、例えば、過マンガン酸カリウム、過マンガン酸ナトリウム等の過マンガン酸の金属塩が挙げられる。この過マンガン酸塩のエッチング液中の濃度は０.０００５ｍｏｌ／Ｌ以上であり、好ましくは０.００５〜０.５ｍｏｌ／Ｌである。また、上記エッチング液のｐＨは２.０以下、ｐＨ１.０以下が好ましい。 Although it does not specifically limit as a permanganate contained in the said etching liquid, For example, metal salts of permanganate, such as potassium permanganate and sodium permanganate, are mentioned. The concentration of this permanganate in the etching solution is 0.0005 mol / L or more, preferably 0.005 to 0.5 mol / L. The pH of the etching solution is preferably 2.0 or less and pH 1.0 or less.
また、上記エッチング液は、上記過マンガン酸塩を水等の溶媒に溶解し、その後エッチング液のｐＨを調整することにより調製される。ｐＨの調製には、無機酸または有機酸を特に制限無く用いることができ、例えば、塩酸、硫酸、硝酸等の無機酸や、酢酸、有機スルホン酸等の有機酸が挙げられる。 The etching solution is prepared by dissolving the permanganate in a solvent such as water, and then adjusting the pH of the etching solution. For the pH adjustment, an inorganic acid or an organic acid can be used without particular limitation, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as acetic acid and organic sulfonic acid.
なお、上記エッチング処理後には、必要によりプラスチック表面の中和・還元処理を行ってもよい。この中和・還元処理には、一般にめっき工程の中和・還元処理に用いられる中和・還元処理液を特に限定なく使用することができるが、還元剤を含むものが好ましい。この中和・還元処理は、中和・還元処理液の液温を１０〜８０℃、好ましくは３０〜７０℃とし、それにプラスチックを１〜２０分間、好ましくは２〜５分間浸漬させることにより行われる。 In addition, after the etching treatment, neutralization / reduction treatment of the plastic surface may be performed as necessary. For this neutralization / reduction treatment, a neutralization / reduction treatment solution generally used for neutralization / reduction treatment in the plating step can be used without particular limitation, but those containing a reducing agent are preferred. This neutralization / reduction treatment is performed by setting the liquid temperature of the neutralization / reduction treatment liquid to 10 to 80 ° C., preferably 30 to 70 ° C., and immersing the plastic in it for 1 to 20 minutes, preferably 2 to 5 minutes. Is called.
上記のように処理されたプラスチックは、次に、触媒付与処理および触媒活性化処理を行う。触媒付与処理は、触媒付与処理液でプラスチック表面を処理することにより行われる。この触媒付与処理には、一般にめっき工程の触媒付与に用いられる触媒付与処理液を特に限定なく用いることができるが、触媒として貴金属を含むものが好ましく、パラジウムを含むものがより好ましく、特にパラジウム／すず混合コロイドを含むものが好ましい。本発明において触媒付与処理は、触媒付与処理液の液温を１０〜６０℃、好ましくは２０〜５０℃とし、それにプラスチックを１〜２０分間、好ましくは２〜５分間浸漬させることにより行われる。 Next, the plastic treated as described above is subjected to a catalyst application treatment and a catalyst activation treatment. The catalyst application treatment is performed by treating the plastic surface with a catalyst application treatment liquid. In this catalyst application treatment, a catalyst application treatment liquid generally used for applying a catalyst in the plating step can be used without any particular limitation. However, a catalyst containing a noble metal is preferable, a catalyst containing palladium is more preferable, and palladium / Those containing tin mixed colloids are preferred. In this invention, a catalyst provision process is performed by making the liquid temperature of a catalyst provision process liquid into 10-60 degreeC, Preferably it is 20-50 degreeC, and a plastic is immersed in it for 1 to 20 minutes, Preferably it is 2 to 5 minutes.
また、触媒活性化処理は、その後に続くめっき処理の種類によって異なるが、例えば、触媒活性化処理後に通常のめっき処理（無電解めっき工程）を行うのであれば、触媒活性化処理は、０.５ｍｏｌ／Ｌ以上、好ましくは１〜４ｍｏｌ／Ｌの塩酸または硫酸を含有する活性化処理液で処理することにより行われる。この触媒活性化処理は、活性化処理液の液温を０〜６０℃、好ましくは３０〜４５℃とし、それにプラスチックを１〜２０分間、好ましくは２〜５分間浸漬させることにより行われる。一方、触媒活性化処理後にダイレクトプレーティングを行うのであれば、触媒活性化処理は、銅イオンを含有するｐＨ７以上、好ましくはｐＨ１２以上の活性化処理液で処理することにより行われる。この活性化処理液に含有される銅イオンの由来は特に制限されず、例えば、硫酸銅等が挙げられる。活性化処理液にてプラスチック表面を処理するには、活性化処理液の液温を０〜６０℃、好ましくは３０〜５０℃とし、それにプラスチックを１〜２０分間、好ましくは２〜５分間浸漬させ処理すればよい。 Further, the catalyst activation treatment varies depending on the type of the subsequent plating treatment. For example, if a normal plating treatment (electroless plating step) is performed after the catalyst activation treatment, the catalyst activation treatment is 0. It is carried out by treatment with an activation treatment solution containing 5 mol / L or more, preferably 1 to 4 mol / L hydrochloric acid or sulfuric acid. This catalyst activation treatment is performed by setting the temperature of the activation treatment liquid to 0 to 60 ° C., preferably 30 to 45 ° C., and immersing the plastic in it for 1 to 20 minutes, preferably 2 to 5 minutes. On the other hand, if direct plating is performed after the catalyst activation treatment, the catalyst activation treatment is performed by treatment with an activation treatment solution containing copper ions at pH 7 or higher, preferably pH 12 or higher. 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 5 minutes. Process.
触媒活性化処理後に無電解めっき工程を行う場合、触媒活性化処理後は、無電解金属めっき処理および電気銅めっき処理を行い、その後最終的な金属めっきを行う。 When the electroless plating process is performed after the catalyst activation process, after the catalyst activation process, an electroless metal plating process and an electrolytic copper plating process are performed, and then final metal plating is performed.
この無電解めっき工程における無電解金属めっき処理は、公知の無電解ニッケルめっき液、無電解銅めっき液、無電解コバルトめっき液等の無電解金属めっきを用いて常法に従って行うことができる。具体的に、無電解ニッケルめっき液でプラスチック表面にめっき処理を行う場合には、ｐＨ８〜１０で３０〜５０℃の液温の無電解ニッケルめっき液にプラスチックを５〜１５分間浸漬させ処理すればよい。この無電解金属めっき処理の後には、必要により常法のストライクめっき処理を行っても良い。このストライクめっき処理は、一般的に用いられるものであれば特に限定されないが、例えば、ニッケルワット浴、硫酸銅浴、ピロリン酸銅浴等を用い、その液温を０〜６０℃、好ましくは３０〜５０℃とし、これにプラスチックを浸漬し、０.５〜５Ａ／ｄｍ２で１〜１０分間処理することにより行われる。 The electroless metal plating treatment in this electroless plating step 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. After this electroless metal plating treatment, a conventional strike plating treatment may be performed if necessary. The strike plating treatment is not particularly limited as long as it is generally used. For example, a nickel watt bath, a copper sulfate bath, a copper pyrophosphate bath or the like is used, and the liquid temperature is 0 to 60 ° C., preferably 30. It is set to -50 degreeC, a plastic is immersed in this, and it processes by 0.5 to 5 A / dm < 2 > for 1 to 10 minutes.
また、この無電解めっき工程における電気銅めっき処理は、常法に従って行うことができ、例えば、硫酸銅浴等の汎用の電気銅めっき浴を用い、これにプラスチックを浸漬し、１〜５Ａ／ｄｍ２で５〜６０分間処理することにより行われる。 Moreover, the electrolytic copper plating process in this electroless-plating process can be performed in accordance with a conventional method, for example, using a general-purpose electrolytic copper plating bath such as a copper sulfate bath, and immersing the plastic in this, 1-5 A / dm 2 for 5 to 60 minutes.
更に、この無電解めっき工程における最終的な電気金属めっきは、銅を除く金属の電気めっきであり、好ましくは電気ニッケルめっきおよび／または電気クロムめっきであり、より好ましくは半光沢ニッケルめっきおよび／または光沢ニッケルめっきおよび／または光沢クロムめっきが挙げられる。この最終的な電気金属めっきは、目的に応じて公知の各種電気めっき浴を用い、常法に従い行うことができる。 Further, the final electrometal plating in this electroless plating process is electroplating of metals other than copper, preferably electro nickel plating and / or electro chrome plating, more preferably semi-bright nickel plating and / or Bright nickel plating and / or bright chromium plating can be mentioned. This final electrometal plating can be performed according to a conventional method using various known electroplating baths according to the purpose.
一方、触媒活性化処理後にダイレクトプレーティングを行うのであれば、触媒活性化処理後は、電気銅めっき処理を行い、その後最終的な電気金属めっきを行う。 On the other hand, if direct plating is performed after the catalyst activation process, after the catalyst activation process, an electrolytic copper plating process is performed, and then a final electrometal plating is performed.
このダイレクトプレーティングにおける電気銅めっき処理は、硫酸銅浴等の汎用の電気銅めっき浴に浸漬し、通常の条件、例えば、１〜５Ａ／ｄｍ２で５〜６０分間処理することにより行われる。 The electrolytic copper plating treatment in this direct plating is performed by immersing in a general-purpose electrolytic copper plating bath such as a copper sulfate bath and treating at normal conditions, for example, 1 to 5 A / dm 2 for 5 to 60 minutes.
また、このダイレクトプレーティングにおける最終的な電気金属めっきは、上記した無電解めっき工程における最終的な電気金属めっきと同様にして行うことができる。 The final electrometal plating in the direct plating can be performed in the same manner as the final electrometal plating in the electroless plating process.
上記した無電解めっき工程およびダイレクトプレーティングの後には、更に、目的に応じてクロムめっきや金などの貴金属めっき、塗装など各種処理を行うことも可能である。 After the above-described electroless plating process and direct plating, various treatments such as noble metal plating such as chromium plating and gold, and painting can be performed according to the purpose.
本発明方法においては、エッチング処理後から最終的な電気金属めっきを行う前までの何れかの処理の後においてプラスチック表面を温水溶液で処理する。この処理に用いられる温水溶液は、プラスチックやプラスチック上のめっき触媒、めっき皮膜を侵すものでなければ特に限定されないが、好ましくは水である。また、温水の温度は４０〜１００℃、好ましくは５０〜９０℃である。更に、プラスチック表面を温水で処理するには、プラスチック表面を温水に１０秒〜３０分、好ましくは１〜２０分接触させる。この温水の接触方法は特に限定されないが、例えば、温水浴中にプラスチックを浸漬する方法や温水をプラスチック表面に噴霧する方法等が挙げられる。 In the method of the present invention, the plastic surface is treated with a warm aqueous solution after any treatment from after the etching treatment to before the final electrometal plating. The warm aqueous solution used for this treatment is not particularly limited as long as it does not invade the plastic, the plating catalyst on the plastic and the plating film, but is preferably water. Moreover, the temperature of warm water is 40-100 degreeC, Preferably it is 50-90 degreeC. Furthermore, in order to treat the plastic surface with warm water, the plastic surface is brought into contact with warm water for 10 seconds to 30 minutes, preferably 1 to 20 minutes. The method of contacting the warm water is not particularly limited, and examples thereof include a method of immersing plastic in a warm water bath and a method of spraying warm water on the plastic surface.
上記した本発明方法で得られるプラスチック表面にめっき皮膜が施されためっき製品は、金属めっき皮膜とプラスチック表面の密着性が向上しているので、例えば、半導体、自動車等の部品等に好適である。 The plated product obtained by applying the plating film to the plastic surface obtained by the above-described method of the present invention has improved adhesion between the metal plating film and the plastic surface, and is suitable for, for example, parts such as semiconductors and automobiles. .
以下、本発明方法を実施例等を挙げて詳細に説明をするが、本発明はこれら実施例に何ら限定されるものではない。 Hereinafter, the method of the present invention will be described in detail with reference to examples and the like, but the present invention is not limited to these examples.
参 考 例 １
従来めっき方法によるプラスチック表面への金属めっき：
試料として５０×１００×３ｍｍのＡＢＳ樹脂（３００１Ｍ：ＵＭＧＡＢＳ株式会社製）を用い、これを下記に示す酸性の過マンガン酸エッチング液またはクロム酸エッチング液を６８℃に加温したものに１０分間浸漬した。次に、これを３５℃の中和・還元処理溶液（ＥＮＩＬＥＸ−ＲＤ：荏原ユージライト株式会社製）に２分間浸漬し、表面を中和・還元した。
Reference example 1
Metal plating on plastic surface by conventional plating method:
A 50 × 100 × 3 mm ABS resin (3001M: manufactured by UMGABS Co., Ltd.) was used as a sample, and this was immersed in an acidic permanganic acid etching solution or chromic acid etching solution shown below heated to 68 ° C. for 10 minutes. did. Next, this was immersed in a 35 ° C. neutralization / reduction treatment solution (ENILEX-RD: manufactured by Sugawara Eugleite Co., Ltd.) for 2 minutes to neutralize and reduce the surface.
＜過マンガン酸エッチング液＞
過マンガン酸カリウム：０.０７ｍｏｌ／Ｌ
硫酸：３.０ｍｏｌ／Ｌ
ｐＨ：１.０以下
＜クロム酸エッチング液＞
無水クロム酸：３.５ｍｏｌ／Ｌ
硫酸３.６ｍｏｌ／Ｌ
ｐＨ：１.０以下
<Permanganic acid etchant>
Potassium permanganate: 0.07 mol / L
Sulfuric acid: 3.0 mol / L
pH: 1.0 or less <chromic acid etchant>
Chromic anhydride: 3.5 mol / L
Sulfuric acid 3.6 mol / L
pH: 1.0 or less
中和・還元された試料を、２５℃の１.２ｍｏｌ／Ｌの塩酸からなるプレディップ液に１分間浸漬した。この試料を、３５℃のパラジウム／すず混合コロイド触媒溶液（ＣＴ−５８０：荏原ユージライト株式会社製）に４分間浸漬し、ＡＢＳ樹脂上に触媒を付与した。 The neutralized and reduced sample was immersed in a pre-dip solution composed of 1.2 mol / L hydrochloric acid at 25 ° C. for 1 minute. This sample was immersed for 4 minutes in a palladium / tin mixed colloidal catalyst solution (CT-580: manufactured by Ebara Eugelite Co., Ltd.) at 35 ° C. to give a catalyst on the ABS resin.
触媒が付与された試料を１.２ｍｏｌ／Ｌの塩酸からなる３５℃の触媒活性化処理液に４分間浸漬し、触媒を活性化させた。次いで、３５℃の無電解ニッケルめっき液（ＥＮＩＬＥＸ ＮＩ−５：荏原ユージライト株式会社製）に１０分間浸漬し、ＡＢＳ樹脂上に無電解ニッケルめっきを施した。 The sample provided with the catalyst was immersed in a catalyst activation treatment liquid at 35 ° C. composed of 1.2 mol / L hydrochloric acid for 4 minutes to activate the catalyst. Subsequently, it was immersed in an electroless nickel plating solution (ENILEX NI-5: manufactured by Ebara Eugleite Co., Ltd.) at 35 ° C. for 10 minutes, and electroless nickel plating was performed on the ABS resin.
その後、２５℃の酸活性溶液（Ｖ−３４５：荏原ユージライト株式会社製）に１分間浸漬し、次いで４５℃のワット浴に２Ａ／ｄｍ２で３分間浸漬してニッケルストライクを行った。更に、２５℃の硫酸銅めっき液（ＥＰ−３０：荏原ユージライト株式会社製）中で、３Ａ／ｄｍ２で４０分間、膜厚が２０μｍとなるように硫酸銅めっきを施した。 Then, it was immersed for 1 minute in an acid active solution (V-345: EBARA Eugleite Co., Ltd.) at 25 ° C., and then immersed in a watt bath at 45 ° C. for 3 minutes at 2 A / dm 2 to perform nickel strike. Furthermore, copper sulfate plating was performed in a copper sulfate plating solution at 25 ° C. (EP-30: manufactured by Ebara Eugleite Co., Ltd.) at 3 A / dm 2 for 40 minutes so that the film thickness was 20 μm.
電気銅めっき後、更に、最終的な電気金属めっきとして、半光沢ニッケルめっき、光沢ニッケルめっきおよび光沢クロムめっきを行った。まず、５５℃の半光沢ニッケルめっき液（ＣＦ−２４Ｔ：荏原ユージライト株式会社製）中で、３Ａ／ｄｍ２で２０分間、膜厚が１０μｍとなるように半光沢ニッケルめっきを施した。その後、５０℃の光沢ニッケルめっき液（＃８８：荏原ユージライト株式会社製）中で、３Ａ／ｄｍ２で２０分間、膜厚が１０μｍとなるように光沢ニッケルめっきを施した。最後に、４０℃の光沢クロムめっき液（Ｅ−４０：荏原ユージライト株式会社製）中で、１０Ａ／ｄｍ２で５分間、膜厚が０.２５μｍとなるように光沢クロムめっきを施した。なお、上記した電気銅めっき後各工程間においては２５℃の水で洗浄を行った。 After electrolytic copper plating, semi-bright nickel plating, bright nickel plating, and bright chromium plating were further performed as the final electric metal plating. First, semi-bright nickel plating was performed in a 55 ° C. semi-bright nickel plating solution (CF-24T: manufactured by Ebara Euligite Co., Ltd.) at 3 A / dm 2 for 20 minutes so that the film thickness was 10 μm. Thereafter, bright nickel plating was applied in a bright nickel plating solution at 50 ° C. (# 88: manufactured by Sugawara Eugleite Co., Ltd.) at 3 A / dm 2 for 20 minutes so that the film thickness became 10 μm. Finally, bright chromium plating was performed in a bright chromium plating solution (E-40: manufactured by Ebara Euligite Co., Ltd.) at 40 ° C. at 10 A / dm 2 for 5 minutes so that the film thickness was 0.25 μm. In addition, it wash | cleaned with 25 degreeC water between each process after the above-mentioned electrolytic copper plating.
硫酸銅めっき処理後の密着強度を、引っ張り強度試験機（ＡＧＳ−Ｈ５００Ｎ：株式会社島津製作所製）を用いて測定した。また、光沢クロムめっき処理後のめっき外観を目視で以下の評価基準に従って評価した。その結果を表１に示した。 The adhesion strength after the copper sulfate plating treatment was measured using a tensile strength tester (AGS-H500N: manufactured by Shimadzu Corporation). Moreover, the plating appearance after the bright chrome plating treatment was visually evaluated according to the following evaluation criteria. The results are shown in Table 1.
＜めっき外観評価基準＞
（評価） （内容）
○ ： 良好
× ： 膨れ箇所有り
<Plating appearance evaluation criteria>
(Evaluation) (Content)
○: Good ×: There is a swollen part
表１の結果から、酸性の過マンガン酸エッチング液ではめっき処理中の密着強度が低いため、最終工程（光沢クロムめっき）まで行うと、密着不足に起因する不良が発生した。なお、ＪＩＳ Ｈ８６３０付属書６に従って硫酸銅めっき処理後に７０℃で１時間アニールをした後の密着強度を上記と同様にして測定したところ、共に１.０ｋｇｆ／ｃｍであった。このことはアニールの工程を行えば、酸性の過マンガン酸およびクロム酸のどちらでエッチングを行っても変わらないことを示した。 From the results shown in Table 1, since the adhesion strength during the plating process is low in the acidic permanganate etching solution, a defect due to insufficient adhesion occurred when the final process (bright chrome plating) was performed. In addition, when the adhesion strength after annealing at 70 ° C. for 1 hour after copper sulfate plating treatment according to JIS H8630 appendix 6 was measured in the same manner as described above, both were 1.0 kgf / cm. This indicates that if the annealing process is performed, etching with either acidic permanganic acid or chromic acid does not change.
実 施 例 １
本発明方法によるプラスチック表面への金属めっき（１）：
上記参考例１の金属めっき工程の、エッチング処理後、中和還元処理後、触媒付与処理後、触媒活性化処理後、無電解ニッケルめっき処理後、ニッケルストライク処理後、硫酸銅めっき処理後、半光沢ニッケルめっき後、光沢ニッケルめっき後または光沢クロムめっき後の何れかにおいて６５℃の温水へ５分間浸漬する温水で洗浄する工程（以下、この工程を「温水洗」ということもある）を行った。この温水洗の工程を行い、硫酸銅めっき処理まで行った後の密着強度を、参考例１と同様にして測定した。また、光沢クロムめっき処理後のめっき外観を参考例１と同様にして評価した。それらの結果を表２に示した。
Example 1
Metal plating on plastic surface by the method of the present invention (1):
After the etching process, the neutralization reduction process, the catalyst application process, the catalyst activation process, the electroless nickel plating process, the nickel strike process, the copper sulfate plating process, the semi-metal plating process of the reference example 1 After the bright nickel plating, either after the bright nickel plating or after the bright chrome plating, a process of washing with warm water immersed in warm water at 65 ° C. for 5 minutes (hereinafter, this process is sometimes referred to as “warm water washing”) was performed. . The adhesion strength after this warm water washing step and the copper sulfate plating treatment was measured in the same manner as in Reference Example 1. The plating appearance after the bright chrome plating treatment was evaluated in the same manner as in Reference Example 1. The results are shown in Table 2.
以上の結果より、エッチング処理後、中和還元処理後、触媒付与処理後、触媒活性化処理後、無電解ニッケルめっき処理後、ニッケルストライク処理後および硫酸銅めっき処理後の何れか、すなわち、エッチング処理後から最終的な電気金属めっき（半光沢ニッケルめっき〜光沢クロムめっき）を施す前までに温水洗を行うことで密着強度が向上し、光沢クロムめっき後の外観も良好になることが分かった。また、電気ニッケルめっきを施している最中もしくはそれ以降に温水洗を行っても効果がないことが分かった。 From the above results, after etching treatment, after neutralization reduction treatment, after catalyst application treatment, after catalyst activation treatment, after electroless nickel plating treatment, after nickel strike treatment and after copper sulfate plating treatment, that is, etching It was found that the adhesion strength is improved by washing with warm water after the treatment and before the final electrometal plating (semi-bright nickel plating to bright chrome plating), and the appearance after the bright chrome plating is also improved. . It was also found that there was no effect even if hot water washing was performed during or after electro nickel plating.
実 施 例 ２
本発明方法によるプラスチック表面への金属めっき（２）：
エッチング液の組成を下記のものにする以外は上記実施例１と同様にしてめっき処理および温水洗の工程を行った。また、この温水洗の工程を行い、硫酸銅めっき処理まで行った後の密着強度を、参考例１と同様にして測定した。また、光沢クロムめっき処理後のめっき外観を参考例１と同様にして評価した。それらの結果を表３に示した。
Example 2
Metal plating on plastic surface by the method of the present invention (2):
A plating process and a hot water washing process were performed in the same manner as in Example 1 except that the composition of the etching solution was as follows. In addition, the adhesion strength after the hot water washing process and the copper sulfate plating treatment were measured in the same manner as in Reference Example 1. Further, the plating appearance after the bright chrome plating treatment was evaluated in the same manner as in Reference Example 1. The results are shown in Table 3.
＜過マンガン酸エッチング液＞
過マンガン酸カリウム：０.０７ｍｏｌ／Ｌ
硝酸：４.０ｍｏｌ／Ｌ
ｐＨ：１.０以下
<Permanganic acid etchant>
Potassium permanganate: 0.07 mol / L
Nitric acid: 4.0 mol / L
pH: 1.0 or less
以上の結果より、エッチング液に含まれる酸を硫酸から硝酸に代えても、エッチング処理後、中和還元処理後、触媒付与処理後、触媒活性化処理後、無電解ニッケルめっき処理後、ニッケルストライク処理後および硫酸銅めっき処理後の何れか、すなわち、エッチング処理後から最終的な電気金属めっき（半光沢ニッケルめっき〜光沢クロムめっき）を施す前までに温水洗を行うことで密着強度が向上し、光沢クロムめっき後の外観も良好になることが分かった。また、電気ニッケルめっきを施している最中もしくはそれ以降に温水洗を行っても効果がないことが分かった。 From the above results, even if the acid contained in the etching solution is changed from sulfuric acid to nitric acid, after the etching treatment, after neutralization reduction treatment, after catalyst application treatment, after catalyst activation treatment, after electroless nickel plating treatment, nickel strike Adhesion strength is improved by washing with warm water either after the treatment or after the copper sulfate plating treatment, that is, after the etching treatment and before the final electrometal plating (semi-bright nickel plating to bright chromium plating). It was also found that the appearance after bright chrome plating was also improved. It was also found that there was no effect even if hot water washing was performed during or after electro nickel plating.
実 施 例 ３
本発明方法によるプラスチック表面への金属めっき（３）：
試料として５０×１００×３ｍｍのＡＢＳ樹脂（３００１Ｍ：ＵＭＧＡＢＳ株式会社製）を用い、これを下記に示す酸性の過マンガン酸エッチング液を６８℃に加温したものに１０分間浸漬した。次に、これを３５℃の中和・還元処理溶液（ＥＮＩＬＥＸ−ＲＤ：荏原ユージライト株式会社製）に２分間浸漬し、表面を中和・還元した。
Example 3
Metal plating on plastic surface by the method of the present invention (3):
A 50 × 100 × 3 mm ABS resin (3001M: manufactured by UMGABS Co., Ltd.) was used as a sample, and this was immersed in an acidic permanganic acid etching solution shown below heated to 68 ° C. for 10 minutes. Next, this was immersed in a 35 ° C. neutralization / reduction treatment solution (ENILEX-RD: manufactured by Sugawara Eugleite Co., Ltd.) for 2 minutes to neutralize and reduce the surface.
＜過マンガン酸エッチング液＞
過マンガン酸カリウム：０.０７ｍｏｌ／Ｌ
硫酸：３.０ｍｏｌ／Ｌ
ｐＨ：１.０以下
<Permanganic acid etchant>
Potassium permanganate: 0.07 mol / L
Sulfuric acid: 3.0 mol / L
pH: 1.0 or less
中和・還元された試料を、２５℃の１．２ｍｏｌ／Ｌの塩酸からなるプレディップ液に１分間浸漬した。この試料を、３５℃のパラジウム／すず混合コロイド触媒溶液（Ｄ−ＰＯＰ ＡＣＴ−ＭＵ：荏原ユージライト株式会社製）に４分間浸漬し、ＡＢＳ樹脂上に触媒を付与した。 The neutralized and reduced sample was immersed in a pre-dip solution composed of 1.2 mol / L hydrochloric acid at 25 ° C. for 1 minute. This sample was immersed in a palladium / tin mixed colloidal catalyst solution (D-POP ACT-MU: manufactured by Sugawara Eugleite Co., Ltd.) at 35 ° C. for 4 minutes to give a catalyst on the ABS resin.
触媒が付与された試料を４５℃の銅イオンを含有するｐＨ１２以上の触媒活性化処理液（Ｄ−ＰＯＰ ＭＥ：荏原ユージライト株式会社製）に３分間浸漬し、触媒を活性化させた。次いで、２５℃の硫酸銅めっき液（ＥＰ−３０：荏原ユージライト株式会社製）中で、３Ａ／ｄｍ２で４０分間、膜厚が２０μｍとなるように硫酸銅めっきを施した。 The sample provided with the catalyst was immersed for 3 minutes in a catalyst activation treatment solution (D-POP ME: EBARA Eugleite Co., Ltd.) containing 45 ° C. copper ions and having a pH of 12 or more to activate the catalyst. Subsequently, copper sulfate plating was performed in a copper sulfate plating solution at 25 ° C. (EP-30: manufactured by Ebara Eugleite Co., Ltd.) at 3 A / dm 2 for 40 minutes so that the film thickness became 20 μm.
電気銅めっき後、更に、最終的な電気金属めっきとして、半光沢ニッケルめっき、光沢ニッケルめっきおよび光沢クロムめっきを行った。まず、５５℃の半光沢ニッケルめっき液（ＣＦ−２４Ｔ：荏原ユージライト株式会社製）中で、３Ａ／ｄｍ２で２０分間、膜厚が１０μｍとなるように半光沢ニッケルめっきを施した。その後、５０℃の光沢ニッケルめっき液（＃８８：荏原ユージライト株式会社製）中で、３Ａ／ｄｍ２で２０分間、膜厚が１０μｍとなるように光沢ニッケルめっきを施した。最後に、４０℃の光沢クロムめっき液（Ｅ−４０：荏原ユージライト株式会社製）中で、１０Ａ／ｄｍ２で５分間、膜厚が０.２５μｍとなるように光沢クロムめっきを施した。 After electrolytic copper plating, semi-bright nickel plating, bright nickel plating, and bright chromium plating were further performed as the final electric metal plating. First, semi-bright nickel plating was performed in a 55 ° C. semi-bright nickel plating solution (CF-24T: manufactured by Ebara Euligite Co., Ltd.) at 3 A / dm 2 for 20 minutes so that the film thickness was 10 μm. Thereafter, bright nickel plating was applied in a bright nickel plating solution at 50 ° C. (# 88: manufactured by Sugawara Eugleite Co., Ltd.) at 3 A / dm 2 for 20 minutes so that the film thickness became 10 μm. Finally, bright chromium plating was performed in a bright chromium plating solution (E-40: manufactured by Ebara Euligite Co., Ltd.) at 40 ° C. at 10 A / dm 2 for 5 minutes so that the film thickness was 0.25 μm.
なお、上記金属めっき工程の、エッチング処理後、中和還元処理後、触媒付与処理後、触媒活性化処理後、硫酸銅めっき処理後、半光沢ニッケルめっき後、光沢ニッケルめっき後または光沢クロムめっき後の何れかにおいて６５℃の温水へ５分間浸漬する温水洗の工程を行った。この温水洗の工程を行い、硫酸銅めっき処理まで行った後の密着強度を、参考例１と同様にして測定した。また、光沢クロムめっき処理後のめっき外観を参考例１と同様にして評価した。それらの結果を表４に示した。 In addition, after the etching treatment, neutralization reduction treatment, after catalyst application treatment, after catalyst activation treatment, after copper sulfate plating treatment, after semi-bright nickel plating, after bright nickel plating, or after bright chromium plating in the above metal plating step In any of the above, a warm water washing step of immersing in 65 ° C. warm water for 5 minutes was performed. The adhesion strength after this warm water washing step and the copper sulfate plating treatment was measured in the same manner as in Reference Example 1. Further, the plating appearance after the bright chrome plating treatment was evaluated in the same manner as in Reference Example 1. The results are shown in Table 4.
以上の結果より、エッチング処理後、中和還元処理後、触媒付与処理後、触媒活性化処理後および硫酸銅めっき処理後の何れか、すなわち、エッチング処理後から最終的な電気金属めっき（半光沢ニッケルめっき〜光沢クロムめっき）を施す前までに温水洗を行うことで密着強度が向上し、光沢クロムめっき後の外観も良好になることが分かった。また、電気ニッケルめっきを施している最中もしくはそれ以降に温水洗を行っても効果がないことが分かった。 From the above results, after the etching treatment, after neutralization reduction treatment, after catalyst application treatment, after catalyst activation treatment and after copper sulfate plating treatment, that is, after the etching treatment, the final electrometal plating (semi-gloss) It was found that the adhesion strength was improved by washing with warm water before applying nickel plating to bright chrome plating, and the appearance after bright chrome plating was also improved. It was also found that there was no effect even if hot water washing was performed during or after electro nickel plating.
本発明方法は、プラスチック表面を温水溶液で処理するだけの簡単な方法により、プラスチック表面とめっき皮膜との密着性や生産性が、従来のクロム酸を含むエッチング液を用いた場合と同等なものとなり、実用的なものである。
以 上
The method of the present invention is a simple method in which the plastic surface is simply treated with a warm aqueous solution, and the adhesion and productivity between the plastic surface and the plating film are equivalent to those obtained when an etching solution containing conventional chromic acid is used. It is practical.
more than
Claims (8)
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