JPWO2017056285A1 - Etching solution for resin molding and its use - Google Patents
Etching solution for resin molding and its use Download PDFInfo
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- JPWO2017056285A1 JPWO2017056285A1 JP2017542633A JP2017542633A JPWO2017056285A1 JP WO2017056285 A1 JPWO2017056285 A1 JP WO2017056285A1 JP 2017542633 A JP2017542633 A JP 2017542633A JP 2017542633 A JP2017542633 A JP 2017542633A JP WO2017056285 A1 JPWO2017056285 A1 JP WO2017056285A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
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Abstract
過マンガン酸イオンを含有する酸性のエッチング液であって、更に、ｐＨ緩衝剤を含有することを特徴とする樹脂成形体用エッチング液およびこれを利用した樹脂成形体のエッチング方法、樹脂成形体へのめっき方法により過マンガン酸の有するエッチング性能はそのままで、安価に過マンガン酸の分解を抑制できる技術を提供する。An acidic etching solution containing permanganate ions, and further containing a pH buffer, an etching solution for a resin molded product, a method for etching a resin molded product using the same, and a resin molded product The present invention provides a technique capable of suppressing the decomposition of permanganic acid at low cost while maintaining the etching performance of permanganic acid as it is.
Description
本発明は、過マンガン酸イオンを含有する樹脂成形体用エッチング液およびその用途に関する。 The present invention relates to an etching solution for resin moldings containing permanganate ions and use thereof.
従来、樹脂成形体表面にめっきにより金属化処理を施す場合は、樹脂成形体表面とめっき皮膜との密着性を高めるために、めっき処理前に樹脂成形体表面をクロム酸と硫酸の混合液により粗化するエッチング処理を行うことが知られている。 Conventionally, when metallization treatment is performed on the surface of the resin molded body by plating, in order to improve the adhesion between the surface of the resin molded body and the plating film, the surface of the resin molded body is mixed with a mixed solution of chromic acid and sulfuric acid before the plating treatment. It is known to perform a roughening etching process.
しかし、上記エッチング処理では、有害な６価クロムを用いて６０℃以上の高温で作業するために、作業環境が悪くなり、またその廃水処理にも注意が必要であるという問題があった。 However, in the above etching process, there is a problem that the working environment is deteriorated because the work is performed at a high temperature of 60 ° C. or more using harmful hexavalent chromium, and the waste water treatment needs attention.
また、過マンガン酸を用いて樹脂成形体の表面をエッチングすることもできるが、使用条件によっては過マンガン酸が速やかに分解することがあり、工業的に使用するには問題がある場合があった。 In addition, although the surface of the resin molded body can be etched using permanganic acid, depending on the use conditions, permanganic acid may decompose rapidly, which may cause problems for industrial use. It was.
この過マンガン酸の分解を抑制するために、ハロゲンオキソ酸、ハロゲンオキソ酸塩、過硫酸塩およびビスマス酸塩からなる群から選ばれる成分を添加する技術が知られている（特許文献１）。 In order to suppress the decomposition of permanganic acid, a technique of adding a component selected from the group consisting of halogen oxoacids, halogen oxoacid salts, persulfate salts, and bismuth acid salts is known (Patent Document 1).
しかしながら、上記技術において過マンガン酸の分解を抑制する成分は価格が高く、およそ実用的なものではなかった。そのため、本発明は、過マンガン酸の有するエッチング性能はそのままで、安価に過マンガン酸の分解を抑制できる技術の提供をその課題とした。 However, in the above technique, components that inhibit the decomposition of permanganic acid are expensive and are not practical. Therefore, an object of the present invention is to provide a technique capable of suppressing the decomposition of permanganic acid at low cost while maintaining the etching performance of permanganic acid.
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、過マンガン酸イオンを含有する酸性のエッチング液に、更に、ｐＨ緩衝剤を含有させることにより過マンガン酸の分解を抑制できることを見出し、本発明を完成させた。 As a result of diligent research to solve the above problems, the present inventors have confirmed that decomposition of permanganic acid can be suppressed by further adding a pH buffer to an acidic etching solution containing permanganate ions. The headline and the present invention were completed.
すなわち、本発明は、過マンガン酸イオンを含有する酸性のエッチング液であって、更に、ｐＨ緩衝剤を含有することを特徴とする樹脂成形体用エッチング液である。 That is, this invention is an acidic etching liquid containing a permanganate ion, Comprising: It is an etching liquid for resin moldings characterized by further containing a pH buffer.
また、本発明は、樹脂成形体を、上記樹脂成形体用エッチング液で処理することを特徴とする樹脂成形体のエッチング方法である。 In addition, the present invention is a method for etching a resin molded body, wherein the resin molded body is treated with the etching solution for a resin molded body.
更に、本発明は、上記エッチング方法で樹脂成形体をエッチングした後、めっきを行うことを特徴とする樹脂成形体へのめっき方法である。 Furthermore, this invention is a plating method to the resin molding characterized by plating, after etching the resin molding by the said etching method.
また更に、本発明は、ｐＨ緩衝剤を有効成分とすることを特徴とする過マンガン酸イオンを含有する酸性のエッチング液における過マンガン酸の分解抑制剤である。 Furthermore, the present invention is a decomposition inhibitor for permanganic acid in an acidic etching solution containing permanganate ions, characterized by comprising a pH buffer as an active ingredient.
本発明の樹脂成形体用エッチング液は、エッチング液中の過マンガン酸の分解が抑制されるため、長時間エッチングをすることができる。 The etching solution for resin moldings of the present invention can be etched for a long time because decomposition of permanganic acid in the etching solution is suppressed.
また、本発明の樹脂成形体用エッチング液は、安価なｐＨ緩衝剤を用いるため、従来の過マンガン酸の分解を抑制するエッチング液よりも安価に調製することができる。 Moreover, since the etching solution for resin moldings of the present invention uses an inexpensive pH buffer, it can be prepared at a lower cost than conventional etching solutions that suppress the decomposition of permanganic acid.
そのため、本発明の樹脂成形体用エッチング液は、実用的に樹脂成形体をエッチングすることができるため、めっき工程に好適に利用できる。 Therefore, the etching solution for a resin molded body of the present invention can be practically etched into the resin molded body, and thus can be suitably used for the plating step.
本発明の樹脂成形体用エッチング液（以下、「本発明液」という）は、過マンガン酸イオンを含有する酸性のエッチング液であって、更に、ｐＨ緩衝剤を含有するものである。 The etching solution for resin moldings of the present invention (hereinafter referred to as “the present invention solution”) is an acidic etching solution containing permanganate ions, and further contains a pH buffer.
本発明液に含有されるｐＨ緩衝剤は、特に限定されないが、例えば、ホウ酸または、リン酸、酢酸、ホウ酸および炭酸から選ばれる酸のアルカリ金属塩が挙げられ、具体的にはリン酸二水素ナトリウム、リン酸二水素カリウム、酢酸ナトリウム、ホウ酸ナトリウム、炭酸ナトリウム等が挙げられ、これらの中でもホウ酸ナトリウム、炭酸ナトリウムが好ましい。なお、これらｐＨ緩衝剤は、１種または２種以上を用いることができる。本発明液におけるｐＨ緩衝剤の濃度は特に限定されないが、例えば、１０〜１５０ｇ／Ｌ、好ましくは２０〜１２０ｇ／Ｌ、特に好ましくは４０〜１００ｇ／Ｌであり、過マンガン酸イオン／ｐＨ緩衝剤の重量比が０.００１〜０.５、好ましくは０.００２〜０.２５、特に好ましくは０.００３〜０.１５である。 The pH buffer contained in the solution of the present invention is not particularly limited, and examples thereof include boric acid or alkali metal salts of acids selected from phosphoric acid, acetic acid, boric acid and carbonic acid. Specifically, phosphoric acid Examples thereof include sodium dihydrogen, potassium dihydrogen phosphate, sodium acetate, sodium borate, sodium carbonate and the like. Among these, sodium borate and sodium carbonate are preferable. In addition, these pH buffer agents can use 1 type (s) or 2 or more types. The concentration of the pH buffering agent in the liquid of the present invention is not particularly limited, and is, for example, 10 to 150 g / L, preferably 20 to 120 g / L, particularly preferably 40 to 100 g / L, and permanganate ion / pH buffering agent. The weight ratio is 0.001 to 0.5, preferably 0.002 to 0.25, particularly preferably 0.003 to 0.15.
本発明液に含有される過マンガン酸イオンは、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アルカリ金属塩から生じるものが挙げられる。なお、これら過マンガン酸のアルカリ金属塩は、１種または２種以上を用いることができる。本発明液における過マンガン酸イオンの濃度は特に限定されないが、例えば、０.０１〜２００ｇ／Ｌ、好ましくは０.０５〜１００ｇ／Ｌ、特に好ましくは０.１〜４０ｇ／Ｌである。 Examples of the permanganate ions contained in the solution of the present invention include those produced from alkali metal salts of permanganate such as potassium permanganate and sodium permanganate. In addition, these alkali metal salts of permanganic acid can use 1 type (s) or 2 or more types. The concentration of permanganate ions in the solution of the present invention is not particularly limited, but is, for example, 0.01 to 200 g / L, preferably 0.05 to 100 g / L, and particularly preferably 0.1 to 40 g / L.
本発明液は酸性、好ましくはｐＨ４以下である。本発明液をこの範囲に調整するために用いられる酸の種類は特に限定されず、例えば、リン酸、硫酸、硝酸、塩酸等の無機酸、酢酸、メタンスルホン酸等の有機酸等が挙げられる。これらの酸の中でも無機酸が好ましく、無機酸の中でも特にリン酸、硫酸が好ましい。なお、これこれら酸は、１種または２種以上を用いることができる。 The solution of the present invention is acidic, preferably pH 4 or less. The type of acid used to adjust the liquid of the present invention within this range is not particularly limited, and examples thereof include inorganic acids such as phosphoric acid, sulfuric acid, nitric acid and hydrochloric acid, and organic acids such as acetic acid and methanesulfonic acid. . Among these acids, inorganic acids are preferable, and among the inorganic acids, phosphoric acid and sulfuric acid are particularly preferable. These acids can be used alone or in combination of two or more.
本発明液は、本発明の効果を損なわない範囲で他の成分を配合してもよいが、好ましい態様としては、過マンガン酸イオン、酸、ｐＨ緩衝剤および水のみからなるものである。 Although this invention liquid may mix | blend another component in the range which does not impair the effect of this invention, as a preferable aspect, it consists only of permanganate ion, an acid, a pH buffer, and water.
本発明液の調製方法は特に限定されず、例えば、過マンガン酸塩とｐＨ緩衝剤を水等の溶媒に溶解した後、上記酸を添加してｐＨを酸性に調整すればよい。 The method for preparing the solution of the present invention is not particularly limited. For example, after dissolving a permanganate and a pH buffering agent in a solvent such as water, the acid may be added to adjust the pH to be acidic.
また、本発明液は、使用時に上記組成となればよいため、上記のようにして調製したものの他に、例えば、ｐＨ緩衝剤と、酸と、過マンガン酸イオンを含有する溶液とを、それぞれ１つずつの容器に収納し、それらを使用時に水等の溶媒中で混合するキットとする態様であってもよいし、ｐＨ緩衝剤を、過マンガン酸を含有する酸性のエッチング液の分解抑制剤として容器に収納しておき、これを別途調製した過マンガン酸イオンを含有する酸性のエッチング液に添加するという態様等であってもよい。 In addition, since the liquid of the present invention only needs to have the above composition at the time of use, in addition to those prepared as described above, for example, a pH buffer, an acid, and a solution containing permanganate ions, It may be a kit in which each is stored in a container and mixed in a solvent such as water at the time of use, or a pH buffer is used to suppress decomposition of an acidic etching solution containing permanganic acid. It may be stored in a container as an agent and added to an acid etching solution containing permanganate ions prepared separately.
斯くして得られる本発明液は、単に過マンガン酸イオンを含有する酸性のエッチング液よりも過マンガン酸の分解が抑制されているため、長時間樹脂成形体をエッチングすることができる。 Since the liquid of the present invention thus obtained suppresses decomposition of permanganic acid more than an acidic etching liquid containing permanganate ions, the resin molded body can be etched for a long time.
本発明液で処理することのできる樹脂は、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。これら樹脂の中でも、特にＡＢＳおよびＰＣ／ＡＢＳが好ましい。 Resins that can be treated with the liquid of the present invention are not particularly limited, and examples thereof include 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 resins, copolymers such as a liquid crystal polymer or the like and the above polymers. Among these resins, ABS and PC / ABS are particularly preferable.
上記樹脂の成形体としては、特に限定されないが、例えば、ラジエーターグリル、ホイールキャップ、エンブレム、ドアハンドル等の自動車関連部品等が挙げられる。 Although it does not specifically limit as a molded object of the said resin, For example, automotive parts, such as a radiator grille, a wheel cap, an emblem, a door handle, etc. are mentioned.
本発明液で、上記樹脂成形体を処理する方法は、特に限定されないが、例えば、本発明液の液温を０〜１００℃、好ましくは３０〜６０℃とし、それに樹脂成形体を、例えば、１〜３０分間、好ましくは５〜２０分間、空気撹拌あるいは揺動撹拌を行い浸漬すればよい。 The method of treating the resin molded body with the liquid of the present invention is not particularly limited. For example, the liquid temperature of the liquid of the present invention is 0 to 100 ° C., preferably 30 to 60 ° C. What is necessary is just to immerse by performing air stirring or rocking stirring for 1 to 30 minutes, preferably 5 to 20 minutes.
上記のようにして本発明液で樹脂成形体を処理した後は、必要により、常法に従って、中和・還元処理や、触媒付与処理等を行えば、無電解めっきを行うことができる。 After the resin molded body is treated with the solution of the present invention as described above, electroless plating can be performed if necessary by performing neutralization / reduction treatment, catalyst application treatment, or the like according to a conventional method.
中和・還元処理は一般にめっき工程の中和・還元処理に用いられるものであれば特に限定されないが、例えば、硫酸ヒドロキシルアミン、塩酸ヒドロキシルアミン、硫酸鉄、塩化鉄、クエン酸、アスコルビン酸、メチオニン等の還元剤を含むものが好ましい。これら中和・還元処理液にて樹脂成形体を処理するには、中和・還元処理液の液温を１０〜８０℃、好ましくは３０〜６０℃とし、それに樹脂成形体を１〜２０分間、好ましくは２〜５分間浸漬させ処理すればよい。 The neutralization / reduction treatment is not particularly limited as long as it is generally used for the neutralization / reduction treatment in the plating step. For example, hydroxylamine sulfate, hydroxylamine hydrochloride, iron sulfate, iron chloride, citric acid, ascorbic acid, methionine Those containing a reducing agent such as In order to treat the resin molded body with the neutralization / reduction treatment liquid, the liquid temperature of the neutralization / reduction treatment liquid is set to 10 to 80 ° C., preferably 30 to 60 ° C. Preferably, the treatment may be performed by dipping for 2 to 5 minutes.
触媒付与処理は、一般にめっき工程の触媒付与に用いられるものであれば特に制限されないが、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／すず混合コロイド触媒溶液が好ましい。これら触媒を樹脂成形体に付与するには、触媒付与処理液の液温を１０〜６０℃、好ましくは２０〜５０℃とし、それに樹脂成形体を１〜２０分間、好ましくは２〜５分間浸漬させ処理すればよい。 The catalyst application treatment is not particularly limited as long as it is generally used for catalyst application in the plating step, but preferably contains a noble metal, more preferably contains palladium, and particularly preferably a palladium / tin mixed colloid catalyst solution. In order to apply these catalysts to the resin molded body, the temperature of the catalyst application treatment liquid is 10 to 60 ° C., preferably 20 to 50 ° C., and the resin molded body is immersed in the resin molded body for 1 to 20 minutes, preferably 2 to 5 minutes. Process.
無電解めっきは、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樹脂成形体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樹脂成形体を５〜１５分間浸漬させ処理すればよい。 The electroless plating 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 the resin molded body is plated with an electroless nickel plating solution, the resin molded body 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. What is necessary is just to process.
無電解めっきは、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樹脂成形体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樹脂成形体を５〜１５分間浸漬させ処理すればよい。 The electroless plating 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 the resin molded body is plated with an electroless nickel plating solution, the resin molded body 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. What is necessary is just to process.
また、樹脂成形体の金属化に直接電気金属めっき（ダイレクトプレーティング）を用いる場合には、触媒付与処理液にて触媒を付与した後に、更に、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を行ってもよい。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、硫酸銅などが挙げられる。活性化処理液にて樹脂成形体を処理するには、活性化処理液の液温を０〜６０℃、好ましくは３０〜５０℃とし、それに樹脂成形体を１〜２０分間、好ましくは２〜５分間浸漬させ処理すればよい。 Moreover, when using direct electrometal plating (direct plating) for metallization of a resin molding, after adding a catalyst with a catalyst application | coating process liquid, it is further pH 7 or more containing copper ion, Preferably pH 12 or more The treatment may be performed with the activation treatment liquid. 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 resin molded body with the activation treatment liquid, the liquid temperature of the activation treatment liquid is set to 0 to 60 ° C., preferably 30 to 50 ° C., and the resin molded body is placed on the resin molding for 1 to 20 minutes, preferably 2 to 2. What is necessary is just to immerse and process for 5 minutes.
上記のようにして樹脂成形体に無電解めっきや電気金属めっき等の金属めっきを施し、金属化した樹脂成形体には、更に、目的に応じて各種電気銅めっきや電気ニッケルめっきを施すことも可能である。 The resin molded body is subjected to metal plating such as electroless plating or electrometal plating as described above, and the metallized resin molded body may be further subjected to various types of electrolytic copper plating and electrolytic nickel plating depending on the purpose. Is possible.
以下、本発明を実施例を挙げて詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples at all.
実 施 例 １
エッチング液の調製：
以下の成分のエッチング液を水中で混合して調製した（ｐＨは０以下）。また、エッチング液中の過マンガン酸の建浴１、２、３時間後の減少率を以下のようにして求めた。その結果も表１に示した。Example 1
Etching solution preparation:
The etching liquid of the following components was mixed and prepared in water (pH is 0 or less). Further, the reduction rate of the permanganic acid in the etching solution after 1, 2, and 3 hours was determined as follows. The results are also shown in Table 1.
＜減少率の求め方＞
各エッチング液（４５０ｍＬ）を５０℃に加温し、０.２５ｄｍ２のＡＢＳ樹脂を各時間浸漬した後、過マンガン酸濃度を測定。浸漬０時間の過マンガン酸濃度と各時間の過マンガン酸濃度から減少率を求めた。<How to find the rate of decrease>
Each etchant (450 mL) was heated to 50 ° C., and 0.25 dm 2 ABS resin was immersed in each time, and then the permanganate concentration was measured. The reduction rate was determined from the permanganic acid concentration at 0 hours of immersion and the permanganic acid concentration at each time.
以上の結果から、リン酸と過マンガン酸イオンを含有するエッチング液にｐＨ緩衝剤を添加することで、過マンガンイオン濃度の減少率を低下させ、エッチング液の高い安定性を示した。 From the above results, by adding a pH buffer to the etching solution containing phosphoric acid and permanganate ions, the reduction rate of the permanganate ion concentration was reduced, and the etching solution showed high stability.
実 施 例 ２
エッチング液の調製：
以下の成分のエッチング液を実施例１と同様に調製した（ｐＨは０以下）。また、エッチング液中の過マンガン酸の３０分後の建浴減少率を実施例１と同様にして求めた。その結果も表２に示した。Example 2
Etching solution preparation:
Etching solutions having the following components were prepared in the same manner as in Example 1 (pH is 0 or less). Further, the rate of decrease of the bathing solution after 30 minutes of permanganic acid in the etching solution was determined in the same manner as in Example 1. The results are also shown in Table 2.
以上の結果から、硫酸においても実施例１と同様にｐＨ緩衝剤を添加することで、過マンガンイオン濃度の減少率を低下させた。 From the above results, the decrease rate of the permanganate ion concentration was reduced by adding a pH buffering agent in sulfuric acid as in Example 1.
実 施 例 ３
めっき：
実施例１の実施品３と同様の組成のエッチング液を調製した。これを５０℃に加温したものにＡＢＳの板を１０分間浸漬した。浸漬後、３５℃の中和・還元処理溶液ＤＳ−３５０（ＪＣＵ株式会社製）に１分間浸漬し、１５ｍｌ／ＬのＣＴ−５８０（ＪＣＵ株式会社製）および２.５ｍｏｌ／Ｌの塩酸を含有する３５℃のパラジウム／すずコロイド触媒溶液に４分間浸漬し、１.２ｍｏｌ／Ｌの塩酸からなる３５℃の活性化処理液に４分間浸漬し、無電解ニッケルめっきを行ったところ、問題なくＡＢＳ上にめっきできた。Example 3
Plating:
An etching solution having the same composition as that of Example 3 of Example 1 was prepared. This was warmed to 50 ° C. and an ABS plate was immersed for 10 minutes. After immersion, the sample is immersed in a neutralization / reduction treatment solution DS-350 (manufactured by JCU Corporation) at 35 ° C. for 1 minute, and contains 15 ml / L CT-580 (manufactured by JCU Corporation) and 2.5 mol / L hydrochloric acid. When immersed in a 35 ° C. palladium / tin colloidal catalyst solution for 4 minutes, immersed in a 35 ° C. activation treatment solution of 1.2 mol / L hydrochloric acid for 4 minutes, and subjected to electroless nickel plating, ABS was used without any problem. I was able to plate it on top.
実 施 例 ４
エッチング液キット：
以下の試薬Ａ〜Ｃを個別のパッケージに封入したエッチング液キットを作製した。
試薬Ａ：過マンガン酸カリウム ５ｇ
試薬Ｂ：リン酸（８９％） ７００ｍｌ
試薬Ｃ：ホウ酸ナトリウム ８０ｇExample 4
Etching solution kit:
An etching solution kit in which the following reagents A to C were sealed in individual packages was produced.
Reagent A: Potassium permanganate 5g
Reagent B: phosphoric acid (89%) 700 ml
Reagent C: 80 g of sodium borate
上記試薬Ａ〜Ｃを開封し、１Ｌの水に溶解してエッチング液が得られた（ｐＨは０以下）。 The reagents A to C were opened and dissolved in 1 L of water to obtain an etching solution (pH is 0 or less).
本発明の樹脂成形体用エッチング液は、樹脂成形体をエッチングすることができるため、めっきの前処理として好適に利用できる。
以 上The etching solution for a resin molded body of the present invention can be suitably used as a pretreatment for plating because the resin molded body can be etched.
that's all
Claims (6)
A decomposition inhibitor of permanganic acid in an acidic etching solution containing permanganate ions, characterized by comprising a pH buffer as an active ingredient.
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/JP2015/077915 WO2017056285A1 (en) | 2015-10-01 | 2015-10-01 | Etching solution for resin molded body and use thereof |
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| JPWO2017056285A1 true JPWO2017056285A1 (en) | 2018-10-04 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52124434A (en) * | 1976-04-14 | 1977-10-19 | Matsushita Electric Ind Co Ltd | Resin plating method and surface treating agent therefor |
| WO2007122869A1 (en) * | 2006-04-18 | 2007-11-01 | Okuno Chemical Industries Co., Ltd. | Composition for etching treatment of resin molded article |
| WO2008132926A1 (en) * | 2007-04-18 | 2008-11-06 | Ebara-Udylite Co., Ltd. | Etching solution, and method for metallization of plastic surface employing the method |
| WO2008143190A1 (en) * | 2007-05-22 | 2008-11-27 | Okuno Chemical Industries Co., Ltd. | Pretreatment process for electroless plating of resin molded body, method for plating resin molded body, and pretreatment agent |
| WO2015060196A1 (en) * | 2013-10-22 | 2015-04-30 | 奥野製薬工業株式会社 | Composition for etching treatment of resin material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6139762A (en) * | 1998-12-11 | 2000-10-31 | Shipley Company, L.L.C. | Methods for manufacture of electronic devices |
| JP4275157B2 (en) * | 2006-07-27 | 2009-06-10 | 荏原ユージライト株式会社 | Metallization method for plastic surfaces |
-
2015
- 2015-10-01 JP JP2017542633A patent/JPWO2017056285A1/en active Pending
- 2015-10-01 WO PCT/JP2015/077915 patent/WO2017056285A1/en active Application Filing
- 2015-10-15 TW TW104133871A patent/TW201713797A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52124434A (en) * | 1976-04-14 | 1977-10-19 | Matsushita Electric Ind Co Ltd | Resin plating method and surface treating agent therefor |
| WO2007122869A1 (en) * | 2006-04-18 | 2007-11-01 | Okuno Chemical Industries Co., Ltd. | Composition for etching treatment of resin molded article |
| WO2008132926A1 (en) * | 2007-04-18 | 2008-11-06 | Ebara-Udylite Co., Ltd. | Etching solution, and method for metallization of plastic surface employing the method |
| WO2008143190A1 (en) * | 2007-05-22 | 2008-11-27 | Okuno Chemical Industries Co., Ltd. | Pretreatment process for electroless plating of resin molded body, method for plating resin molded body, and pretreatment agent |
| WO2015060196A1 (en) * | 2013-10-22 | 2015-04-30 | 奥野製薬工業株式会社 | Composition for etching treatment of resin material |
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| TW201713797A (en) | 2017-04-16 |
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