JP2006316297A - Coating agent for hindering being plated thereon and pretreatment method for plating - Google Patents

Coating agent for hindering being plated thereon and pretreatment method for plating Download PDF

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JP2006316297A
JP2006316297A JP2005138045A JP2005138045A JP2006316297A JP 2006316297 A JP2006316297 A JP 2006316297A JP 2005138045 A JP2005138045 A JP 2005138045A JP 2005138045 A JP2005138045 A JP 2005138045A JP 2006316297 A JP2006316297 A JP 2006316297A
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plating
resin
coating agent
plated
molded body
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JP4663394B2 (en
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Toshihiro Tai
利弘 田井
Masahiko Itakura
雅彦 板倉
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Daicel Polymer Ltd
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Daicel Polymer Ltd
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Priority to TW095116486A priority patent/TW200643214A/en
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1605—Process or apparatus coating on selected surface areas by masking
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating agent for hindering being plated thereon, which prevents a plated film from forming on a desired part even when the desired part is immersed in an electroless plating bath. <P>SOLUTION: The coating agent for hindering being plated thereon includes a water-repellent resin of 0.1 to 100 pts.mass with respect to an olefinic resin of 100 pts.mass, and one or more compounds of 0.1 to 100 pts.mass selected from among compounds containing antimony and bismuth, as needed. The olefinic resin is preferably polyethylene, and the water-repellent resin is preferably a fluororesin and/or a silicone resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、金属や樹脂からなる成形体表面をめっきするときに使用する難めっき性被覆剤、及びそれを用いためっきの前処理方法に関する。   The present invention relates to a difficult-to-platable coating agent used when plating the surface of a molded body made of metal or resin, and a plating pretreatment method using the same.

自動車を軽量化する目的から、自動車部品としてＡＢＳ樹脂やポリアミド樹脂等の樹脂成形体が使用されており、この樹脂成形体に高級感や美感を付与するため、銅、ニッケル等のめっきが施されている。   For the purpose of reducing the weight of automobiles, resin molded products such as ABS resin and polyamide resin are used as automotive parts, and copper, nickel, etc. are plated to give this resin molded product a high-class feeling and beauty. ing.

従来、ＡＢＳ樹脂等の成形体にめっきを施す場合、樹脂成形体とめっき層との密着強度を高めるため、脱脂工程の後に樹脂成形体を粗面化するエッチング工程が必須である。例えば、ＡＢＳ樹脂成形体やポリプロピレン成形体をめっきする場合、脱脂処理の後に、クロム酸浴（三酸化クロム及び硫酸の混液）を用い、６５〜７０℃、１０〜１５分でエッチング処理する必要があり、廃水には有毒な６価のクロム酸イオンが含まれる。このため、６価のクロム酸イオンを３価のイオンに還元した後に中和沈殿させる処理が必須となる。   Conventionally, when plating is performed on a molded body such as an ABS resin, an etching process for roughening the resin molded body after the degreasing process is essential in order to increase the adhesion strength between the resin molded body and the plating layer. For example, when plating an ABS resin molded body or a polypropylene molded body, it is necessary to perform an etching treatment at 65 to 70 ° C. for 10 to 15 minutes using a chromic acid bath (mixed solution of chromium trioxide and sulfuric acid) after the degreasing treatment. Yes, wastewater contains toxic hexavalent chromate ions. For this reason, the process which neutralizes and precipitates after reducing a hexavalent chromate ion to a trivalent ion becomes essential.

このように現場での作業時の安全性や廃水による環境への影響を考慮すると、クロム浴を使用したエッチング処理をしないことが望ましいが、その場合には、ＡＢＳ樹脂等から得られる成形体へのめっき層の密着強度を高めることができないという問題がある。   In this way, in consideration of safety during work at the site and the environmental impact of wastewater, it is desirable not to perform etching using a chromium bath, but in that case, to a molded body obtained from ABS resin, etc. There is a problem that the adhesion strength of the plating layer cannot be increased.

特許文献１、２の発明は、このような従来技術の問題を解決し、クロム浴を使用したエッチング処理を不要としたにも拘わらず、高い密着強度を有する金属めっき層を有するめっき樹脂成形体が得られたものである。
特開２００３−８２１３８号公報 特開２００３−１６６０６７号公報 特開平１０−５３８７８号公報 The inventions of Patent Documents 1 and 2 solve such problems of the prior art, and a plated resin molded article having a metal plating layer having a high adhesion strength in spite of eliminating the need for an etching process using a chromium bath. Is obtained.
JP 2003-82138 A Japanese Patent Laid-Open No. 2003-166067 JP-A-10-53878

樹脂成形体にめっきする場合、樹脂成形体を金属製治具で保持した状態で無電解めっき浴に浸漬する。クロム酸浴によるエッチング工程を経た場合、金属製治具表面にはクロム酸が残留し、これが触媒毒として作用する。このため、無電解めっきをするときに金属製治具表面にめっきが析出することはないが、特許文献１、２の発明では、クロム酸浴によるエッチング工程がないため、金属製治具表面にもめっきが析出するという問題がある。   When plating on a resin molded body, the resin molded body is immersed in an electroless plating bath while being held by a metal jig. When an etching process using a chromic acid bath is performed, chromic acid remains on the surface of the metal jig, and this acts as a catalyst poison. For this reason, the plating does not deposit on the surface of the metal jig when performing electroless plating. However, in the inventions of Patent Documents 1 and 2, there is no etching step using a chromic acid bath. However, there is a problem that plating is deposited.

特許文献３の発明では、樹脂成形体の非めっき部分に塗布するためのレジスト用塗料、レジスト用インク等に適用するめっき析出阻害用組成物が開示されている。しかし、同文献の実施例にも記載のとおり、クロム酸浴によるエッチング工程を前提とするめっき方法で使用するものである。   The invention of Patent Document 3 discloses a composition for inhibiting plating precipitation applied to a resist paint, a resist ink, and the like for application to a non-plated portion of a resin molded body. However, as described in the examples of this document, it is used in a plating method based on an etching process using a chromic acid bath.

本発明は、金属や樹脂からなる成形体表面を無電解めっき等する際、所望部分をめっきさせないようにできる難めっき性被覆剤、及びそれを用いためっきの前処理方法を提供することを課題とする。   It is an object of the present invention to provide a non-plating-resistant coating agent capable of preventing a desired portion from being plated when performing electroless plating or the like on the surface of a molded body made of a metal or a resin, and a plating pretreatment method using the same. And

本発明は、課題の解決手段として、オレフィン系樹脂１００質量部に対して、撥水性樹脂を０．１〜１００質量部及び必要に応じてアンチモン、ビスマスを含む化合物から選ばれる１以上を０．１〜１００質量部含有する難めっき性被覆剤を提供する。   As a means for solving the problem, the present invention provides 0.1 to 100 parts by weight of a water-repellent resin and, if necessary, a compound containing antimony and bismuth to 100 parts by weight of an olefin resin. Provided is a non-platable coating agent containing 1 to 100 parts by mass.

また本発明は、他の課題の解決手段として、成形体表面の非めっき部分に対して、請求項１又は２記載の難めっき性被覆剤を粉体塗装する、めっきの前処理方法を提供する。   In addition, the present invention provides a plating pretreatment method as a means for solving other problems, in which a non-plating coating material according to claim 1 or 2 is powder coated on a non-plated portion on the surface of a molded body. .

本発明の難めっき性被覆剤は粉末状のものであり、塗料、インクのように溶剤を含むものではない。   The difficult-to-platable coating agent of the present invention is in a powder form and does not contain a solvent like paint and ink.

本発明において「難めっき性」とは、成形体表面に無電解めっきをする場合おいて、めっきの析出を防止すること乃至はめっきが析出し難くすることを含む意味である。   In the present invention, “difficult to plate” means to prevent deposition of plating or make plating difficult to deposit when electroless plating is performed on the surface of a molded body.

本発明の難めっき性被覆剤を用い、粉体塗装法によって成形体表面を被覆することにより、無電解めっき浴に浸漬した場合にも、前記成形体表面にめっきが析出することがない。よって、成形体の所望部分がめっきされないようにすることができる（即ち成形体の所望部分がめっきされるようにすることができる）。   Even when immersed in an electroless plating bath, plating is not deposited on the surface of the formed body by coating the surface of the formed body by the powder coating method using the difficult-to-platable coating agent of the present invention. Therefore, it is possible to prevent the desired portion of the molded body from being plated (that is, to allow the desired portion of the molded body to be plated).

＜難めっき性被覆剤＞
本発明で用いるオレフィン系樹脂は、成形体表面の非めっき部分に皮膜を形成し、前記部分を難めっき性にするためのベース成分となるものである。なお、粉体塗装ができる範囲であれば、オレフィン系樹脂以外の熱可塑性樹脂を配合することもできるが、オレフィン系樹脂との合計量中５０質量％以下が好ましい。 <Hard plating coating agent>
The olefin resin used in the present invention is a base component for forming a film on a non-plated portion on the surface of the molded body and making the portion difficult to plate. In addition, if it is the range which can be powder-coated, thermoplastic resins other than an olefin resin can also be mix | blended, However, 50 mass% or less is preferable in the total amount with an olefin resin.

オレフィン系樹脂としては、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、３−メチルブテン−１，４−メチルペンテン−１等のα−オレフィンの単独重合体、又はこれらα−オレフィンのランダム若しくはブロック等の共重合体、或いはこれらのα−オレフィンを主成分として含有し（好ましくは５０質量％以上）、その他のモノマーを共重合させた共重合体を挙げることができる。   As the olefin resin, single weight of α-olefin such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 3-methylbutene-1,4-methylpentene-1, etc. Or a copolymer of these α-olefins, such as random or block, or a copolymer containing these α-olefins as a main component (preferably 50% by mass or more) and copolymerized with other monomers. Can be mentioned.

他のモノマーとしては、ブタジエン、イソプレン、ジシクロペンジエン、１，４−ヘキサジエン、４−エチリデン−２−ノルボルネン、ジシクロペンタジエン等のジエン類、アクリル酸、メタクリル酸、マレイン酸、酢酸ビニル、メタクリル酸メチル、マレイン酸イミド等の不飽和酸又はその誘導体、スチレン、α−メチルスチレン等の芳香族アルケニル化合物等を挙げることができ、これらは１又は２以上組合わせて用いることができる。   Other monomers include dienes such as butadiene, isoprene, dicyclopentadiene, 1,4-hexadiene, 4-ethylidene-2-norbornene, dicyclopentadiene, acrylic acid, methacrylic acid, maleic acid, vinyl acetate, methacrylic acid. Examples thereof include unsaturated acids such as acid methyl and maleic imide or derivatives thereof, and aromatic alkenyl compounds such as styrene and α-methylstyrene, and these can be used alone or in combination.

オレフィン系樹脂は、非晶性又は結晶性のものを用いることができるが、好ましくは結晶性を示すものである。これらの中でも、ポリエチレン、ポリプロピレン、ポリ（１−ブテン）、エチレン−プロピレン共重合体、ポリ（３−メチルブテン−１）、ポリ（４−メチルペンテン−１）が好ましく、特にポリエチレン（ポリエチレンホモポリマー、エチレン単位と５モル％以下の他のオレフィン単位とのコポリマー、エチレン単位と１モル％以下のオレフィン単位を除く他の共重合可能なモノマー単位とのコポリマー）が好ましい。   The olefin resin may be amorphous or crystalline, but preferably exhibits crystallinity. Among these, polyethylene, polypropylene, poly (1-butene), ethylene-propylene copolymer, poly (3-methylbutene-1), and poly (4-methylpentene-1) are preferable, and particularly polyethylene (polyethylene homopolymer, Preferred are copolymers of ethylene units and other olefin units of 5 mol% or less, and copolymers of ethylene units and other copolymerizable monomer units excluding 1 mol% or less of olefin units.

ポリエチレンは、粉体塗装法を適用して、成形体表面に非めっき部となる被覆層を形成できるものであれば、平均分子量、密度、分子構造（直鎖構造又は分岐鎖構造）等は特に制限されるものではない。   If polyethylene can apply the powder coating method and can form the coating layer used as a non-plating part on the surface of a molded object, especially average molecular weight, density, molecular structure (straight chain structure or branched chain structure), etc. It is not limited.

本発明で用いる撥水性樹脂は、ベースとなるオレフィン系樹脂中に分散させることで、本発明の被覆剤に難めっき性を付与するための成分である。   The water-repellent resin used in the present invention is a component for imparting difficult plating properties to the coating agent of the present invention by being dispersed in the base olefin resin.

撥水性樹脂としては、フッ素樹脂、シリコーン樹脂、ポリイソブチレン等を挙げることができ、Polym Handbook 3rd Ed Wiley, Interscience (1989)及び柿内弘“塗料樹脂の化学”, 昭晃堂, p241 (1972)等に示される、ポリマーブレンド系での溶解度指数（SP値）が８以下のものが望ましい。 The water-repellent resin, fluorine resin, there may be mentioned silicone resin, polyisobutylene, Polym Handbook 3 rd Ed Wiley, Interscience (1989) and Kakinai Hiroshi "paint resin chemistry", Shokodo, P241 (1972) It is desirable that the solubility index (SP value) in the polymer blend system is 8 or less.

フッ素樹脂としては、フッ素−炭素結合を有するものであれば特に制限はなく、例えば、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリテトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、ポリフッ化ビリニデン、ポリフッ化ビニル、エチレン−フルオロエチレン交互共重合体、ポリフッ化アクリルを挙げることができる。   The fluororesin is not particularly limited as long as it has a fluorine-carbon bond. For example, polytetrafluoroethylene, polychlorotrifluoroethylene, polytetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride, polyfluoride. And vinyl fluoride, ethylene-fluoroethylene alternating copolymer, and polyfluorinated acrylic.

シリコーン樹脂としては、シリコーン樹脂の種類は、ケイ素−酸素結合を有するものであれば特に制限はなく、例えば、ジメチルポリシロキサン、ジメチルハイドロジエンポリシロキサン、ジメチルポリシロキサンが主骨格の各種重合体、ジメチルハイドロジエンポリシロキサンが主骨格の各種重合体を挙げることができる。   As the silicone resin, the type of silicone resin is not particularly limited as long as it has a silicon-oxygen bond. For example, dimethylpolysiloxane, dimethylhydropolysiloxane, various polymers having dimethylpolysiloxane as a main skeleton, dimethylpolysiloxane. Examples thereof include various polymers having a main skeleton of hydrodiene polysiloxane.

撥水性樹脂の配合量は、オレフィン系樹脂１００質量部に対して、撥水性樹脂が０．１〜１００質量部、好ましくは０．１〜５０質量部、より好ましくは０．１〜３０質量部である。   The blending amount of the water repellent resin is 0.1 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the olefin resin. It is.

本発明で用いるアンチモン、ビスマスを含む化合物は、必要に応じて配合される成分であり、クロム酸と同様に触媒毒として作用することで、成形体表面へのめっき析出防止作用を高めるように作用する成分である。アンチモン、ビスマスを含む化合物は、これらから選択される１種類のものを単独で用いることができるほか、アンチモンを含む化合物から選ばれる２種以上又はビスマスを含む化合物から選ばれる２種以上を組み合わせて用いることができる。更に、アンチモンを含む化合物及びビスマスを含む化合物から選ばれる２種以上を組み合わせて用いることができる。   The compound containing antimony and bismuth used in the present invention is a component to be blended as necessary, and acts as a catalyst poison in the same manner as chromic acid, so as to increase the effect of preventing plating deposition on the surface of the molded body. It is an ingredient to do. As the compound containing antimony and bismuth, one kind selected from them can be used alone, or two or more kinds selected from compounds containing antimony or two kinds or more selected from compounds containing bismuth are combined. Can be used. Furthermore, two or more selected from a compound containing antimony and a compound containing bismuth can be used in combination.

アンチモン化合物としては、塩化アンチモン、三酸化アンチモン、五酸化アンチモン、アンチモン酸カリウム、水酸化アンチモン、三硫化アンチモン、五硫化アンチモン等の不溶性乃至難溶性無機アンチモン化合物、酒石酸アンチモン・カリウム、グルコン酸アンチモン・ナトリウム、ピロガロール・アンチモンキレートなどの有機アンチモン化合物などを挙げることができる。   Antimony compounds include antimony chloride, antimony trioxide, antimony pentoxide, potassium antimonate, antimony hydroxide, antimony trisulfide, antimony pentasulfide, and other insoluble and hardly soluble inorganic antimony compounds, antimony potassium potassium tartrate, Examples thereof include organic antimony compounds such as sodium and pyrogallol / antimony chelate.

ビスマス化合物としては、三酸化ビスマス、五酸化ビスマス、三硫化ビスマス、硫酸ビスムチル、硝酸酸化ビスマス（III）水和物、炭酸酸化ビスマス（III）半水和物、リン酸ビスマス等の無機ビスマス化合物、クエン酸ビスマス、ピロガロール・ビスマスキレート等の有機ビスマス化合物等を挙げることができる。   As the bismuth compound, inorganic bismuth compounds such as bismuth trioxide, bismuth pentoxide, bismuth trisulfide, bismuthyl sulfate, bismuth nitrate (III) nitrate, bismuth carbonate carbonate (III) hemihydrate, bismuth phosphate, And organic bismuth compounds such as bismuth citrate and pyrogallol / bismuth chelate.

アンチモン、ビスマスを含む化合物から選ばれる１以上の配合量は、オレフィン系樹脂１００質量部に対して、アンチモン、ビスマスを含む化合物から選ばれる１以上が０．１〜１００質量部、好ましくは０．１〜５０質量部、より好ましくは０．１〜３０質量部である。   The blending amount of one or more selected from the compound containing antimony and bismuth is 0.1 to 100 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the olefin resin. 1-50 mass parts, More preferably, it is 0.1-30 mass parts.

本発明の難めっき性被覆剤は、粉体塗装法を適用することを考慮すると、平均粒径が１〜１０，０００μmが好ましく、１〜１，０００μmがより好ましく、１〜１００μmが更に好ましい。粒系が細かいほど均一な塗膜を得ることができる。   In consideration of applying the powder coating method, the difficult-plating coating material of the present invention preferably has an average particle size of 1 to 10,000 μm, more preferably 1 to 1,000 μm, and still more preferably 1 to 100 μm. As the grain system is finer, a more uniform coating can be obtained.

本発明の難めっき性被覆剤は、オレフィン系樹脂及び撥水性樹脂、更に必要に応じて配合されるアンチモン、ビスマスが均一になるように混合して得ることができ、必要に応じて粉砕、分級（粒径の調整）等をすることもできる。なお、本発明の難めっき性被覆剤は、有機溶媒は含まない。   The difficult-to-platable coating agent of the present invention can be obtained by mixing so that the olefin resin and the water repellent resin, and further, antimony and bismuth blended as necessary, are pulverized and classified as necessary. (Adjustment of particle size) can also be performed. In addition, the hard-plating coating agent of this invention does not contain an organic solvent.

＜めっきの前処理方法＞
本発明のめっきの前処理方法は、めっき工程中に無電解めっき工程を含むとき、無電解めっき工程に至る前の所望時期において、成形体表面の一部又は全部に対して、難めっき性を付与するものである。 <Pretreatment method of plating>
When the plating pretreatment method of the present invention includes an electroless plating process in the plating process, the plating pretreatment method has a difficult plating property on a part or all of the surface of the formed body at a desired time before the electroless plating process. It is given.

本発明の前処理方法は、特に特許文献１、２に記載の樹脂成形体表面をめっきする方法において、めっき対象となる樹脂成形体を保持するための金属製治具に難めっき性を付与して、前記金属製治具がめっきされないようにする場合に好適である。   The pre-treatment method of the present invention is a method for plating the surface of a resin molded body described in Patent Documents 1 and 2, particularly, by imparting difficult plating to a metal jig for holding a resin molded body to be plated. Thus, it is suitable for preventing the metal jig from being plated.

次に、図１により、本発明のめっきの前処理方法を説明する。図１は、本発明の前処理方法を適用した金属製治具及びその使用状態を示す側面図である。   Next, referring to FIG. 1, the pretreatment method for plating according to the present invention will be described. FIG. 1 is a side view showing a metal jig to which the pretreatment method of the present invention is applied and its use state.

金属製治具１０の非めっき部分（被覆部１３）に相当する部分に対して、本発明の難めっき性被覆剤を粉体塗装する。   The non-plating part (coating part 13) of the metal jig 10 is powder-coated with the difficult-to-platable coating agent of the present invention.

粉体塗装法は周知の塗装法（静電塗装法/流動浸漬法など、粉体塗装技術要覧（第3版）, （株）塗料報知新聞社 (2005)）であり、例えば、難めっき性被覆剤を熱溶融して分散したものを、金属製治具１０の斜線を付した被覆部１３に相当する表面に散布し、金属製治具１０を加熱して塗膜（被覆部１３）を形成させる方法である。金属製治具１０は、一端部側にめっき対象となる成形体２０を固定するためのクランプ部１１、１２を有しており、このクランプ部１１、１２も被覆する。   The powder coating method is a well-known coating method (electrostatic coating method / fluid dipping method, etc., powder coating technology handbook (3rd edition), Paint Newspaper Co., Ltd. (2005)). The coating material is melted and dispersed on the surface corresponding to the hatched coating portion 13 of the metal jig 10, and the metal jig 10 is heated to apply the coating film (coating portion 13). It is a method of forming. The metal jig 10 has clamp portions 11 and 12 for fixing the molded body 20 to be plated on one end side, and also covers the clamp portions 11 and 12.

塗膜（被覆部１３）の厚みは、０．１mm以上であれば、無電解めっき時において被覆部１３にめっきが析出することが防止できるが、作業時の接触により塗膜が破壊される可能性があるため厚くつけるほうが好ましい。好ましくは０．１〜１０mm、さらに好ましくは０．１〜５mmである。   If the thickness of the coating film (covering part 13) is 0.1 mm or more, it is possible to prevent plating from being deposited on the coating part 13 during electroless plating, but the coating film can be destroyed by contact during operation. It is preferable to apply a thicker layer. Preferably it is 0.1-10 mm, More preferably, it is 0.1-5 mm.

このようにして本発明のめっきの前処理方法を適用した金属製治具１０を用いて、例えば、特許文献１の実施例に記載の「メッキ樹脂成形体の製造法」のとおり、クロム酸浴によるエッチング工程を含まない、脱脂工程、触媒付与工程、第１活性化工程、第２活性化工程、ニッケルの無電解メッキ工程、酸活性化工程、及び銅の電気メッキ工程の順序で熱可塑性樹脂成形体をめっきする場合において、ニッケルの無電解メッキ工程では、以下のとおりに処理する。   In this way, using the metal jig 10 to which the plating pretreatment method of the present invention is applied, for example, as described in “Method of manufacturing a plated resin molded body” described in the example of Patent Document 1, a chromic acid bath Thermoplastic resin in the order of degreasing process, catalyst application process, first activation process, second activation process, nickel electroless plating process, acid activation process, and copper electroplating process In the case of plating the molded body, the nickel electroless plating process is performed as follows.

まず、金属製治具１０のクランプ部１１、１２により熱可塑性樹脂成形体２０を挟んで固定する。次に、この状態にて、無電解めっき浴中に浸漬する。このとき、熱可塑性樹脂成形体２０を含む被覆部１３の部分は浸漬するが、金属表面が露出した部分１４は浸漬しないようにする。   First, the thermoplastic resin molded body 20 is sandwiched and fixed by the clamp portions 11 and 12 of the metal jig 10. Next, it is immersed in an electroless plating bath in this state. At this time, the portion of the covering portion 13 including the thermoplastic resin molded body 20 is immersed, but the portion 14 where the metal surface is exposed is not immersed.

その後、無電解めっき浴から引き上げたとき、熱可塑性樹脂成形体２０の表面にはめっきが析出しているが、金属製治具１０の被覆部１３にはめっきは析出していない。このように無電解めっき後、金属製治具１０の端部を電源に接続して、銅の電気めっき工程に移行する。   Thereafter, when the electroless plating bath is pulled up, plating is deposited on the surface of the thermoplastic resin molded body 20, but plating is not deposited on the covering portion 13 of the metal jig 10. Thus, after the electroless plating, the end of the metal jig 10 is connected to a power source, and the process proceeds to a copper electroplating process.

なお、金属製治具１０の被覆部１３に割れや傷が生じた場合には、加熱炉内に入れ、オレフィン系樹脂の融点以上に加熱すれば、割れや傷は容易に修復される。このため、本発明の前処理方法を適用した金属製治具１０は、繰り返し使用することができる。一方、本発明の前処理方法を適用しない場合は、金属製治具１０の表面に析出めっきが蓄積されるため、金属製治具１０を繰り返して使用することが困難になる。   In addition, when a crack and a crack arise in the coating | coated part 13 of the metal jig | tool 10, if it puts in a heating furnace and heats more than melting | fusing point of olefin resin, a crack and a crack will be repaired easily. For this reason, the metal jig 10 to which the pretreatment method of the present invention is applied can be used repeatedly. On the other hand, when the pretreatment method of the present invention is not applied, precipitation plating accumulates on the surface of the metal jig 10, making it difficult to repeatedly use the metal jig 10.

従来法（特許文献３の発明）のように、クロム酸浴によるエッチング工程を経た場合には、クロム酸の触媒毒により、無電解めっき時にも金属製治具１０表面にはめっきは析出しないが、本発明の前処理方法を適用することにより、クロム酸浴によるエッチング工程をしない場合でも、金属製治具１０表面にはめっきを析出させないようにできる。   When an etching process using a chromic acid bath is performed as in the conventional method (invention of Patent Document 3), plating is not deposited on the surface of the metal jig 10 even during electroless plating due to the catalyst poison of chromic acid. By applying the pretreatment method of the present invention, plating can be prevented from being deposited on the surface of the metal jig 10 even when the etching process using a chromic acid bath is not performed.

また、特開平５−２３９６６０号公報及びWO９８／４５５０５（特許第３２０８４１０号公報）に記載されたダイレクトプレーティング法を適用する場合には、金属製治具表面には殆どめっきは析出しない。しかし、ダイレクトプレーティング法を実施するときの最適条件の幅が狭いため、本発明の前処理方法を適用することにより、ダイレクトプレーティング法を実施するときの最適条件の幅をより広くできる点で有利である。   In addition, when the direct plating method described in JP-A-5-239660 and WO98 / 45505 (Japanese Patent No. 3208410) is applied, the plating is hardly deposited on the surface of the metal jig. However, since the range of optimum conditions when performing the direct plating method is narrow, by applying the pretreatment method of the present invention, the range of optimum conditions when performing the direct plating method can be broadened. It is advantageous.

実施例１、２及び比較例１
表１に示す各成分（質量％表示）をＶ型タンブラーで混合後、二軸押出機（日本製鋼製，ＴＥＸ３０，シリンダー温度１６０℃）にて溶融混練し、ペレットを得た。このペレットを冷凍粉砕して難めっき性被覆剤（平均粒径１,０００μm）を調製した。この実施例１、２及び比較例１の難めっき性被覆剤を用い、図１に示す金属製治具１０に対して粉体塗装して、被覆部１３を形成させた。 Examples 1 and 2 and Comparative Example 1
Each component (mass% display) shown in Table 1 was mixed with a V-type tumbler and then melt-kneaded with a twin-screw extruder (manufactured by Nippon Steel, TEX30, cylinder temperature 160 ° C.) to obtain pellets. This pellet was frozen and pulverized to prepare a hard-to-platable coating agent (average particle size: 1,000 μm). Using the hard-to-platable coating materials of Examples 1 and 2 and Comparative Example 1, the metal jig 10 shown in FIG.

粉体塗装は、流動浸漬法を用いた。金属製冶具を350℃のオーブンにて加熱し、難めっき性被覆剤を空気によって攪拌している槽に漬けた。１分静置したのち、200℃のオーブンで５分加熱し、表面を溶融させて平滑にして、最後に水没させて冷却した。   For powder coating, a fluidized immersion method was used. The metal jig was heated in an oven at 350 ° C., and the hard-to-platable coating material was immersed in a tank stirred with air. After leaving still for 1 minute, it heated for 5 minutes in 200 degreeC oven, the surface was melt | dissolved and smoothed, and it was finally submerged and cooled.

下記組成からなる成分をＶ型タンブラーで混合後、二軸押出機（日本製鋼製，ＴＥＸ３０，シリンダー温度２３０℃）にて溶融混練し、ペレットを得た。次に、射出成形機（シリンダー温度２４０℃、金型温度６０℃）により１００×５０×３ｍｍの成形体を得た。この熱可塑性樹脂成形体と、実施例１、２又は比較例１の難めっき性被覆剤で処理した図１に示す金属製治具１０を用い、下記の各工程でめっき樹脂成形体を製造した。   Components having the following composition were mixed with a V-type tumbler, and then melt-kneaded with a twin-screw extruder (manufactured by Nippon Steel, TEX30, cylinder temperature 230 ° C.) to obtain pellets. Next, a molded body of 100 × 50 × 3 mm was obtained by an injection molding machine (cylinder temperature 240 ° C., mold temperature 60 ° C.). Using this thermoplastic resin molded body and the metal jig 10 shown in FIG. 1 treated with the hard-to-platable coating material of Examples 1 and 2 or Comparative Example 1, a plated resin molded body was manufactured in the following steps. .

（熱可塑性樹脂成形体の成分）
ポリアミド（ポリアミド6，宇部興産株式会社製，UBEナイロン6 1013B，吸水率1.8％）樹脂成分の合計量中６０質量％
ＡＢＳ樹脂（スチレン量４５質量％、アクリロニトリル１５質量％、ポリブタジエン系ゴム４０質量％，吸水率0.2％）樹脂成分の合計量中３０質量％
酸変性ＡＢＳ樹脂（スチレン量４２質量％、アクリロニトリル１６質量％、ゴム量４０質量％、メタクリル酸２重量％，吸水率0.2％）樹脂成分の合計量中１０質量％
ジペンタエリスリトール，樹脂成分１００質量部に対して１０質量部
（めっき工程）
（１） 脱脂工程
成形体を、エースクリンＡ−２２０（奥野製薬工業（株）製）５０ｇ／Ｌ水溶液（液温４０℃）に２０分浸漬した。 (Components of molded thermoplastic resin)
Polyamide (Polyamide 6, Ube Industries, UBE nylon 6 1013B, water absorption 1.8%) 60% by mass in the total amount of resin components
ABS resin (styrene content 45% by mass, acrylonitrile 15% by mass, polybutadiene rubber 40% by mass, water absorption 0.2%) 30% by mass in the total amount of resin components
Acid-modified ABS resin (styrene content 42% by weight, acrylonitrile 16% by weight, rubber amount 40% by weight, methacrylic acid 2% by weight, water absorption 0.2%) 10% by weight in the total amount of resin components
Dipentaerythritol, 10 parts by mass per 100 parts by mass of resin component (plating process)
(1) Degreasing process The molded body was immersed in an aceclin A-220 (Okuno Pharmaceutical Co., Ltd.) 50 g / L aqueous solution (liquid temperature 40 ° C.) for 20 minutes.

（２） 酸による接触処理工程
１．０規定の塩酸１００ｍｌ（液温４０℃）中に５分間浸漬した。 (2) Step of contact treatment with acid The substrate was immersed in 100 ml of 1.0 N hydrochloric acid (liquid temperature 40 ° C.) for 5 minutes.

（３） 触媒付与工程
３５質量％塩酸１５０ｍｌ／Ｌと、キャタリストＣ（奥野製薬工業（株）製）４０ｍｌ／Ｌ水溶液との混合水溶液（液温２５℃）中に３分間浸漬した。 (3) Catalyst application process It immersed for 3 minutes in the mixed aqueous solution (liquid temperature of 25 degreeC) of 35 mass% hydrochloric acid 150ml / L and catalyst C (Okuno Pharmaceutical Co., Ltd. product) 40ml / L aqueous solution.

（４） 第１活性化工程
成形体を、９８質量％硫酸１００ｍｌ／Ｌ水溶液（液温４０℃）中に３分間浸漬した。 (4) 1st activation process The molded object was immersed in 98 mass% sulfuric acid 100ml / L aqueous solution (liquid temperature of 40 degreeC) for 3 minutes.

（５） 第２活性化工程
成形体を、水酸化ナトリウム１５ｇ／Ｌ水溶液（液温４０℃）中に２分間浸漬した。 (5) 2nd activation process The molded object was immersed for 2 minutes in the sodium hydroxide 15g / L aqueous solution (liquid temperature of 40 degreeC).

（６） ニッケルの無電解めっき工程
成形体を実施例１、２又は比較例１の難めっき性被覆剤で処理した金属製治具１０で挟んで固定して、成形体と共に被覆部１３の部分を、化学ニッケルＨＲ−ＴＡ（奥野製薬工業（株）製）１５０ｍｌ／Ｌと、化学ニッケルＨＲ−ＴＢ（奥野製薬工業（株）製）１５０ｍｌ／Ｌの混合水溶液（液温４０℃）に５分間浸漬した。 (6) Nickel electroless plating step The molded body is sandwiched and fixed by the metal jig 10 treated with the hard-to-platable coating material of Examples 1 and 2 or Comparative Example 1, and the part of the covering portion 13 together with the molded body For 5 minutes in a mixed aqueous solution (liquid temperature 40 ° C.) of 150 ml / L of chemical nickel HR-TA (Okuno Pharmaceutical Co., Ltd.) and 150 ml / L of chemical nickel HR-TB (Okuno Pharmaceutical Co., Ltd.) Soaked.

（７） 酸活性化工程
成形体を、トップサン（奥野製薬工業（株）製）１００ｇ／Ｌ水溶液（液温２５℃）に１分間浸漬した。 (7) Acid activation process The molded body was immersed in 100 g / L aqueous solution (liquid temperature 25 ° C.) of Topsun (Okuno Pharmaceutical Co., Ltd.) for 1 minute.

（８） 銅の電気めっき工程
成形体を、実施例１と同じめっき浴（液温２５℃）に浸漬して、１２０分間電気めっきを行った。 (8) Copper electroplating step The molded body was immersed in the same plating bath (liquid temperature 25 ° C.) as in Example 1 and electroplated for 120 minutes.

Figure 2006316297
Figure 2006316297

得られためっき樹脂成形体の密着強度の最高値は、いずれも１００ｋＰａであり、外観も平滑で美しいものであった。しかし、ニッケルの無電解めっき工程後においても、実施例１、２の被覆剤で処理した金属製治具１０の被覆部１３表面にはニッケルめっきは析出していなかったが、比較例１の被覆剤で処理した金属製治具１０の被覆部１３表面にはニッケルめっきが析出していた。   The maximum value of the adhesion strength of the obtained plated resin molding was 100 kPa, and the appearance was smooth and beautiful. However, even after the nickel electroless plating step, nickel plating was not deposited on the surface of the coating portion 13 of the metal jig 10 treated with the coating agent of Examples 1 and 2, but the coating of Comparative Example 1 Nickel plating was deposited on the surface of the covering portion 13 of the metal jig 10 treated with the agent.

本発明のめっきの前処理方法の説明図。Explanatory drawing of the pre-processing method of the plating of this invention.

Claims (5)

オレフィン系樹脂１００質量部に対して、撥水性樹脂を０．１〜１００質量部及び必要に応じてアンチモン、ビスマスを含む化合物から選ばれる１以上を０．１〜１００質量部含有する難めっき性被覆剤。   Difficult plating property containing 0.1 to 100 parts by mass of water repellent resin with respect to 100 parts by mass of olefin resin and 0.1 to 100 parts by mass of one or more compounds selected from compounds containing antimony and bismuth as required. Coating agent. オレフィン系樹脂がポリエチレンであり、撥水性樹脂がフッ素樹脂及び／又はシリコーン樹脂である請求項１記載の難めっき性被覆剤。   The hard-to-platable coating agent according to claim 1, wherein the olefin resin is polyethylene and the water-repellent resin is a fluororesin and / or a silicone resin. 成形体表面の非めっき部分に対して、請求項１又は２記載の難めっき性被覆剤を粉体塗装する、めっきの前処理方法。   A pretreatment method for plating, in which a non-plating coating agent according to claim 1 or 2 is powder-coated on a non-plated portion on the surface of a molded body. めっき対象となる樹脂成形体を保持するための金属製治具に請求項１又は２記載の難めっき性被覆剤を粉体塗装することにより難めっき性を付与して、前記金属製治具がめっきされないようにするめっきの前処理方法。   A metal jig for holding a resin molded body to be plated is provided with a difficult plating property by powder coating the difficult-plating coating agent according to claim 1 or 2, and the metal jig Pre-treatment method for plating that prevents plating. めっきの前処理方法が、重金属を含む酸による接触処理工程を含まないことを特徴とする請求項４記載のめっきの前処理方法。


The plating pretreatment method according to claim 4, wherein the plating pretreatment method does not include a contact treatment step with an acid containing a heavy metal.


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JP2009030151A (en) * 2007-07-04 2009-02-12 Okuno Chem Ind Co Ltd Plating holder used for plating of resin molded article
JP2015170713A (en) * 2014-03-06 2015-09-28 富士通株式会社 Method for manufacturing wiring structure, wiring structure, and electronic equipment using the same

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JP2009030151A (en) * 2007-07-04 2009-02-12 Okuno Chem Ind Co Ltd Plating holder used for plating of resin molded article
JP2015170713A (en) * 2014-03-06 2015-09-28 富士通株式会社 Method for manufacturing wiring structure, wiring structure, and electronic equipment using the same

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