JP2015190056A - Electroless plating method and electroless plating - Google Patents
Electroless plating method and electroless plating Download PDFInfo
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Abstract
【課題】めっき前処理に伴う繊維材料の強度低下を回避しつつ、被めっき物がポリアリレート繊維、パラ系アラミド繊維、ＰＯＢ繊維等の高強度繊維であっても、均一なめっき析出が可能であって、密着性に優れためっき皮膜を形成することができる技術を提供すること。【解決手段】Ｐｄ系触媒担持工程と、Ｐｄ系触媒活性化工程と、無電解めっき工程を有する無電解めっき方法において、前記Ｐｄ系触媒担持工程に先立って、表面が負に帯電した被めっき物を、めっき前処理液に浸漬させるめっき前処理液浸漬工程を有し、該めっき前処理液として、水溶性カチオン系ポリマーを水に溶解させて得た、アルカリ性のカチオン系ポリマー水溶液であって、非共有電子対を有する元素を含有するものを用いる。【選択図】図２An object of the present invention is to enable uniform plating deposition even when the object to be plated is a high strength fiber such as polyarylate fiber, para-aramid fiber, POB fiber, etc. And providing the technique which can form the plating film excellent in adhesiveness. In an electroless plating method including a Pd-based catalyst supporting step, a Pd-based catalyst activating step, and an electroless plating step, the object to be plated whose surface is negatively charged prior to the Pd-based catalyst supporting step. An aqueous solution of an alkaline cationic polymer obtained by dissolving a water-soluble cationic polymer in water as the plating pretreatment liquid. A material containing an element having an unshared electron pair is used. [Selection] Figure 2
Description
本発明は、無電解めっき方法および無電解めっき物に関するものである。 The present invention relates to an electroless plating method and an electroless plated product.
繊維材料の表面にめっきを施す技術として、繊維材料に「脱脂→エッチング→中和および湿潤化→触媒付与→触媒活性化」の各工程からなる前処理を施した後、無電解めっき処理を行う方法が知られている（例えば、特許文献１）。 As a technique for plating the surface of the fiber material, the fiber material is subjected to a pretreatment consisting of the steps of “degreasing → etching → neutralization and wetting → catalyst application → catalyst activation”, and then electroless plating is performed. A method is known (for example, Patent Document 1).
しかし、上記技術では、エッチング（被めっき物の表面に、物理的または化学的な手段で微細な凹凸を形成する処理）により、繊維材料の強度が低下する問題があった。 However, the above-described technique has a problem that the strength of the fiber material is reduced by etching (treatment for forming fine irregularities on the surface of the object to be plated by physical or chemical means).
上記問題（繊維材料の強度低下）を回避しつつ、めっき皮膜と被めっき物との密着性を向上させる技術として、めっきの前処理として、エッチングに変えて、ラジカル処理を施す方法が開示されている（特許文献２）。 As a technique for improving the adhesion between the plating film and the object to be plated while avoiding the above problems (decrease in strength of the fiber material), a method of performing radical treatment instead of etching as a pretreatment for plating is disclosed. (Patent Document 2).
しかし、特許文献２の技術では、特に、ポリアリレート繊維、パラ系アラミド繊維、ＰＯＢ繊維等の高強度繊維を被めっき物とする場合、めっき析出が不均一となる問題や、めっき皮膜と被めっき物との密着性が悪いという問題があった。 However, in the technique of Patent Document 2, in particular, when high strength fibers such as polyarylate fibers, para-aramid fibers, and POB fibers are to be plated, there is a problem that plating deposition is not uniform, plating film and plating There was a problem of poor adhesion to objects.
本発明の目的は前記の問題を解決し、めっき前処理に伴う繊維材料の強度低下を回避しつつ、被めっき物がポリアリレート繊維、パラ系アラミド繊維、ＰＯＢ繊維等の高強度繊維であっても、均一なめっき析出が可能であって、密着性に優れためっき皮膜を形成することができる技術を提供することである。 The object of the present invention is to solve the above-mentioned problems, while avoiding a decrease in the strength of the fiber material due to the pretreatment of plating, while the object to be plated is a high-strength fiber such as polyarylate fiber, para-aramid fiber, POB fiber, etc. Furthermore, it is to provide a technique capable of forming a plating film which is capable of uniform plating deposition and has excellent adhesion.
上記課題を解決するためになされた請求項１記載の発明は、Ｐｄ系触媒担持工程と、Ｐｄ系触媒活性化工程と、無電解めっき工程を有する無電解めっき方法であって、前記Ｐｄ系触媒担持工程に先立って、表面が負に帯電した被めっき物を、めっき前処理液に浸漬させるめっき前処理液浸漬工程を有し、該めっき前処理液として、水溶性カチオン系ポリマーを水に溶解させて得た、アルカリ性のカチオン系ポリマー水溶液であって、非共有電子対を有する元素を含有するものを用いることを特徴とするものである。 The invention according to claim 1, which has been made to solve the above problems, is an electroless plating method comprising a Pd-based catalyst supporting step, a Pd-based catalyst activation step, and an electroless plating step, wherein the Pd-based catalyst Prior to the supporting step, the substrate has a plating pretreatment solution dipping step in which a negatively charged surface is immersed in a pretreatment solution for plating, and a water-soluble cationic polymer is dissolved in water as the pretreatment solution for plating. An alkaline cationic polymer aqueous solution obtained by using an aqueous solution containing an element having an unshared electron pair is used.
請求項２記載の発明は、請求項１記載の無電解めっき方法において、前記カチオン系ポリマー水溶液が、水溶性ポリアミン化合物を含有するポリアミン水溶液であることを特徴とすることを特徴とするものである。 The invention according to claim 2 is characterized in that, in the electroless plating method according to claim 1, the cationic polymer aqueous solution is a polyamine aqueous solution containing a water-soluble polyamine compound. .
請求項３記載の発明は、請求項２記載の無電解めっき方法において、前記水溶性ポリアミン化合物が、分子量３０００〜１５００００の水溶性ポリアミン化合物であることを特徴とするものである。 A third aspect of the invention is the electroless plating method according to the second aspect, wherein the water-soluble polyamine compound is a water-soluble polyamine compound having a molecular weight of 3000 to 150,000.
請求項４記載の発明は、請求項３記載の無電解めっき方法において、前記分子量３０００〜１５００００の水溶性ポリアミン化合物が、ポリアリルアミンであることを特徴とするものである。 The invention according to claim 4 is the electroless plating method according to claim 3, wherein the water-soluble polyamine compound having a molecular weight of 3000 to 150,000 is polyallylamine.
請求項５記載の発明は、請求項４記載の無電解めっき方法において、前記ポリアリルアミンが、アリルアミン塩酸塩重合体、アリルアミン重合体、アリルアミンアミド硫酸塩重合体、アリルアミン塩酸塩ジアリルアミン塩酸塩共重合体、ジアリルアミン塩酸塩ジアルキルジアリルアミン塩化物のうち、少なくとも何れかであることを特徴とするものである。 The invention according to claim 5 is the electroless plating method according to claim 4, wherein the polyallylamine is an allylamine hydrochloride polymer, an allylamine polymer, an allylamine amide sulfate polymer, an allylamine hydrochloride diallylamine hydrochloride copolymer. , Diallylamine hydrochloride and dialkyl diallylamine chloride, at least one of them.
請求項６記載の発明は、請求項１〜５の何れかに記載の無電解めっき方法において、前記浸漬は、めっき前処理液を６０〜８０℃に維持して、５〜１５分間行うことを特徴とするものである。 The invention according to claim 6 is the electroless plating method according to any one of claims 1 to 5, wherein the immersion is performed for 5 to 15 minutes while maintaining the plating pretreatment liquid at 60 to 80 ° C. It is a feature.
請求項７記載の発明は、請求項１〜６の何れかに記載の無電解めっき方法において、前記めっき前処理液浸漬工程に先立って、被めっき物の表面をプラズマ処理するプラズマ処理工程を有することを特徴とするものである。 Invention of Claim 7 has a plasma treatment process which plasma-treats the surface of a to-be-plated object in the electroless-plating method in any one of Claims 1-6 prior to the said plating pretreatment liquid immersion process. It is characterized by this.
請求項８記載の発明は、請求項７記載の無電解めっき方法において、前記プラズマ処理により、被めっき物の表面をアミノ化することを特徴とするものである。 The invention according to claim 8 is the electroless plating method according to claim 7, wherein the surface of the object to be plated is aminated by the plasma treatment.
請求項９記載の発明は、請求項７記載の無電解めっき方法において、前記プラズマ処理により、被めっき物の表面を酸化することを特徴とするものである。 A ninth aspect of the invention is characterized in that, in the electroless plating method of the seventh aspect, the surface of the object to be plated is oxidized by the plasma treatment.
請求項１０記載の無電解めっき物は、請求項１記載の方法により製造されたことを特徴とするものである。 The electroless plated product according to claim 10 is produced by the method according to claim 1.
本発明では、Ｐｄ系触媒担持工程と、Ｐｄ系触媒活性化工程と、無電解めっき工程を有する無電解めっき方法において、前記Ｐｄ系触媒担持工程に先立って、表面が負に帯電した被めっき物を、めっき前処理液に浸漬させるめっき前処理液浸漬工程を有し、該めっき前処理液として、水溶性カチオン系ポリマーを水に溶解させて得た、アルカリ性のカチオン系ポリマー水溶液であって、非共有電子対を有する元素を含有するものを用いる構成を採用している。 In the present invention, in an electroless plating method including a Pd-based catalyst supporting step, a Pd-based catalyst activating step, and an electroless plating step, the object to be plated whose surface is negatively charged prior to the Pd-based catalyst supporting step. An aqueous solution of an alkaline cationic polymer obtained by dissolving a water-soluble cationic polymer in water as the plating pretreatment liquid. A configuration using an element containing an element having an unshared electron pair is employed.
カチオン系ポリマー水溶液中は、構造中にカチオンを多く有するため、表面が負に帯電した被めっき物に対し、クーロン力による強力な吸着力を発揮し、かつ、高分子による皮膜効果も加味することができる。このため、めっき前処理液浸漬工程を経た被めっき物は、表面にポリカチオンが強固に吸着した構造を有するものとなる。 The cationic polymer aqueous solution has a large number of cations in the structure, so it exerts a strong adsorptive force due to Coulomb force on the negatively charged surface of the object and also takes into account the film effect of the polymer. Can do. For this reason, the to-be-plated object which passed through the plating pretreatment liquid immersion process has a structure in which polycations are firmly adsorbed on the surface.
このカチオン系ポリマーは、水溶性カチオン系ポリマーを水に溶解させ、かつ、ｐＨをアルカリ領域に調整して得られたものであり、「非共有電子対を有する元素」を有するものである。このため、めっき前処理液浸漬工程を経た被めっき物の表面には、「非共有電子対を有する元素」が多数存在することとなる。 This cationic polymer is obtained by dissolving a water-soluble cationic polymer in water and adjusting the pH to an alkaline region, and has an “element having an unshared electron pair”. For this reason, many “elements having unshared electron pairs” exist on the surface of the object to be plated that has undergone the plating pretreatment liquid immersion step.
本発明では、被めっき物の表面において、この「非共有電子対を有する元素」が、電子供与体（塩基）として働き、Ｐｄ系触媒担持工程で使用されるＰｄカチオン錯体（酸）と電荷移動型錯体を形成するため、被めっき物の表面に、Ｐｄ系触媒を均一かつ強固に結び付けることができる。これにより、均一なめっき析出および密着性に優れためっき皮膜の形成を実現することができる。 In the present invention, on the surface of the object to be plated, this “element having an unshared electron pair” acts as an electron donor (base), and the Pd cation complex (acid) used in the Pd-based catalyst supporting step and charge transfer. Since the type complex is formed, the Pd-based catalyst can be uniformly and firmly bound to the surface of the object to be plated. Thereby, formation of the plating film excellent in uniform plating precipitation and adhesiveness is realizable.
請求項４記載の発明のように、記分子量３０００〜１５００００の高分子量のポリアミン化合物を使用することにより、特に被めっき物として、繊維材料を使用する場合、絡み付き、均一なめっき析出および密着性に優れためっき皮膜の形成を実現することができる。 By using a high molecular weight polyamine compound having a molecular weight of 3000 to 150,000 as in the invention described in claim 4, particularly when a fiber material is used as an object to be plated, entanglement, uniform plating precipitation and adhesion are achieved. An excellent plating film can be formed.
以下に本発明の好ましい実施形態を示す。
本実施形態の無電解めっき方法は、図１に示すように、湯洗工程（工程１）と、乾燥工程（工程２）と、プラズマ処理工程（工程３）と、めっき前処理液浸漬工程（工程４）と、Ｐｄ系触媒担持工程（工程５）と、第１の水洗工程（工程６）と、Ｐｄ系触媒活性化工程（工程７）と、第２の水洗工程（工程８）と、無電解めっき工程（工程９）と、第３の水洗工程（工程１０）と乾燥工程（工程１１）の各工程で構成されている。以下、各工程について説明する。
Preferred embodiments of the present invention are shown below.
As shown in FIG. 1, the electroless plating method of this embodiment includes a hot water washing step (step 1), a drying step (step 2), a plasma treatment step (step 3), and a plating pretreatment liquid immersion step ( Step 4), Pd-based catalyst supporting step (Step 5), first water washing step (Step 6), Pd-based catalyst activation step (Step 7), second water washing step (Step 8), It comprises an electroless plating step (step 9), a third water washing step (step 10), and a drying step (step 11). Hereinafter, each step will be described.
（工程１：湯洗工程）
湯洗工程では、被めっき物の表面に付着した油剤、汚れ等の除去が行われる。なお、油剤、汚れが付着していない場合には、湯洗工程は省略することができる。
(Process 1: Hot water washing process)
In the hot water washing process, oil agent, dirt, and the like attached to the surface of the object to be plated are removed. In addition, when the oil agent and dirt are not attached, the hot water washing step can be omitted.
（工程２：乾燥工程）
乾燥工程では、湯洗工程を経た被めっき物の乾燥が行われる。乾燥方法は特に限定されず、例えば、温風乾燥等、任意の方法を採用することができる。
(Process 2: Drying process)
In the drying process, the object to be plated after the hot water washing process is dried. The drying method is not particularly limited, and any method such as warm air drying can be employed.
（工程３：プラズマ処理工程）
プラズマ処理工程では、公知の「プラズマ処理による表面改質」手法を用いて、被めっき物表面にプラズマを照射して、被めっき物表面をアミノ化あるいは酸化させる処理を行う。具体的手法は特に限定されず、めっき処理に先立って、被めっき物の表面にプラズマ処理を施して、被めっき物とめっき金属との密着性を向上させるための公知の手法を適宜採用することができる。なお、本発明においてプラズマ処理工程は、省略することもできる。
(Process 3: Plasma treatment process)
In the plasma treatment step, a known “surface modification by plasma treatment” technique is used to irradiate the surface of the object with plasma and aminate or oxidize the surface of the object. The specific method is not particularly limited, and a known method for improving the adhesion between the object to be plated and the plating metal by applying plasma treatment to the surface of the object to be plated prior to the plating process is appropriately adopted. Can do. In the present invention, the plasma treatment process can be omitted.
（工程４：めっき前処理液浸漬工程）
めっき前処理液浸漬工程では、表面が負に帯電した被めっき物を、めっき前処理液に浸漬させる処理を行う。なお、被めっき物の表面が正に帯電している場合、溶液浸漬処理等で負に帯電させることができる。ここで、めっき前処理液としては、水溶性カチオン系ポリマーを水に溶解させて得た、カチオン系ポリマー水溶液が使用される。水溶性カチオン系ポリマーの種類により、水溶液がアルカリを示す場合と酸性を示す場合の、双方のケースがあるが、このうち、水溶性カチオン系ポリマーを水に溶解させた状態で、水溶液が酸性を示すものは、アルカリの添加により、水溶液をアルカリ性に調整して使用される。なお、このめっき前処理液のｐＨは、ｐＨ１１以上とすることが望ましく、水溶性カチオン系ポリマーを水に溶解させた状態で、水溶液がアルカリを示すものも、そのｐＨが１１未満の場合には、アルカリの添加によるｐＨ調整を行うことが望ましい。浸漬は、めっき前処理液を６０〜８０℃に維持して、５〜１５分間行うことが好ましい。なお、ｐＨを高くするほど、浸漬時間は短くすることができる。また、めっき前処理液の温度を高くするほど、浸漬時間は短くすることができる。
(Process 4: Plating pretreatment liquid immersion process)
In the plating pretreatment liquid dipping step, a treatment for immersing the object to be plated whose surface is negatively charged in the pretreatment for plating solution is performed. In addition, when the surface of the object to be plated is positively charged, it can be negatively charged by a solution dipping process or the like. Here, as the plating pretreatment liquid, a cationic polymer aqueous solution obtained by dissolving a water-soluble cationic polymer in water is used. Depending on the type of water-soluble cationic polymer, there are both cases where the aqueous solution exhibits alkali and acidic properties. Among these, the aqueous solution is acidic with the water-soluble cationic polymer dissolved in water. What is shown is used by adjusting the aqueous solution to alkaline by the addition of alkali. In addition, it is desirable that the pH of this plating pretreatment solution is pH 11 or higher. In the case where the aqueous solution shows alkali in a state in which the water-soluble cationic polymer is dissolved in water, It is desirable to adjust the pH by adding an alkali. The dipping is preferably performed for 5 to 15 minutes while maintaining the plating pretreatment liquid at 60 to 80 ° C. In addition, immersion time can be shortened, so that pH is made high. Moreover, immersion time can be shortened, so that the temperature of a plating pretreatment liquid is made high.
カチオン系ポリマー水溶液中は、構造中にカチオンを多く有するため、図２に示すように、表面が負に帯電した被めっき物に対し、クーロン力による強力な吸着力を発揮し、かつ、高分子による皮膜効果も加味することができる。このため、めっき前処理液浸漬工程を経た被めっき物は、表面にカチオン系ポリマーが強固に吸着した構造を有するものとなる。このカチオン系ポリマー水溶液は、水溶性カチオン系ポリマーを水に溶解させて得られたものであり、非共有電子対を有する元素（たとえばＮ）を含有するものである。このため、めっき前処理液浸漬工程を経た被めっき物の表面には、「非共有電子対を有する元素（たとえばＮ）」が多数存在することとなる。なお、プラズマ処理工程で、被めっき物表面にＣＯＯＨ基を導入した場合、ＣＯＯＨ基は、前記のアルカリ性下において、ＣＯＯ−として存在するため、カチオン系ポリマーの吸着を更に強固にし、後述のＰｄ系触媒活性化工程で還元析出したＰｄ触媒の保持性向上に貢献すると考えられる。 Since the cationic polymer aqueous solution has a large number of cations in the structure, as shown in FIG. 2, it exerts a strong adsorption force due to the Coulomb force to the object to be negatively charged on the surface, and the polymer The film effect by can also be taken into consideration. For this reason, the to-be-plated object which passed through the plating pretreatment liquid immersion process has a structure in which the cationic polymer is firmly adsorbed on the surface. This aqueous cationic polymer solution is obtained by dissolving a water-soluble cationic polymer in water, and contains an element having an unshared electron pair (for example, N). For this reason, many “elements having unshared electron pairs (for example, N)” exist on the surface of the object to be plated that has undergone the plating pretreatment liquid immersion step. In addition, when COOH groups are introduced into the surface of the object to be plated in the plasma treatment step, COOH groups exist as COO − under the above alkalinity. It is thought that it contributes to the improvement of the retention property of the Pd catalyst reduced and precipitated in the catalyst activation step.
被めっき物の表面において、この「非共有電子対を有する元素（たとえばＮ）」が、電子供与体（塩基）として働き、次のＰｄ系触媒担持工程（工程４）で使用されるＰｄカチオン錯体（酸）と電荷移動型錯体を形成するため、被めっき物の表面に、Ｐｄ系触媒を均一かつ強固に結び付けることができる。本発明では、これにより、均一なめっき析出および密着性に優れためっき皮膜の形成を実現している。 This “element having an unshared electron pair (for example, N)” acts as an electron donor (base) on the surface of the object to be plated, and is used in the next Pd-based catalyst supporting step (step 4). Since the charge transfer complex is formed with the (acid), the Pd-based catalyst can be uniformly and firmly bound to the surface of the object to be plated. In the present invention, this makes it possible to form a plating film excellent in uniform plating deposition and adhesion.
カチオン系ポリマー水溶液としては、分子量３０００〜１５００００の水溶性ポリアミン化合物を水に溶解させたポリアミン水溶液を使用することが好ましい。分子量３０００未満では、前記のクーロン力によって被めっき物を吸着する力が不十分となり好ましくない。また、分子量１５００００超では、立体障害が生じ、これにより、被めっき物の吸着能力が低下する他、水溶液の粘性も高くなるため、好ましくない。 As the cationic polymer aqueous solution, it is preferable to use a polyamine aqueous solution in which a water-soluble polyamine compound having a molecular weight of 3000 to 150,000 is dissolved in water. When the molecular weight is less than 3000, the force for adsorbing the object to be plated by the Coulomb force becomes insufficient. On the other hand, if the molecular weight exceeds 150,000, steric hindrance occurs, which reduces the adsorption ability of the object to be plated and increases the viscosity of the aqueous solution, which is not preferable.
分子量３０００〜１５００００の水溶性ポリアミン化合物としては、ポリアリルアミンを使用することが好ましく、例えば、アリルアミン塩酸塩重合体、アリルアミン重合体、アリルアミンアミド硫酸塩重合体、アリルアミン塩酸塩ジアリルアミン塩酸塩共重合体、ジアリルアミン塩酸塩ジアルキルジアリルアミン塩化物等から任意のものを選択して使用することができる。特に、アリルアミン（ａｌｌｙｌａｍｉｎｅ,ＣＨ２＝ＣＨＣＨ２ＮＨ２ ）系の水溶性カチオン系ポリマーで、分子中に、アルカリ性下で安定なポリアミン構造を有し、かつ１級或いは２級アミン構造を併せ持つものは、アルカリ性下でカチオン構造をとるＰｄ錯イオンの捕捉、および、還元されたＰｄ触媒の保持に有効である。 As the water-soluble polyamine compound having a molecular weight of 3000 to 150,000, polyallylamine is preferably used. For example, allylamine hydrochloride polymer, allylamine polymer, allylamine amide sulfate polymer, allylamine hydrochloride diallylamine hydrochloride copolymer, Any one of diallylamine hydrochloride dialkyldiallylamine chloride and the like can be selected and used. In particular, allylamine (CH 2 ═CHCH 2 NH 2 ) -based water-soluble cationic polymer having a polyamine structure that is stable under alkali and having a primary or secondary amine structure in the molecule. It is effective for trapping Pd complex ions having a cation structure under alkalinity and holding a reduced Pd catalyst.
（工程５：Ｐｄ系触媒担持工程）
Ｐｄ系触媒担持工程では、公知の手法を用いて、Ｐｄ系触媒を被めっき物の表面に吸着させる処理が行われる。本実施形態では、パラジウム錯体を含有する触媒溶液を４０℃に維持して、ここに、被めっき物を５分浸漬する処理を行っている。
(Step 5: Pd-based catalyst supporting step)
In the Pd-based catalyst supporting step, a process for adsorbing the Pd-based catalyst on the surface of the object to be plated is performed using a known method. In the present embodiment, a catalyst solution containing a palladium complex is maintained at 40 ° C., and the object to be plated is immersed in this for 5 minutes.
（工程６：第１の水洗工程）
第１の水洗工程では、Ｐｄ系触媒担持工程を経た被めっき物の水洗が行われる。水洗により余分な付着物が除去される。水洗方法は特に限定されず、例えば、流水槽をくぐらせる等任意の方法を採用することができる。
(Process 6: 1st water washing process)
In the first water washing step, the object to be plated after the Pd-based catalyst supporting step is washed with water. Excess deposits are removed by washing with water. The washing method is not particularly limited, and any method such as passing through a running water tank can be employed.
（工程７：Ｐｄ系触媒活性化工程）
Ｐｄ系触媒活性化工程では、前記のＰｄ系触媒担持工程で被めっき物の表面に吸着させたＰｄ系触媒を、公知の手法を用いて活性化させる処理が行われる。本実施形態では、ジメチルアミンボランを還元剤として含有する触媒活性化溶液を２５℃に維持して、ここに、被めっき物を５分浸漬する処理を行っている。
(Step 7: Pd catalyst activation step)
In the Pd-based catalyst activation step, the Pd-based catalyst adsorbed on the surface of the object to be plated in the Pd-based catalyst supporting step is activated using a known method. In the present embodiment, a catalyst activation solution containing dimethylamine borane as a reducing agent is maintained at 25 ° C., and the object to be plated is immersed in this for 5 minutes.
（工程８：第２の水洗工程）
第２の水洗工程では、Ｐｄ系触媒活性化工程を経た被めっき物の水洗が行われる。水洗により余分な付着物が除去される。水洗方法は特に限定されず、例えば、流水槽をくぐらせる等任意の方法を採用することができる。
(Step 8: Second water washing step)
In the second water washing step, the object to be plated that has undergone the Pd-based catalyst activation step is washed with water. Excess deposits are removed by washing with water. The washing method is not particularly limited, and any method such as passing through a running water tank can be employed.
（工程９：無電解めっき工程）
無電解めっき工程では、通常の無電解めっき手法に従って、被めっき物をめっき液中に浸漬させる処理を行う。被めっき物をめっき液中に浸漬させると、上記工程で被めっき物に担持させたＰｄ触媒を核としてめっき皮膜が形成される。具体的には、めっき液に含まれる還元剤がＰｄ表面で酸化されるときに放出される電子により、めっき液に含まれる金属イオンを還元して、その金属を被めっき物表面に析出させることにより、めっき皮膜が形成される。なお、本実施形態では、無電解銅めっきを行っているが、その他、無電解ニッケルめっきや無電解銀めっき等、任意の無電解めっきとすることができる。
(Process 9: Electroless plating process)
In the electroless plating step, a treatment for immersing the object to be plated in the plating solution is performed according to a normal electroless plating method. When the object to be plated is immersed in the plating solution, a plating film is formed using the Pd catalyst supported on the object to be plated in the above process as a nucleus. Specifically, metal ions contained in the plating solution are reduced by electrons released when the reducing agent contained in the plating solution is oxidized on the Pd surface, and the metal is deposited on the surface of the object to be plated. Thus, a plating film is formed. In this embodiment, electroless copper plating is performed, but any other electroless plating such as electroless nickel plating or electroless silver plating can be used.
（工程１０：第３の水洗工程）
第３の水洗工程では、無電解めっき工程を経た被めっき物の水洗が行われる。水洗により余分な付着物が除去される。水洗方法は特に限定されず、例えば、流水槽をくぐらせる等、任意の方法を採用することができる。
(Step 10: third water washing step)
In the third water washing step, the object to be plated after the electroless plating step is washed with water. Excess deposits are removed by washing with water. The washing method is not particularly limited, and any method such as passing through a running water tank can be employed.
（工程１１：乾燥工程）
乾燥工程では、第３の水洗工程を経た被めっき物の乾燥が行われる。乾燥方法は特に限定されず、例えば、温風乾燥等、任意の方法を採用することができる。
(Step 11: Drying step)
In the drying step, the object to be plated that has undergone the third water washing step is dried. The drying method is not particularly limited, and any method such as warm air drying can be employed.
（実施例１〜２、比較例１〜２）
被めっき物として、ポリアリレート繊維（クラレ製ベクトラン、１６７０ｄｔｅｘ、油剤あり）を使用し、（工程１：湯洗工程）、（工程２：乾燥工程）、（工程３：プラズマ処理工程）、（工程４：めっき前処理液浸漬工程）、の各工程に関しては、各々、表１に示す条件を適用し、工程４のめっき前処理液としては、ジアリルアミン塩酸塩ジアルキルジアリルアミン塩化物であるジメチルジアリルアミンクロライド／ジアリルアミンクロライド重縮合物(分子量約４０，０００)を、濃度４％、温度７０℃、ｐＨ１１に調整、浸漬時間１０分の各条件で使用して、めっき析出の状態、および、めっき密着性を評価した結果を表１に示している。なお、めっき析出の状態は、目視で評価し、均一なめっき析出が確認されたものを◎、やや均一なものを○、やや不均一なものを△、不均一なものを×とした。めっき密着性は、テープ剥離試験で評価し、非常に良好な密着性が確認されたものを◎、良好な密着性が確認されたものを○、密着性にやや劣るものを△、密着性が悪いものを×とした。 Polyarylate fibers (Kuraray Vectran, 1670 dtex, with oil agent) are used as the objects to be plated, (Step 1: Hot water washing step), (Step 2: Drying step), (Step 3: Plasma treatment step), (Step 4: Pre-plating solution immersion step), the conditions shown in Table 1 were applied, and the pre-plating solution in Step 4 was dimethyldiallylamine chloride / diallylamine hydrochloride dialkyldiallylamine chloride / Diallylamine chloride polycondensate (molecular weight of about 40,000) was adjusted to a concentration of 4%, a temperature of 70 ° C. and a pH of 11 and used under various conditions of immersion for 10 minutes to evaluate the state of plating deposition and plating adhesion. The results are shown in Table 1. In addition, the state of plating deposition was evaluated by visual observation, and the case where uniform plating deposition was confirmed was evaluated as ◎, the case of slightly uniform as ◯, the case of slightly non-uniform as Δ, and the case of non-uniformity as ×. The plating adhesion was evaluated by a tape peeling test, where ◎ indicates that very good adhesion is confirmed, ○ indicates that good adhesion is confirmed, △ indicates that adhesion is slightly inferior, and adhesion is Bad ones were marked with x.
表１に示すように、上記めっき前処理液によるめっき前処理を行ったもの（実施例１、２）では、行わないもの（比較例１、２）に比べて、何れも、均一なめっき析出および良好なめっき密着性を示すことが確認された。実施例１、２を比較すると、被めっき物表面をアミノ化する処理を施すことにより、めっき析出の均一性およびめっき密着性が向上することが確認された。 As shown in Table 1, the plating pretreatment with the plating pretreatment solution (Examples 1 and 2) was more uniform than the ones not performed (Comparative Examples 1 and 2). It was also confirmed that good plating adhesion was exhibited. When Examples 1 and 2 were compared, it was confirmed that the uniformity of plating deposition and the plating adhesion were improved by performing a treatment for aminating the surface of the object to be plated.
（実施例３〜４、比較３）
表２に示すように、プラズマ処理とめっき前処理液浸漬処理を併用することにより、プラズマ処理の種類に関わらず、何れも、均一なめっき析出および良好なめっき密着性を示すことが確認された（実施例３，４）。また、めっき前処理液浸漬処理を行わない場合には、被めっき物表面をプラズマ処理した場合でも、めっき析出が不均一となり、めっき密着性が悪くなることが確認された（比較例３）。 As shown in Table 2, it was confirmed that by using the plasma treatment and the plating pretreatment liquid immersion treatment in combination, uniform plating deposition and good plating adhesion were exhibited regardless of the type of plasma treatment. (Examples 3 and 4). In addition, when the plating pretreatment liquid immersion treatment was not performed, it was confirmed that even when the surface of the object to be plated was subjected to plasma treatment, plating deposition became non-uniform and plating adhesion deteriorated (Comparative Example 3).
（実施例５〜２５）
表３に示すように、分子量３０００〜１５００００の水溶性ポリアミン化合物を含有するポリアミン水溶液をめっき前処理液として使用し、かつ、プラズマ処理とめっき前処理液浸漬処理を併用することにより、何れも、均一なめっき析出および良好なめっき密着性を示すことが確認された（実施例７、９、１１、１３、１５、１７、１９、２１）。 As shown in Table 3, by using a polyamine aqueous solution containing a water-soluble polyamine compound having a molecular weight of 3000 to 150,000 as the plating pretreatment liquid, and using the plasma treatment and the plating pretreatment liquid immersion treatment in combination, It was confirmed that uniform plating deposition and good plating adhesion were exhibited (Examples 7, 9, 11, 13, 15, 17, 19, 21).
また、分子量３０００未満の水溶性ポリアミン化合物を使用した場合（実施例５）や、分子量１５００００超の水溶性ポリアミン化合物を使用した場合（実施例２４）、めっき析出がやや不均一となり、めっき密着性にやや劣ることが確認された。 Further, when a water-soluble polyamine compound having a molecular weight of less than 3000 is used (Example 5), or when a water-soluble polyamine compound having a molecular weight of more than 150,000 is used (Example 24), plating deposition becomes slightly uneven, and plating adhesion It was confirmed that it was slightly inferior.
Claims (10)
前記Ｐｄ系触媒担持工程に先立って、表面が負に帯電した被めっき物を、めっき前処理液に浸漬させるめっき前処理液浸漬工程を有し、
該めっき前処理液として、水溶性カチオン系ポリマーを水に溶解させて得た、アルカリ性のカチオン系ポリマー水溶液であって、非共有電子対を有する元素を含有するものを用いる
ことを特徴とする無電解めっき方法。 An electroless plating method comprising a Pd-based catalyst supporting step, a Pd-based catalyst activation step, and an electroless plating step,
Prior to the Pd-based catalyst supporting step, a plating pretreatment liquid dipping step of dipping the object to be plated, whose surface is negatively charged, in a plating pretreatment solution,
As the plating pretreatment liquid, an alkaline cationic polymer aqueous solution obtained by dissolving a water-soluble cationic polymer in water, which contains an element having an unshared electron pair, is used. Electroplating method.
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