JP5339735B2 - Electroless plating forming material, catalyst adhesion coating solution, electroless plating forming method, and plating method - Google Patents
Electroless plating forming material, catalyst adhesion coating solution, electroless plating forming method, and plating method Download PDFInfo
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- JP5339735B2 JP5339735B2 JP2008022568A JP2008022568A JP5339735B2 JP 5339735 B2 JP5339735 B2 JP 5339735B2 JP 2008022568 A JP2008022568 A JP 2008022568A JP 2008022568 A JP2008022568 A JP 2008022568A JP 5339735 B2 JP5339735 B2 JP 5339735B2
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- meth
- electroless plating
- catalyst
- monomer
- hydrophilic
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Description
本発明は、無電解メッキ可能な処理を非導電性基材に施してなる無電解メッキ形成材料に関する。 The present invention relates to an electroless plating material formed by applying a treatment capable of electroless plating to a non-conductive substrate.
無電解メッキ法は、プラスチック、セラミックス、紙、ガラス、繊維などの非導電性基材表面を導電性表面に変えることができる工業的手法として広く用いられている。特に、非導電性基材表面に電解メッキを施す際に、電解メッキの前処理として非導電性基材上に無電解メッキが施されている。 The electroless plating method is widely used as an industrial technique that can change the surface of a non-conductive substrate such as plastic, ceramics, paper, glass, and fiber to a conductive surface. In particular, when electrolytic plating is performed on the surface of a non-conductive substrate, electroless plating is performed on the non-conductive substrate as a pretreatment for electrolytic plating.
しかし、非導電性基材の表面に無電解メッキを直接施すことは困難である。これは、非導電性基材の基材表面が平滑であるため、無電解メッキの前処理としての触媒層を付着させることが困難なためである。 However, it is difficult to directly apply electroless plating to the surface of the non-conductive substrate. This is because the substrate surface of the non-conductive substrate is smooth and it is difficult to attach a catalyst layer as a pretreatment for electroless plating.
そこで従来は、機械的処理や化学的処理によって非導電性基材を粗面化することにより、基材表面に触媒を付着可能としていた。しかし、基材を粗面化してしまうと全体が不透明となってしまい、透明性が求められる用途に適さないという問題があった。 Therefore, conventionally, the catalyst can be attached to the surface of the base material by roughening the non-conductive base material by mechanical treatment or chemical treatment. However, if the base material is roughened, the whole becomes opaque, and there is a problem that it is not suitable for applications requiring transparency.
かかる問題を解決するものとして、非導電性基材上に水溶性高分子を含有するゲル状薄膜（触媒付着層）を形成する手段が提案されている（特許文献１）。 In order to solve such a problem, means for forming a gel-like thin film (catalyst adhesion layer) containing a water-soluble polymer on a non-conductive substrate has been proposed (Patent Document 1).
しかし、特許文献１の方法は、ゲル状薄膜が触媒を付着するものの、触媒付着工程でゲル状薄膜を触媒浴に浸漬した際や、電解メッキ後の現像工程でゲル状薄膜に現像液が接した際に、ゲル状薄膜が非導電性基材から剥離したり溶出したりしてしまう場合があった。 However, in the method of Patent Document 1, although the gel-like thin film adheres the catalyst, the developer comes into contact with the gel-like thin film when the gel-like thin film is immersed in the catalyst bath in the catalyst attaching step or in the development step after electrolytic plating. In some cases, the gel-like thin film may be peeled off or eluted from the non-conductive substrate.
かかる問題を解決するものとして、ゲル状薄膜を硬化させ、触媒浴や現像液に用いられる溶剤に対する耐久性を向上させる手段が考えられる。しかし、ゲル状薄膜を硬化させた場合、ゲル状薄膜と非導電性基材との接着性が低下してしまい、触媒付着工程、現像工程その他工程においてゲル状薄膜が非導電性基材から剥離する現象を十分に防止できない。 In order to solve such a problem, a means for curing the gel-like thin film and improving the durability against the solvent used in the catalyst bath or the developer may be considered. However, when the gel-like thin film is cured, the adhesion between the gel-like thin film and the non-conductive substrate is reduced, and the gel-like thin film is peeled off from the non-conductive substrate in the catalyst adhesion process, development process and other processes. This phenomenon cannot be sufficiently prevented.
上記課題を解決するものとして、本発明者は、非導電性基材上に、水酸基を有する樹脂及びイソシアネート系化合物から形成されてなる硬化層、水酸基を含有してなる親水性及び／又は水溶性樹脂から形成されてなる触媒付着層を有する無電解メッキ形成材料を開発した（特願２００６−８０９４２：ＷＯ２００７／１０８３５１）。 In order to solve the above problems, the present inventor has developed a cured layer formed of a hydroxyl group-containing resin and an isocyanate compound, a hydroxyl group-containing hydrophilic and / or water-soluble material on a non-conductive substrate. An electroless plating forming material having a catalyst adhesion layer formed from a resin has been developed (Japanese Patent Application No. 2006-80942: WO2007 / 108351).
しかし、特願２００６−８０９４２の無電解メッキ形成材料は、上記課題を解決するものの、触媒付着層の絶縁性が必ずしも十分でなく、プリント配線板などの絶縁性が求められる用途に適さないという問題があった。従前の無電解メッキ形成材料も同様に触媒付着層の絶縁性が不十分であった。 However, although the electroless plating forming material of Japanese Patent Application No. 2006-80942 solves the above-described problems, the insulating property of the catalyst adhesion layer is not necessarily sufficient, and the problem is that it is not suitable for applications requiring insulating properties such as printed wiring boards. was there. The conventional electroless plating material also has insufficient insulation of the catalyst adhesion layer.
そこで、本発明者は、触媒付着性が良好であり、また、触媒付着工程、現像工程その他工程において、触媒付着層が非導電性基材から剥離したりメッキ液に溶出したりすることがなく、さらに絶縁性に優れた無電解メッキ形成材料を提供することを目的とする。 Therefore, the present inventors have good catalyst adhesion, and the catalyst adhesion layer does not peel off from the non-conductive substrate or elute into the plating solution in the catalyst adhesion process, the development process and other processes. It is another object of the present invention to provide an electroless plating material that is further excellent in insulation.
上記課題を解決する本発明の無電解メッキ形成材料は、非導電性基材上に触媒付着層を有する無電解メッキ形成材料において、前記触媒付着層が、（メタ）アクリル基を有するモノマーを５０ｍｏｌ％以上含む親水性（メタ）アクリル系樹脂を含み、前記（メタ）アクリル基を有するモノマーは、自己架橋性を有する親水性の（メタ）アクリル基を有するモノマーであるＮ−メチロール（メタ）アクリルアミドと疎水性の（メタ）アクリル基を有するモノマー、又はＮ−メチロール（メタ）アクリルアミドと他の親水性の（メタ）アクリル基を有するモノマー及び疎水性の（メタ）アクリル基を有するモノマーのいずれかであることを特徴とするものである。 The electroless plating forming material of the present invention that solves the above problems is the electroless plating forming material having a catalyst adhesion layer on a non-conductive substrate, wherein the catalyst adhesion layer contains 50 mol of a monomer having a (meth) acryl group. N-methylol (meth) acrylamide, which is a monomer having a hydrophilic (meth) acrylic group having a self-crosslinking property, is a monomer having a hydrophilic (meth) acrylic resin containing at least%. any of a monomer having a monomer having a hydrophobic (meth) acrylic group, or N- methylol (meth) acrylamide and other hydrophilic (meth) monomers and hydrophobic having an acryl group and (meth) acrylic group It is characterized by being.
本発明の無電解メッキ形成材料は、好ましくは、前記親水性（メタ)アクリル基を有するモノマーと疎水性（メタ）アクリル基を有するモノマーのモル比が、５：５〜１４：８６であることを特徴とするものである。 In the electroless plating material of the present invention, preferably, the molar ratio of the monomer having a hydrophilic (meth) acryl group and the monomer having a hydrophobic (meth) acryl group is 5: 5 to 14:86. It is characterized by.
本発明の無電解メッキ形成材料は、好ましくは、前記親水性（メタ）アクリル系樹脂は、Ｎ−メチロール（メタ）アクリルアミドを５ｍｏｌ％以上含むことを特徴とするものである。 The electroless plating material of the present invention is preferably characterized in that the hydrophilic (meth) acrylic resin contains 5 mol% or more of N-methylol (meth) acrylamide .
本発明の無電解メッキ形成材料は、好ましくは、前記親水性（メタ）アクリル系樹脂は、触媒付着層を構成する全樹脂の５０重量％以上含まれることを特徴とするものである。 The electroless plating material of the present invention is preferably characterized in that the hydrophilic (meth) acrylic resin is contained in an amount of 50% by weight or more of the total resin constituting the catalyst adhesion layer .
本発明の無電解メッキ形成材料は、好ましくは、前記自己架橋性を有する親水性モノマーの一部が自己架橋されてなることを特徴とするものである。 The electroless plating material of the present invention is preferably characterized in that a part of the self-crosslinking hydrophilic monomer is self-crosslinked.
また、本発明の触媒付着用塗布液は、非導電性基材上に無電解メッキ用触媒を付着させるための触媒付着用塗布液であって、前記触媒付着用塗布液は、（メタ）アクリル基を有するモノマーを５０ｍｏｌ％以上含む親水性（メタ）アクリル系樹脂を含み、前記（メタ）アクリル基を有するモノマーは、自己架橋性を有する親水性の（メタ）アクリル基を有するモノマーであるＮ−メチロール（メタ）アクリルアミドと疎水性の（メタ）アクリル基を有するモノマー、又はＮ−メチロール（メタ）アクリルアミドと他の親水性の（メタ）アクリル基を有するモノマー及び疎水性の（メタ）アクリル基を有するモノマーのいずれかであることを特徴とするものである。
The catalyst adhesion coating liquid of the present invention is a catalyst adhesion coating liquid for adhering an electroless plating catalyst on a non-conductive substrate, and the catalyst adhesion coating liquid is (meth) acrylic. A hydrophilic (meth) acrylic resin containing 50 mol% or more of a monomer having a group, and the monomer having a (meth) acrylic group is a monomer having a hydrophilic (meth) acrylic group having a self-crosslinking property -Methylol (meth) acrylamide and a monomer having a hydrophobic (meth) acryl group, or N-methylol (meth) acrylamide and another monomer having a hydrophilic (meth) acryl group and a hydrophobic (meth) acryl group It is any of the monomers which have this.
また、本発明の無電解メッキの形成方法は、本発明の無電解メッキ形成材料の触媒付着層に触媒を付着させた後、無電解メッキを行うことを特徴とするものである。 In addition, the electroless plating forming method of the present invention is characterized in that electroless plating is performed after a catalyst is attached to the catalyst adhesion layer of the electroless plating forming material of the present invention.
また、本発明のメッキ方法は、非導電性基材上に触媒付着層が形成されてなる無電解メッキ形成材料の、触媒付着層に触媒を付着するステップ（１）と、触媒を付着した無電解メッキ形成材料をメッキすべき金属化合物を含む無電解メッキ液に浸漬し、無電解メッキを行うステップ（２）と、無電解メッキが形成された無電解メッキ形成材料を電解メッキ浴に浸漬し通電して電解メッキを行うステップ（３）とを含む非導電性基材のメッキ方法において、前記無電解メッキ形成材料として、本発明の無電解メッキ形成材料を用いたことを特徴とするものである。 In addition, the plating method of the present invention includes a step (1) of depositing a catalyst on a catalyst adhesion layer of an electroless plating forming material in which a catalyst adhesion layer is formed on a non-conductive substrate; Step (2) of immersing the electroplating forming material in an electroless plating solution containing a metal compound to be plated and performing electroless plating, and immersing the electroless plating forming material on which the electroless plating is formed in an electroplating bath In the method of plating a non-conductive substrate including the step (3) of performing electroplating by energization, the electroless plating forming material of the present invention is used as the electroless plating forming material. is there.
また、本発明のメッキ方法は、非導電性基材上に触媒付着層が形成されてなる無電解メッキ形成材料の、触媒付着層に触媒を付着するステップ（１）と、触媒を付着した無電解メッキ形成材料をメッキすべき金属化合物を含む無電解メッキ液に浸漬し、無電解メッキを行うステップ（２）と、無電解メッキが形成された無電解メッキ形成材料を電解メッキ浴に浸漬し通電して電解メッキを行うステップ（３）とを含む非導電性基材のメッキ方法において、前記無電解メッキ形成材料として、非導電性基材の表面に本発明の触媒付着用塗布液を塗布することにより触媒付着層を形成した無電解メッキ形成材料を用いたことを特徴とするものである。 In addition, the plating method of the present invention includes a step (1) of depositing a catalyst on a catalyst adhesion layer of an electroless plating forming material in which a catalyst adhesion layer is formed on a non-conductive substrate; Step (2) of immersing the electroplating forming material in an electroless plating solution containing a metal compound to be plated and performing electroless plating, and immersing the electroless plating forming material on which the electroless plating is formed in an electroplating bath In the method for plating a non-conductive substrate including the step (3) of performing electroplating by energization, the catalyst-adhesive coating solution of the present invention is applied to the surface of the non-conductive substrate as the electroless plating forming material. Thus, an electroless plating material having a catalyst adhesion layer formed thereon is used.
また、本発明のメッキ方法は、好ましくは、前記無電解メッキ形成材料を加熱し、親水性（メタ）アクリル系樹脂の架橋を進行させるステップ（４）を含むことを特徴とするものである。 In addition, the plating method of the present invention preferably includes a step (4) of heating the electroless plating forming material to advance the crosslinking of the hydrophilic (meth) acrylic resin.
また、本発明のメッキ方法は、好ましくは、前記ステップ（４）は、ステップ（１）の後であってステップ（３）の前に行うことを特徴とするものである。 The plating method of the present invention is preferably characterized in that the step (4) is performed after the step (1) and before the step (3).
本発明の無電解メッキ形成材料は、触媒付着層が、自己架橋性を有する親水性モノマーを構成モノマーとして含む親水性（メタ）アクリル系樹脂を含むことから、触媒付着性能が良好であり、触媒付着層が非導電性基材から剥離したりメッキ液に溶出したりすることがなく、さらに絶縁性が良好でありメッキ層が変色することもない。 The electroless plating forming material of the present invention has a good catalyst adhesion performance because the catalyst adhesion layer contains a hydrophilic (meth) acrylic resin containing a hydrophilic monomer having self-crosslinking property as a constituent monomer. The adhesion layer is not peeled off from the non-conductive substrate or eluted into the plating solution, and further, the insulation is good and the plating layer is not discolored.
また、本発明の無電解メッキの形成方法によれば、非導電性基材上に短時間で容易に無電解メッキを形成することができ、かつ作業中に非導電性基材上の触媒付着層が剥離してしまうこともない。 Further, according to the electroless plating forming method of the present invention, the electroless plating can be easily formed on the nonconductive substrate in a short time, and the catalyst adheres to the nonconductive substrate during the operation. The layer does not peel off.
まず、本発明の無電解メッキ形成材料について説明する。本発明の無電解メッキ形成材料は、非導電性基材上に触媒付着層を有する無電解メッキ形成材料において、前記触媒付着層が、自己架橋性を有する親水性モノマーを構成モノマーとして含む親水性（メタ）アクリル系樹脂を含むことを特徴とするものである。以下、本発明の無電解メッキ形成材料の実施の形態について説明する。 First, the electroless plating material of the present invention will be described. The electroless plating forming material of the present invention is an electroless plating forming material having a catalyst adhesion layer on a non-conductive substrate, wherein the catalyst adhesion layer has a hydrophilic monomer having a self-crosslinking property as a constituent monomer. It contains a (meth) acrylic resin. Hereinafter, embodiments of the electroless plating material of the present invention will be described.
非導電性基材としては、ポリエステル、ＡＢＳ（アクリロニトリル−ブタジエン−スチレン）、ポリスチレン、ポリカーボネート、アクリル、液晶ポリマー（ＬＣＰ）、ポリオレフィン、セルロース樹脂、ポリスルホン、ポリフェニレンスルフィド、ポリエーテルスルホン、ポリエーテルエーテルケトン、ポリイミドなどのプラスチックフィルム、ガラス、セラミックス、紙、繊維などがあげられる。これらの中でも、メッキ形成後に非導電性基材側から良好な金属光沢を観察するという点で、プラスチック、ガラスなどの透明基材が好適に使用できる。また、非導電性基材は、平面状のものに限られず、立体形状のものであってもよい。 Non-conductive substrates include polyester, ABS (acrylonitrile-butadiene-styrene), polystyrene, polycarbonate, acrylic, liquid crystal polymer (LCP), polyolefin, cellulose resin, polysulfone, polyphenylene sulfide, polyethersulfone, polyetheretherketone, Examples thereof include plastic films such as polyimide, glass, ceramics, paper, and fibers. Among these, transparent substrates such as plastic and glass can be suitably used in that good metallic luster is observed from the non-conductive substrate side after plating is formed. Further, the non-conductive base material is not limited to a planar shape, and may be a three-dimensional shape.
非導電性基材は、触媒付着層との接着性を向上させるための易接着処理を施したものでもよい。易接着処理としては、コロナ放電処理やプラズマ処理などがあげられる。 The non-conductive substrate may be subjected to an easy adhesion treatment for improving the adhesion with the catalyst adhesion layer. Examples of the easy adhesion treatment include corona discharge treatment and plasma treatment.
また、非導電性基材が不透明でも構わない場合には、基材表面をあらしたものでもよい。基材表面をあらしておけば、基材の表面粗さに起因して触媒付着層の表面をあらすことができ、触媒を付着させやすくすることができる。 In addition, when the non-conductive substrate may be opaque, it may be a surface of the substrate. If the surface of the substrate is exposed, the surface of the catalyst adhesion layer can be exposed due to the surface roughness of the substrate, and the catalyst can be easily adhered.
触媒付着層は、無電解メッキに対して触媒活性を有する金属微粒子（触媒）を付着させる役割を有するものである。本発明では、このような触媒付着層として、自己架橋性を有する親水性モノマーを構成モノマーとして含む親水性（メタ）アクリル系樹脂を含むものを用いることから、触媒付着性能が良好であり、触媒付着層が非導電性基材から剥離したりメッキ液に溶出したりすることがなく、かつ絶縁性を良好にすることができる。また、触媒付着層の組成によっては、メッキ層の触媒付着層との界面が黒っぽく変色することがあるが、本発明で用いる触媒付着層によれば、メッキ層の触媒付着層との界面の変色を防止できる。 The catalyst adhesion layer has a role of adhering metal fine particles (catalyst) having catalytic activity for electroless plating. In the present invention, since such a catalyst adhesion layer includes a hydrophilic (meth) acrylic resin containing a hydrophilic monomer having a self-crosslinking property as a constituent monomer, the catalyst adhesion performance is good, and the catalyst The adhesion layer is not peeled off from the non-conductive substrate or eluted into the plating solution, and the insulation can be improved. In addition, depending on the composition of the catalyst adhesion layer, the interface between the plating layer and the catalyst adhesion layer may change to blackish. However, according to the catalyst adhesion layer used in the present invention, the color change at the interface between the plating layer and the catalyst adhesion layer. Can be prevented.
親水性（メタ）アクリル系樹脂は、構成モノマーとして、少なくとも自己架橋性を有する親水性モノマーを含む。自己架橋性を有する親水性モノマーを含むことにより、架橋度合いを工程の段階に応じて調整することができる。言い換えると、触媒付着層の触媒付着性、溶出防止性および絶縁性を工程の段階に応じて調整することができる。例えば、触媒付着前の段階では一部の自己架橋性を有する親水性モノマーのみを架橋させておき（未架橋の自己架橋性を有する親水性モノマーを残しておき）、触媒付着後に架橋を進行させるようにすれば、触媒の付着を良好しつつ、かつ前記性能と相反する性能である触媒付着層の溶出防止性や絶縁性を架橋の進行により向上させることができる。また、自己架橋性モノマーのため、構成モノマーとして自己架橋性を有しない親水性モノマーを有していた場合、当該親水性モノマーの親水性を損なうことなく架橋を進めることができる。また、元来親水性のモノマーであることから、自己架橋した後でも疎水性モノマーに比べて触媒付着性が良好であるため、触媒付着層を触媒付着性に優れつつ溶出防止性および絶縁性に優れるものとしやすくできる。 The hydrophilic (meth) acrylic resin contains at least a hydrophilic monomer having self-crosslinking property as a constituent monomer. By including a hydrophilic monomer having self-crosslinkability, the degree of crosslinking can be adjusted according to the stage of the process. In other words, the catalyst adhesion, elution prevention, and insulation of the catalyst adhesion layer can be adjusted according to the stage of the process. For example, in the stage before adhesion of the catalyst, only a part of the hydrophilic monomer having self-crosslinkability is crosslinked (leaving the uncrosslinked hydrophilic monomer having self-crosslinkability), and the crosslinking proceeds after adhesion of the catalyst. By doing so, it is possible to improve the elution prevention property and the insulating property of the catalyst adhesion layer, which are performances contrary to the above performance, while improving the adhesion of the catalyst, by the progress of the crosslinking. Moreover, since it is a self-crosslinkable monomer and has a hydrophilic monomer that does not have self-crosslinkability as a constituent monomer, the crosslinking can proceed without impairing the hydrophilicity of the hydrophilic monomer. In addition, since it is originally a hydrophilic monomer, it has better catalyst adhesion than hydrophobic monomers even after self-crosslinking, so that the catalyst adhesion layer has excellent catalyst adhesion while preventing elution and insulation. Excellent and easy to do.
自己架橋性を有する親水性モノマーとしては、重合性二重結合を有しかつ自己架橋性を有するモノマーが用いられる。このようなモノマーとしては、Ｎ−メチロール（メタ）アクリルアミド、ジメチロール（メタ）アクリルアミド、Ｎ−メチロールプロパン（メタ）アクリルアミドなどメチロール基を含むモノマーの１種又は２種以上を用いることができる。また、自己架橋性を有する親水性モノマーの中でも、Ｎ−メチロール（メタ）アクリルアミドのような（メタ）アクリル基を有するモノマーは、触媒付着性やメッキ層の変色防止性に優れる点で好ましい。 As the hydrophilic monomer having self-crosslinking property, a monomer having a polymerizable double bond and having self-crosslinking property is used. As such a monomer, 1 type (s) or 2 or more types of monomers containing methylol groups, such as N-methylol (meth) acrylamide, dimethylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, can be used. Of the hydrophilic monomers having self-crosslinking properties, monomers having a (meth) acrylic group such as N-methylol (meth) acrylamide are preferable in terms of excellent catalyst adhesion and anti-discoloring property of the plating layer.
自己架橋性を有する親水性モノマーは、触媒付着前や触媒付着後に架橋させることができる。また、自己架橋は一度に完全に架橋させなくても、触媒付着前と触媒付着後に段階を分けて架橋させることもできる。実際の架橋のタイミングは、他の種類のモノマーとの兼ね合いにもよる。すなわち、親水性（メタ）アクリル系樹脂が自己架橋性を有する親水性モノマーのみからなる場合、溶出防止性を確保するため触媒付着前に一部のモノマーを架橋させておく必要がある。親水性（メタ）アクリル系樹脂が他に疎水性モノマーを含む場合には、両者の割合にもよるが必ずしも触媒付着前に架橋させる必要はない。親水性（メタ）アクリル系樹脂が他に自己架橋性を有しない親水性モノマーを含む場合には、両者の割合にもよるが触媒付着前に全て架橋させても構わない。このように、自己架橋性を有する親水性モノマーを架橋させるタイミングは、親水性（メタ）アクリル系樹脂を構成するモノマーの種類に応じて、適宜調整して行うことができるが、触媒付着前に第一段階の架橋を行い、触媒付着後に第二段階の架橋を行う方法が好ましい。このように段階を分けて架橋させることにより、触媒の付着を良好しつつ、メッキ浴に触媒付着層が溶出するのを防止し、かつ架橋の進行により触媒付着層の絶縁性を向上させやすくすることができる。 さらに、自己架橋性を有する親水性モノマーを用いることにより、無電解メッキによるメッキ層やその後の電解メッキによるメッキ層を割れにくくすることができる。 The hydrophilic monomer having self-crosslinking property can be crosslinked before or after the catalyst is adhered. In addition, the self-crosslinking can be carried out in stages before and after the catalyst adhesion, without being completely crosslinked at a time. The actual timing of crosslinking depends on the balance with other types of monomers. That is, when the hydrophilic (meth) acrylic resin is composed only of a hydrophilic monomer having self-crosslinking properties, it is necessary to crosslink some of the monomers before adhesion of the catalyst in order to ensure elution prevention. When the hydrophilic (meth) acrylic resin additionally contains a hydrophobic monomer, it is not always necessary to crosslink the catalyst before adhering to the catalyst, depending on the ratio of the two. When the hydrophilic (meth) acrylic resin contains other hydrophilic monomers that do not have self-crosslinking properties, all of them may be crosslinked before adhesion of the catalyst, depending on the ratio of the two. As described above, the timing for crosslinking the self-crosslinking hydrophilic monomer can be appropriately adjusted according to the type of monomer constituting the hydrophilic (meth) acrylic resin, but before the catalyst adheres to it. A method in which the first-stage crosslinking is performed and the second-stage crosslinking is performed after adhesion of the catalyst is preferable. By cross-linking in this way, the adhesion of the catalyst is improved, the catalyst adhesion layer is prevented from eluting into the plating bath, and the insulation of the catalyst adhesion layer is easily improved by the progress of the crosslinking. be able to. Furthermore, by using a hydrophilic monomer having a self-crosslinking property, it is possible to make the plating layer by electroless plating and the plating layer by subsequent electrolytic plating difficult to break.
自己架橋性を有する親水性モノマーは、９０〜１３０℃で５〜６０分程度加熱することによりほぼ完全に自己架橋させることができる。段階を踏んで架橋させる場合には、例えば最初に６０〜１００℃で０．５〜５分程度の加熱を行い、次いで９０〜１３０℃で５〜６０分程度加熱すればよい。 The hydrophilic monomer having self-crosslinking property can be almost completely self-crosslinked by heating at 90 to 130 ° C. for about 5 to 60 minutes. In the case of crosslinking in steps, for example, heating may be performed first at 60 to 100 ° C. for about 0.5 to 5 minutes, and then at 90 to 130 ° C. for about 5 to 60 minutes.
親水性（メタ）アクリル系樹脂は、構成モノマーとして、自己架橋性を有さない親水性モノマーを含むことが好ましい。自己架橋性を有さない親水性モノマーを含むことにより、自己架橋性を有する親水性モノマーの架橋が進みすぎた場合であっても、触媒付着層に触媒付着性を備えさせることができる。 The hydrophilic (meth) acrylic resin preferably contains a hydrophilic monomer having no self-crosslinking property as a constituent monomer. By including a hydrophilic monomer that does not have self-crosslinkability, even if the crosslinking of the hydrophilic monomer having self-crosslinkability has progressed too much, the catalyst adhesion layer can be provided with catalyst adhesion.
自己架橋性を有さない親水性モノマーとしては、重合性二重結合を有し、かつカルボキシル基、水酸基、ヒドロキシメチル基、アミノ基、スルホン酸基、ポリエチレンオキサイド基、硫酸エステル塩基、リン酸エステル塩基などを有するモノマーなどを用いることができる。このようなモノマーとしては、「２−ヒドロキシルエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレートなどの水酸基を有する（メタ）アクリレート類」、「カルボキシル基を含むアクリル酸、メタクリル酸、マレイン酸またはそのモノアルキルエステル、イタコン酸またはそのモノアルキルエステル、フマル酸またはそのモノアルキルエステルなどのエチレン性不飽和カルボン酸」、「アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド等の（メタ）アクリルアミド類」、「Ｎ−メチルアミノエチルメタクリレート、Ｎ−メチルアミノエチルアクリレート、ジメチルアミノエチルメタクリレート、ジメチルアミノエチルアクリレート、ジエチルアミノエチルメタクリレート、ジエチルアミノエチルメタクリレート等のアクリル酸またはメタクリル酸のアルキルアミノエステル類」、「Ｎ−（２−ジメチルアミノエチル）アクリルアミド、Ｎ−（２−ジメチルアミノエチル）メタクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド等のアルキルアミノ基を有する不飽和アミド類」、「ビニルピリジン等のモノビニルピリジン類」、「ジメチルアミノエチルビニルエーテルなどのアルキルアミノ基を有するビニルエーテル類」、「ビニルスルホン酸、スチレンスルホン酸およびその塩、２−アクリロイルアミノ−２−メチルプロパンスルホン酸、およびその塩等のスルホン基を有するもの」、「ビニルピロリドン」などの１種又は２種以上を用いることができる。 Hydrophilic monomers that do not have self-crosslinkability include polymerizable double bonds and carboxyl groups, hydroxyl groups, hydroxymethyl groups, amino groups, sulfonic acid groups, polyethylene oxide groups, sulfate ester bases, phosphate esters A monomer having a base or the like can be used. Examples of such monomers include “(meth) acrylates having a hydroxyl group such as 2-hydroxylethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate”, “acrylic acid containing carboxyl group, methacrylic acid, maleic acid” Or an ethylenically unsaturated carboxylic acid such as monoalkyl ester, itaconic acid or monoalkyl ester thereof, fumaric acid or monoalkyl ester thereof, “(meth) acrylamides such as acrylamide, N, N-dimethylacrylamide”, “ N-methylaminoethyl methacrylate, N-methylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. Alkylamino groups such as “alkylaminoesters of acrylic acid or methacrylic acid”, “N- (2-dimethylaminoethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide, N, N-dimethylaminopropylacrylamide” Having unsaturated amides "," monovinylpyridines such as vinylpyridine "," vinyl ethers having an alkylamino group such as dimethylaminoethyl vinyl ether "," vinylsulfonic acid, styrenesulfonic acid and salts thereof, 2-acryloylamino- 1 type, or 2 or more types, such as "thing which has sulfone groups, such as 2-methylpropanesulfonic acid and its salt," "vinylpyrrolidone" can be used.
これらの中でも、触媒付着性やメッキ層の変色防止性に優れる（メタ）アクリル基を有するモノマーが好適であり、その中でも、水酸基を有する（メタ）アクリレート類が特に好適である。 Among these, a monomer having a (meth) acryl group that is excellent in catalyst adhesion and anti-discoloring property of the plating layer is preferable, and among these, a (meth) acrylate having a hydroxyl group is particularly preferable.
親水性（メタ）アクリル系樹脂は、構成モノマーとして、疎水性モノマーを含むことが好ましい。疎水性モノマーを含むことにより、触媒付着層の溶出防止性を調整しやすくすることができる。 The hydrophilic (meth) acrylic resin preferably contains a hydrophobic monomer as a constituent monomer. By including the hydrophobic monomer, it is possible to easily adjust the elution prevention property of the catalyst adhesion layer.
疎水性モノマーとしては、重合性二重結合を有し、かつ親油性の炭化水素基、芳香環基、または脂環基を有するものなどを用いることができる。このようなモノマーとしては、「メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、デシル（メタ）アクリレートなどのアルキル（メタ）アクリレート」、「（メタ）アクリル酸グリシジル」、「スチレン、２−メチルスチレン、ビニルトルエン、ｔ−ブチルスチレン、クロルスチレン、ビニルアニソール、ビニルナフタレン、ジビニルベンゼン等の芳香族ビニル類」、「塩化ビニリデン、フッ化ビニリデン等のハロゲン化ビニリデン類」、エチレン、プロピレン、イソプロピレン、ブタジエン、塩化ビニル、ビニルエーテル、ビニルケトン、クロロプレン、（メタ）アクリロニトリルなどの１種又は２種以上を用いることができる。 As the hydrophobic monomer, one having a polymerizable double bond and having a lipophilic hydrocarbon group, aromatic ring group, or alicyclic group can be used. Such monomers include “methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Alkyl (meth) acrylates such as octyl (meth) acrylate and decyl (meth) acrylate "," glycidyl (meth) acrylate "," styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole " , Aromatic vinyls such as vinylnaphthalene and divinylbenzene ”,“ vinylidene halides such as vinylidene chloride and vinylidene fluoride ”, ethylene, propylene, isopropylene, butadiene, vinyl chloride, vinyl ether, vinyl ketone, Roropuren, can be used alone or in combination, such as (meth) acrylonitrile.
これらの中でも、触媒付着性やメッキ層の変色防止性に優れる（メタ）アクリル基を有するモノマーが好適であり、その中でも、アルキル（メタ）アクリレートが特に好適である。また、（メタ）アクリル酸グリシジルは、上述した自己架橋性を有する親水性モノマーと同じく自己架橋可能であり、同様の効果（絶縁性の向上等）を発揮可能である点で好ましい。 Among these, a monomer having a (meth) acryl group excellent in catalyst adhesion and anti-discoloring property of the plating layer is preferable, and among them, alkyl (meth) acrylate is particularly preferable. Further, glycidyl (meth) acrylate is preferable in that it can be self-crosslinked in the same manner as the above-described hydrophilic monomer having self-crosslinkability, and can exhibit the same effects (improvement of insulation, etc.).
親水性（メタ）アクリル系樹脂を構成するモノマーは、少なくとも上述した自己架橋性を有する親水性モノマーを用い、必要に応じて自己架橋性を有さない親水性モノマーや疎水性モノマーを用いるが、前記構成モノマーのうち少なくとも１種は（メタ）アクリル基を有するモノマーを用いる。また、（メタ）アクリル基を有するモノマーは、触媒付着性やメッキ層の変色防止性を良好にするため、親水性（メタ）アクリル系樹脂を構成する全モノマーのうち５０ｍｏｌ％以上とすることが好ましく、６０ｍｏｌ％以上とすることがより好ましい。 As the monomer constituting the hydrophilic (meth) acrylic resin, at least the above-described hydrophilic monomer having self-crosslinking property is used, and if necessary, a hydrophilic monomer or hydrophobic monomer having no self-crosslinking property is used. At least one of the constituent monomers is a monomer having a (meth) acryl group. In addition, the monomer having a (meth) acrylic group may be 50 mol% or more of the total monomer constituting the hydrophilic (meth) acrylic resin in order to improve the catalyst adhesion and the anti-discoloration property of the plating layer. Preferably, it is more preferably 60 mol% or more.
（メタ）アクリル基を有するモノマーはいずれのモノマーであっても良いが、触媒付着性やメッキ層の変色防止性の観点から、自己架橋性および非自己架橋性の親水性モノマーが（メタ）アクリル基を有するモノマーであることが好ましく、さらに疎水性モノマーを含めた全てのモノマーが（メタ）アクリル基を有するモノマーであることがより好ましい。 The monomer having a (meth) acrylic group may be any monomer, but from the viewpoint of catalyst adhesion and the ability to prevent discoloration of the plating layer, self-crosslinking and non-self-crosslinking hydrophilic monomers are (meth) acrylic. A monomer having a group is preferable, and all monomers including a hydrophobic monomer are more preferably monomers having a (meth) acryl group.
親水性（メタ）アクリル系樹脂を構成するモノマーの割合は、以下のようにすることが好ましい。まず、自己架橋性を有する親水性モノマーの割合は、他のモノマーである自己架橋性を有さない親水性モノマー及び／又は疎水性モノマーを含む場合、溶出防止性および絶縁性を向上させるため、全体の５ｍｏｌ％以上とすることが好ましく、１０ｍｏｌ％以上とすることがより好ましい。また、自己架橋性を有さない親水性モノマーおよび疎水性モノマーの割合は、自己架橋性を有する親水性モノマーの割合や架橋のさせ方により異なるため一概には言えない。すなわち、自己架橋性を有する親水性モノマーは、架橋していない部分は専ら親水性モノマーとして働くが、架橋した部分は疎水性モノマーとして働くからである。 The ratio of the monomer constituting the hydrophilic (meth) acrylic resin is preferably as follows. First, when the ratio of the hydrophilic monomer having self-crosslinking property includes a hydrophilic monomer and / or a hydrophobic monomer that does not have self-crosslinking property, which is another monomer, in order to improve the elution prevention property and the insulation property, The total content is preferably 5 mol% or more, and more preferably 10 mol% or more. Further, the ratio of the hydrophilic monomer having no self-crosslinkability and the hydrophobic monomer varies depending on the ratio of the hydrophilic monomer having self-crosslinkability and the way of crosslinking, and thus cannot be generally described. That is, in the hydrophilic monomer having self-crosslinking property, the non-crosslinked portion functions exclusively as a hydrophilic monomer, but the crosslinked portion functions as a hydrophobic monomer.
親水性（メタ）アクリル系樹脂としては、自己架橋性を有する親水性モノマーを単独重合させたもの、あるいは自己架橋性を有する親水性モノマーと、自己架橋性を有さない親水性モノマーおよび／または疎水性モノマーとを共重合させてなる樹脂があげられる。さらに、親水性（メタ）アクリル系樹脂としては、一種のモノマー（自己架橋性を有する親水性モノマー、自己架橋性を有さない親水性モノマーあるいは疎水性モノマー）から枝部分となるマクロモノマーを合成し、当該マクロモノマーと幹部分となる他のモノマーとを共重合させてなる櫛形樹脂があげられる。これらの中でも、分子相互が絡み合うことにより触媒付着層の溶出防止性に優れる櫛形樹脂が好ましい。 As the hydrophilic (meth) acrylic resin, a polymer obtained by homopolymerizing a hydrophilic monomer having self-crosslinking property, a hydrophilic monomer having self-crosslinking property, a hydrophilic monomer having no self-crosslinking property and / or Examples thereof include resins obtained by copolymerizing a hydrophobic monomer. Furthermore, as a hydrophilic (meth) acrylic resin, a macromonomer that becomes a branch part is synthesized from a kind of monomer (hydrophilic monomer having self-crosslinking property, hydrophilic monomer having no self-crosslinking property or hydrophobic monomer). And the comb-shaped resin formed by copolymerizing the said macromonomer and the other monomer used as a trunk part is mention | raise | lifted. Among these, a comb-shaped resin that is excellent in the elution prevention property of the catalyst adhesion layer due to the intertwining of molecules is preferable.
櫛形樹脂の幹部分となるモノマーは何れのモノマーであっても良いが、疎水性モノマーから幹部分を構成することが好ましい。このように基本骨格となる幹部分を疎水性モノマーから構成して、枝部分で親水性を発現させることにより、親水性を高めて触媒付着性を向上させる一方で、相反する性能である触媒付着層の溶出も防止しやすくすることができる。 The monomer that serves as the trunk portion of the comb-shaped resin may be any monomer, but the trunk portion is preferably composed of a hydrophobic monomer. In this way, the trunk part that becomes the basic skeleton is composed of a hydrophobic monomer, and by developing hydrophilicity at the branch part, the hydrophilicity is increased and the catalyst adhesion is improved, while the catalyst adhesion is a contradictory performance Elution of the layer can be easily prevented.
親水性（メタ）アクリル系樹脂の数平均分子量は３千〜８万であることが好ましい。３千以上とすることにより容易に皮膜化でき、８万以下とすることにより加工性が容易な粘性にできる。 The number average molecular weight of the hydrophilic (meth) acrylic resin is preferably 3,000 to 80,000. When it is 3,000 or more, it can be easily formed into a film, and when it is 80,000 or less, the workability can be easily changed to viscosity.
触媒付着層には上述した親水性（メタ）アクリル系樹脂以外の樹脂を含んでいてもよい。このような樹脂としては、例えば、ポリビニルブチラール、ポリエステル樹脂、ポリウレタン系樹脂などがあげられる。これら親水性（メタ）アクリル系樹脂以外の樹脂は親水性であっても疎水性であっても構わないが、溶出を防ぐため非水溶性であることが好ましい。但し、他の樹脂を含有させる場合でも、上述した親水性（メタ）アクリル系樹脂は、触媒付着層を構成する全樹脂の５０重量％以上含まれることが好ましく、８０重量％以上含まれることがより好ましく、９０重量％以上含まれることがさらに好ましい。 The catalyst adhesion layer may contain a resin other than the hydrophilic (meth) acrylic resin described above. Examples of such a resin include polyvinyl butyral, polyester resin, polyurethane resin, and the like. Resins other than these hydrophilic (meth) acrylic resins may be hydrophilic or hydrophobic, but are preferably water-insoluble in order to prevent elution. However, even when other resins are contained, the above-described hydrophilic (meth) acrylic resin is preferably contained in an amount of 50% by weight or more of the total resin constituting the catalyst adhesion layer, and may be contained in an amount of 80% by weight or more. More preferably, it is more preferably 90% by weight or more.
触媒付着層の厚みは親水性（メタ）アクリル系樹脂を構成するモノマーの種類などにより異なるため一概には言えないが、０．０５〜３μｍが好ましく、０．０５〜０．５μｍがより好ましい。０．０５μｍ以上とすることにより、触媒を付着しやすくすることができ、３μｍ以下とすることにより、後述するパターン形成時に側面から現像液が進入して触媒付着層が剥離することを防止したり、絶縁特性の低下を防止することができる。また、０．５μｍ以下とすることにより、触媒付着層上に形成する無電解メッキ層および電解メッキ層を割れにくくすることができる。 Although the thickness of the catalyst adhesion layer varies depending on the type of monomer constituting the hydrophilic (meth) acrylic resin and cannot be generally specified, it is preferably 0.05 to 3 μm, more preferably 0.05 to 0.5 μm. By setting the thickness to 0.05 μm or more, the catalyst can be easily adhered, and by setting the thickness to 3 μm or less, it is possible to prevent the developer from entering from the side surface and peeling the catalyst adhesion layer during pattern formation described later. In addition, it is possible to prevent a decrease in insulation characteristics. Moreover, by setting it as 0.5 micrometer or less, the electroless-plating layer and electrolytic plating layer which are formed on a catalyst adhesion layer can be made hard to break.
触媒付着層は、当該層を構成する樹脂などの材料を適当な溶媒に溶解させた塗布液を、バーコーティング法などの公知の塗布法により非導電性基材上に塗布し、乾燥すること、あるいは、非導電性基材を構成する材料と触媒付着層を構成する材料とを共押し出しして成形することなどにより形成することができる。なお、触媒付着層は非導電性基材上の全面に設けられている必要はなく、一部分に設けられていてもよい。触媒付着層を非導電性基材の一部分に設けることにより、当該部分に選択的に触媒を付着させることができ、ひいては当該部分に選択的に無電解メッキ、電解メッキを行うことができる。 The catalyst adhesion layer is obtained by applying a coating solution obtained by dissolving a material such as a resin constituting the layer in a suitable solvent onto a non-conductive substrate by a known coating method such as a bar coating method, and drying. Or it can form by co-extrusion and shaping | molding the material which comprises a nonelectroconductive base material, and the material which comprises a catalyst adhesion layer. In addition, the catalyst adhesion layer does not need to be provided on the whole surface on a nonelectroconductive base material, and may be provided in a part. By providing the catalyst adhesion layer on a part of the non-conductive base material, the catalyst can be selectively adhered to the part, and thus the part can be selectively subjected to electroless plating and electrolytic plating.
以上、本発明の無電解メッキ形成材料の実施の形態として、触媒付着層を説明したが、上記触媒付着層を形成するための塗布液は、任意の被メッキ材料に塗布して無電解メッキ用触媒を付着させるための触媒付着用塗布液とすることができる。この触媒付着用塗布液を、上述した非導電性基材と同様の材料からなる任意の被メッキ材料の表面に塗布することにより、或いは被メッキ材料を触媒付着用塗布液に浸漬することにより、触媒付着層を形成し、無電解メッキ形成材料とすることができる。 As described above, the catalyst adhesion layer has been described as an embodiment of the electroless plating forming material of the present invention. However, the coating liquid for forming the catalyst adhesion layer is applied to any material to be plated for electroless plating. It can be set as the coating liquid for catalyst adhesion for making a catalyst adhere. By applying this coating liquid for catalyst adhesion to the surface of any material to be plated made of the same material as the non-conductive substrate described above, or by immersing the material to be plated in the coating liquid for catalyst adhesion, A catalyst adhesion layer can be formed and used as an electroless plating material.
以上のように、本発明の無電解メッキ形成材料あるいは本発明の触媒付着用塗布液により表面に触媒付着層を形成した被メッキ材料は、触媒付着層に自己架橋性を有する親水性モノマーを構成モノマーとして含む親水性（メタ）アクリル系樹脂を含むことから、触媒付着性能が良好であり、触媒付着層が非導電性基材から剥離したりメッキ液や触媒液に溶出したりすることがなく、さらに絶縁性が良好でありメッキ層が変色することもない。 As described above, the electroless plating forming material of the present invention or the material to be plated on which the catalyst adhesion layer is formed by the coating solution for catalyst adhesion of the present invention constitutes a hydrophilic monomer having self-crosslinking property on the catalyst adhesion layer. Because it contains a hydrophilic (meth) acrylic resin included as a monomer, the catalyst adhesion performance is good, and the catalyst adhesion layer does not peel from the non-conductive substrate or elute into the plating solution or catalyst solution. Furthermore, the insulating property is good and the plating layer is not discolored.
次に、本発明の無電解メッキの形成方法およびメッキ方法の実施の形態について説明する。 Next, an embodiment of the electroless plating forming method and the plating method of the present invention will be described.
本発明の無電解メッキの形成方法およびメッキ方法は、上述した本発明の無電解メッキ形成材料または触媒付着用塗布液を用いることが特徴であり、まず、無電解メッキ形成材料の触媒付着層に、あるいは触媒付着用塗布液を塗布した被メッキ材料の表面に、触媒を付着させる。 The electroless plating forming method and plating method of the present invention are characterized by using the above-described electroless plating forming material of the present invention or a catalyst adhesion coating solution. Alternatively, the catalyst is adhered to the surface of the material to be plated coated with the catalyst adhesion coating solution.
無電解メッキに対して触媒活性を有する金属微粒子（触媒）は、金、銀、ルテニウム、ロジウム、パラジウム、スズ、イリジウム、オスミウム、白金などを単独又は混合して用いることができる。これら触媒はコロイド溶液として用いることが好ましい。触媒のコロイド溶液を製造するには、触媒を含有する水溶性塩を水に溶解させ、界面活性剤を加えて激しく撹拌しながら還元剤を添加する方法が一般的であるが、他の公知の方法を用いてもよい。 Gold, silver, ruthenium, rhodium, palladium, tin, iridium, osmium, platinum or the like can be used alone or in combination as the metal fine particles (catalyst) having catalytic activity for electroless plating. These catalysts are preferably used as colloidal solutions. In order to produce a colloidal solution of a catalyst, a method of dissolving a water-soluble salt containing a catalyst in water, adding a surfactant and adding a reducing agent with vigorous stirring is generally used. A method may be used.
無電解メッキ形成材料の触媒付着層に触媒を付着させるには、この触媒のコロイド溶液を用いて、感受性化処理（センジタイジング）、活性化処理（アクチベーティング）を順次行う方法、あるいはキャタライジング、アクセレーティングを順次行う方法があげられる。本発明では、触媒付着層として触媒の付着性に優れた樹脂を用いていることから、触媒付着工程を極めて短時間で済ますことができ、また、短時間のため触媒付着層が触媒液に溶出することを防止することができる。 In order to attach the catalyst to the catalyst adhesion layer of the electroless plating forming material, a method of performing sensitization treatment (sending) and activation treatment (activation) sequentially using a colloidal solution of this catalyst, or a catalyst A method of sequentially performing rising and acceleration. In the present invention, since the resin having excellent catalyst adhesion is used as the catalyst adhesion layer, the catalyst adhesion process can be completed in a very short time, and the catalyst adhesion layer is eluted in the catalyst solution because of the short time. Can be prevented.
なお、触媒付着層に触媒を付着させる前に、無電解メッキ形成材料に対して、酸／アルカリ洗浄で脱脂処理を行うことが好ましい。本発明では、触媒付着層として親水性樹脂を用いていることから、脱脂処理も極めて短時間で済ますことができる。 In addition, before making a catalyst adhere to a catalyst adhesion layer, it is preferable to perform a degreasing process by acid / alkali washing | cleaning with respect to the electroless-plating formation material. In the present invention, since the hydrophilic resin is used as the catalyst adhesion layer, the degreasing treatment can be completed in a very short time.
また、一般的には、触媒付着層に触媒を付着させる前に、脱脂処理の他にさらにコンディショニングやプレディップという工程を行うが、本発明では、触媒付着層としてぬれ性に優れた樹脂を用いていることから、当該工程を省略することができる。 In general, before attaching the catalyst to the catalyst adhesion layer, a process called conditioning and pre-dip is performed in addition to the degreasing treatment. In the present invention, a resin having excellent wettability is used as the catalyst adhesion layer. Therefore, this step can be omitted.
触媒付着層に触媒を付着させた後は、無電解メッキを行う。無電解メッキは例えば、メッキすべき金属の水溶性化合物（通常は金属塩）、錯化剤、ｐＨ調整剤、還元剤およびメッキ助剤を含む無電解メッキ浴中に、触媒を付着させた無電解メッキ形成材料を浸漬することにより行うことができる。浴組成、温度、ｐＨ、浸漬時間などの諸条件を調整することにより、無電解メッキの厚みを調整することができる。 After the catalyst is adhered to the catalyst adhesion layer, electroless plating is performed. In electroless plating, for example, a non-electrolytic plating bath containing a water-soluble compound (usually a metal salt) of a metal to be plated, a complexing agent, a pH adjusting agent, a reducing agent and a plating aid is used. It can be performed by immersing the electrolytic plating material. The thickness of the electroless plating can be adjusted by adjusting various conditions such as bath composition, temperature, pH, and immersion time.
無電解メッキのメッキ用金属としては、無電解銅、無電解ニッケル、無電解銅・ニッケル・リン合金、無電解ニッケル・リン合金、無電解ニッケル・ホウ素合金、無電解コバルト・リン合金、無電解金、無電解銀、無電解パラジウム、無電解スズなどがあげられる。 Electroless plating metals include electroless copper, electroless nickel, electroless copper / nickel / phosphorous alloy, electroless nickel / phosphorous alloy, electroless nickel / boron alloy, electroless cobalt / phosphorous alloy, electroless Examples thereof include gold, electroless silver, electroless palladium, and electroless tin.
錯化剤、ｐＨ調整剤、メッキ助剤、還元剤は従来公知のものを使用することができる。 Conventionally known complexing agents, pH adjusting agents, plating aids, and reducing agents can be used.
無電解メッキを形成した後は、必要に応じて電解メッキを行う。この電解メッキに先立って、触媒付着層の架橋を進行させることが好ましい。架橋は、例えば触媒付着層の無電解メッキ形成材料を加熱することにより進行させる。加熱温度はや加熱時間は上述したとおりである。 After the electroless plating is formed, electrolytic plating is performed as necessary. Prior to this electrolytic plating, it is preferable to advance the crosslinking of the catalyst adhesion layer. Crosslinking proceeds by, for example, heating the electroless plating forming material of the catalyst adhesion layer. The heating temperature and the heating time are as described above.
自己架橋性モノマーは加熱しなくてもある程度架橋は進行するが、加熱することにより架橋を促進し、触媒付着層の無電解メッキ浴や電解メッキ浴への溶出を防止するとともに、絶縁性を高めることができる。また、触媒付着層の硬度が高くなるため、無電解メッキ層や電解メッキ層の割れを防止することができる。 Crosslinking proceeds to some extent even if the self-crosslinkable monomer is not heated, but by heating, the crosslinking is promoted, and the elution of the catalyst adhesion layer into the electroless plating bath and electrolytic plating bath is prevented and the insulation is improved. be able to. Moreover, since the hardness of a catalyst adhesion layer becomes high, the crack of an electroless-plating layer or an electroplating layer can be prevented.
架橋を進行させるタイミングは特に限定されないが、メッキ層の割れを防止するためには、触媒付着層に触媒を付着した後、電解メッキを行う前であることが好ましい。例えば無電解メッキの直前や電解メッキの直前に行うことができる。 The timing for proceeding with the crosslinking is not particularly limited. However, in order to prevent cracking of the plating layer, it is preferable that after the catalyst is attached to the catalyst adhesion layer, before the electrolytic plating is performed. For example, it can be performed immediately before electroless plating or immediately before electrolytic plating.
電解メッキは、無電解メッキが形成された無電解メッキ形成材料を、公知の電解メッキ浴に浸漬して通電することにより行うことができる。電流密度や通電時間を調整することにより、電解メッキの厚みを調整することができる。 Electrolytic plating can be performed by immersing the electroless plating forming material on which electroless plating is formed in a known electrolytic plating bath and energizing it. The thickness of the electrolytic plating can be adjusted by adjusting the current density and the energization time.
電解メッキの形成後は、必要に応じてパターン処理を行う。パターン処理は、例えば、電解メッキ上にフォトレジストを塗布し、露光を行い、露光部分あるいは未露光部分のフォトレジストを、電解メッキ、無電解メッキ、触媒付着層とともに現像液により除去することにより行うことができる。 After the electrolytic plating is formed, pattern processing is performed as necessary. The pattern processing is performed, for example, by applying a photoresist on electrolytic plating, performing exposure, and removing the exposed or unexposed photoresist with electrolytic developer, electroless plating, and catalyst adhesion layer with a developer. be able to.
以上のように、無電解メッキあるいは無電解メッキおよび電解メッキが形成された無電解メッキ形成材料は、プリント配線板、電磁波シールド部材、面状発熱体、帯電防止シート、アンテナなどに用いることができる。 As described above, the electroless plating or the electroless plating forming material on which the electroless plating and the electroplating are formed can be used for printed wiring boards, electromagnetic wave shielding members, planar heating elements, antistatic sheets, antennas, and the like. .
以下、実施例により本発明を更に説明する。なお、「部」、「％」は特に示さない限り、重量基準とする。 The following examples further illustrate the present invention. “Parts” and “%” are based on weight unless otherwise specified.
１．親水性（メタ）アクリル系樹脂ａ〜ｄの合成
（１）冷却管および攪拌装置を備えた反応容器中に、Ｎ−メチロールアクリルアミド（自己架橋性を有する親水性モノマー）とメチルメタクリレート（疎水性モノマー）とを、５：５のモル比で混入し、さらに希釈溶媒として酢酸エチルを加えて反応モノマー濃度を５０％とした。次いで、窒素ガスで反応容器内を充分に置換した後、オイルバスにて反応溶液の温度を６０〜９０℃に加熱した。加熱後、モノマー量に対して０．１５％の重合開始剤を添加し、反応を６〜８時間継続させて共重合させ、親水性（メタ）アクリル系樹脂ａ（固形分５０％）を得た。
（２）Ｎ−メチロールアクリルアミドとメチルメタクリレートとのモル比を２：８に変更した他は上記と同様にして、親水性（メタ）アクリル系樹脂ｂ（固形分５０％）を得た。
（３）上記（１）および（２）において、Ｎ−メチロールアクリルアミド（自己架橋性を有する親水性モノマー）の代わりに、２−ヒドロキシルエチルメタクリレート（自己架橋性を有さない親水性モノマー）を用いて、親水性（メタ）アクリル系樹脂ｃ（固形分５０％）および親水性（メタ）アクリル系樹脂ｄ（固形分５０％）を得た。
1. Synthesis of hydrophilic (meth) acrylic resins a to d (1) In a reaction vessel equipped with a condenser and a stirrer, N-methylolacrylamide (hydrophilic monomer having self-crosslinking property) and methyl methacrylate (hydrophobic monomer) ) In a molar ratio of 5: 5, and ethyl acetate was added as a diluent solvent to make the reaction monomer concentration 50%. Next, after sufficiently replacing the inside of the reaction vessel with nitrogen gas, the temperature of the reaction solution was heated to 60 to 90 ° C. in an oil bath. After heating, 0.15% of a polymerization initiator is added to the amount of monomer, and the reaction is continued for 6 to 8 hours for copolymerization to obtain a hydrophilic (meth) acrylic resin a (solid content 50%). It was.
(2) A hydrophilic (meth) acrylic resin b (solid content 50%) was obtained in the same manner as above except that the molar ratio of N-methylolacrylamide and methyl methacrylate was changed to 2: 8.
(3) In the above (1) and (2), 2-hydroxyethyl methacrylate (hydrophilic monomer having no self-crosslinking property) is used instead of N-methylolacrylamide (hydrophilic monomer having self-crosslinking property). Thus, a hydrophilic (meth) acrylic resin c (solid content 50%) and a hydrophilic (meth) acrylic resin d (solid content 50%) were obtained.
２．無電解メッキ形成材料の作製
［実施例１]
厚み１００μｍのポリエステルフィルム（ルミラーT60：東レ社）の一方の面に、親水性（メタ）アクリル系樹脂ａを溶媒で希釈してなる触媒付着層塗布液を塗布し、９０℃で３分加熱し、厚み１μｍの触媒付着層を形成し、実施例１の無電解メッキ形成材料を得た。
2. Production of electroless plating material [Example 1]
A catalyst adhesion layer coating solution obtained by diluting a hydrophilic (meth) acrylic resin a with a solvent is applied to one surface of a 100 μm thick polyester film (Lumirror T60: Toray Industries, Inc.) and heated at 90 ° C. for 3 minutes. Then, a catalyst adhesion layer having a thickness of 1 μm was formed, and the electroless plating material of Example 1 was obtained.
［実施例２]
実施例１の親水性（メタ）アクリル系樹脂ａを親水性（メタ）アクリル系樹脂ｂに変更した以外は実施例１と同様にして実施例２の無電解メッキ形成材料を得た。
[Example 2]
An electroless plating material of Example 2 was obtained in the same manner as in Example 1 except that the hydrophilic (meth) acrylic resin a in Example 1 was changed to the hydrophilic (meth) acrylic resin b.
［実施例３]
実施例１の親水性（メタ）アクリル系樹脂ａを下記の樹脂に変更した以外は実施例１と同様にして、実施例３の無電解メッキ形成材料を得た。
＜実施例３の樹脂＞
・親水性（メタ）アクリル系樹脂
（ケミトリーL-40M：綜研化学社、櫛形樹脂、疎水性モノマーの割合８６ｍｏｌ％）
（枝成分：Ｎ−メチロールアクリルアミドおよび２−ヒドロキシルエチルメタクリレート／何れも親水性モノマー、幹成分：メチルメタクリレート／疎水性モノマー）
[Example 3]
An electroless plating material of Example 3 was obtained in the same manner as in Example 1 except that the hydrophilic (meth) acrylic resin a in Example 1 was changed to the following resin.
<Resin of Example 3>
・ Hydrophilic (meth) acrylic resin (Chemitry L-40M: Soken Chemical Co., Ltd., comb resin, ratio of hydrophobic monomer 86 mol%)
(Branch component: N-methylolacrylamide and 2-hydroxylethyl methacrylate / both hydrophilic monomers, trunk component: methyl methacrylate / hydrophobic monomer)
［比較例１]
実施例１の親水性（メタ）アクリル系樹脂ａを親水性（メタ）アクリル系樹脂ｃに変更した以外は実施例１と同様にして比較例１の無電解メッキ形成材料を得た。
[Comparative Example 1]
The electroless plating material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the hydrophilic (meth) acrylic resin a in Example 1 was changed to the hydrophilic (meth) acrylic resin c.
［比較例２]
実施例１の親水性（メタ）アクリル系樹脂ａを親水性（メタ）アクリル系樹脂ｄに変更した以外は実施例１と同様にして比較例２の無電解メッキ形成材料を得た。
[Comparative Example 2]
The electroless plating material of Comparative Example 2 was obtained in the same manner as in Example 1 except that the hydrophilic (meth) acrylic resin a in Example 1 was changed to the hydrophilic (meth) acrylic resin d.
［比較例３]
厚み１００μｍのポリエステルフィルム（ルミラーT60：東レ社）の一方の面に、下記処方の硬化層塗布液を塗布し、１００℃で３０秒間乾燥させ、厚み１μｍの硬化層を形成した。硬化層形成後直ちに硬化層上に下記処方の触媒付着層塗布液を塗布し、１１０℃で５分間乾燥させ、厚み１．５μｍの触媒付着層を形成し、比較例３の無電解メッキ形成材料を得た。
[Comparative Example 3]
A cured layer coating solution having the following formulation was applied to one surface of a 100 μm thick polyester film (Lumirror T60: Toray Industries, Inc.) and dried at 100 ° C. for 30 seconds to form a cured layer having a thickness of 1 μm. Immediately after forming the cured layer, a catalyst adhesion layer coating solution having the following formulation is applied onto the cured layer and dried at 110 ° C. for 5 minutes to form a catalyst adhesion layer having a thickness of 1.5 μm. Got.
＜硬化層塗布液＞
・ポリエステル樹脂 １０部
（バイロン200：東洋紡績社、固形分１００％）
・イソシアネート系化合物 １部
（タケネートD160N：三井化学ポリウレタン社）
・メチルエチルケトン ４０部
・トルエン ４０部
・アノン １０部
<Curing layer coating solution>
・ 10 parts of polyester resin (Byron 200: Toyobo Co., Ltd., 100% solid content)
・ Isocyanate compound 1 part (Takenate D160N: Mitsui Chemicals Polyurethanes)
・ Methyl ethyl ketone 40 parts ・ Toluene 40 parts ・ Anone 10 parts
＜触媒付着層塗布液＞
・ポリビニルアルコール １部
（ゴーセノールNH20：日本合成化学工業社）
・水 ９部
<Catalyst adhesion layer coating solution>
・ Polyvinyl alcohol 1 part (Gohsenol NH20: Nippon Synthetic Chemical Industry)
・ 9 parts of water
［比較例４]
比較例３の硬化層塗布液のポリエステル樹脂を、同じくポリエステル樹脂（エリーテルUE3350：ユニチカ社、固形分１００％）に変更し、イソシアネート系化合物の添加量を１４部に変更した以外は比較例３と同様にして比較例４の無電解メッキ形成材料を得た。
[Comparative Example 4]
Comparative Example 3 except that the polyester resin of the cured layer coating solution of Comparative Example 3 was similarly changed to a polyester resin (Elitel UE3350: Unitika Ltd., solid content 100%) and the addition amount of the isocyanate compound was changed to 14 parts. Similarly, an electroless plating material of Comparative Example 4 was obtained.
実施例１〜３および比較例１〜４の無電解メッキ形成材料に下記の（１）〜（４）の工程を行い、触媒付着層上に無電解メッキ、電解メッキを形成した。 The following steps (1) to (4) were performed on the electroless plating forming materials of Examples 1 to 3 and Comparative Examples 1 to 4, and electroless plating and electrolytic plating were formed on the catalyst adhesion layer.
（１）脱脂処理：アルカリ水溶液を用いて６０秒脱脂処理を行った。
（２）触媒付与：触媒浴としてパラジウムおよびスズ混合のコロイド溶液を用い、感受性化処理を６０秒、活性化処理を３０秒順次行った。
（３）無電解メッキ：下記組成の無電解メッキ浴を用い、浴温６０℃、浸漬時間１５分の条件で無電解メッキを行った。
＜無電解メッキ浴＞
・硫酸銅五水和物 ０．０３Ｍ
・ＥＤＴＡ四水和物 ０．２４Ｍ
・ホルマリン ０．２０Ｍ
・ジピリジル １０ｐｐｍ
・界面活性剤 １００ｐｐｍ
（４）電解メッキ：電解メッキ浴として硫酸銅メッキ浴（キューブライトTHプロセス：在原ユージライト社）を用い、約３０μｍの厚みとなるまで電解メッキを行った。
(1) Degreasing treatment: Degreasing treatment was performed for 60 seconds using an alkaline aqueous solution.
(2) Catalyst application: A palladium and tin mixed colloidal solution was used as a catalyst bath, and the sensitization treatment was sequentially performed for 60 seconds and the activation treatment for 30 seconds.
(3) Electroless plating: Electroless plating was performed using an electroless plating bath having the following composition under conditions of a bath temperature of 60 ° C. and an immersion time of 15 minutes.
<Electroless plating bath>
・ Copper sulfate pentahydrate 0.03M
・ EDTA tetrahydrate 0.24M
・ Formalin 0.20M
・ Dipyridyl 10ppm
・ Surfactant 100ppm
(4) Electrolytic plating: Electrolytic plating was performed using a copper sulfate plating bath (Cubelite TH process: Azuma Yugilite Co., Ltd.) as an electrolytic plating bath to a thickness of about 30 μm.
無電解メッキ、電解メッキが形成された実施例１〜３および比較例１〜４の無電解メッキ形成材料について以下（１）〜（５）の項目の評価を行った。結果を表１に示す。 The following items (1) to (5) were evaluated for the electroless plating forming materials of Examples 1 to 3 and Comparative Examples 1 to 4 on which electroless plating and electrolytic plating were formed. The results are shown in Table 1.
（１）メッキの均一性
メッキが均一に形成されているかについて目視で評価を行った。ムラなく均一にメッキが形成されているものを「○」、ムラがあり不均一なものを「×」とした。
(1) Uniformity of plating Visually evaluated whether the plating was formed uniformly. “◯” indicates that the plating is uniformly formed without unevenness, and “X” indicates that there is unevenness and unevenness.
（２）接着性
メッキ面に隙間間隔１ｍｍの桝目が１００個できるように切れ目を入れ、切れ目を入れた箇所にセロハン粘着テープを貼って剥がした後に、膜（電解メッキ、無電解メッキ、触媒付着層、硬化層）が非導電性基材に接着している面積割合を目視で観察した。
(2) Adhesion Cut the plating surface so that 100 squares with a gap of 1 mm can be made, and apply the cellophane adhesive tape to the part where the cut is made, and then peel off the film (electrolytic plating, electroless plating, catalyst adhesion) The area ratio of the layer and the cured layer) adhered to the non-conductive substrate was visually observed.
（３）溶出防止性
純水に１０分間浸漬した後、取り出して十分に乾燥させ、浸漬前からの重量変化を測定した。その結果、触媒付着層が溶出せず重量変化がないものを「○」、触媒付着層の重量の２０％以上が溶出したものを「×」とした。
(3) Elution prevention property After being immersed in pure water for 10 minutes, it was taken out and dried sufficiently, and the weight change from before immersion was measured. As a result, the catalyst adhering layer did not elute and the weight did not change, “◯”, and the catalyst adhering layer 20% or more of the weight eluted was “x”.
（４）絶縁性（表面抵抗率）
実施例１〜３および比較例１〜４の無電解メッキ形成材料について、無電解メッキを形成した後に１３０℃で５分間、追加熱処理を行い、その後に電解メッキを形成した。電解メッキ形成後さらにレジスト膜をメッキ面に塗布し、酸エッチングによりパターンを形成後、レジスト膜をアルカリで剥離した。その後、メッキパターンがエッチングで除去されて露出した触媒付着層の表面抵抗率（ＪＩＳ Ｋ７１９４：１９９４）を測定した。また、触媒付着層形成直後の触媒付着層の表面抵抗率を測定した。追加熱処理の前後で、表面抵抗率が１０の何乗台から１０の何乗台に変化したかを表１に示す。なお、表１の左の数値は触媒付着層形成直後の数値であり、右の数値は追加熱処理後の数値である。左の数値より右の数値が大きければ、追加熱処理により絶縁性が向上していることを示すことになる。なお、表中の数値の単位は「Ω／□」である。
(4) Insulation (surface resistivity)
About the electroless-plating formation material of Examples 1-3 and Comparative Examples 1-4, after forming electroless plating, additional heat processing was performed for 5 minutes at 130 degreeC, and electrolytic plating was formed after that. After electrolytic plating was formed, a resist film was further applied to the plated surface, a pattern was formed by acid etching, and the resist film was peeled off with alkali. Then, the surface resistivity (JIS K7194: 1994) of the catalyst adhesion layer exposed by removing the plating pattern by etching was measured. Further, the surface resistivity of the catalyst adhesion layer immediately after formation of the catalyst adhesion layer was measured. Table 1 shows how many steps the surface resistivity has changed from 10 to 10 before and after the additional heat treatment. In addition, the numerical value on the left of Table 1 is a numerical value immediately after formation of the catalyst adhesion layer, and the numerical value on the right is a numerical value after the additional heat treatment. If the value on the right is larger than the value on the left, it indicates that the insulation is improved by the additional heat treatment. The unit of numerical values in the table is “Ω / □”.
（５）メッキ層の変色
無電解メッキを施した直後のメッキ層の色を基材側から観察した。その結果、メッキ層の色が鮮やかな銅色であったものを「○」、黒ずんでいたものを「×」とした。
(5) Discoloration of the plating layer The color of the plating layer immediately after the electroless plating was observed from the substrate side. As a result, “◯” indicates that the color of the plating layer is bright copper color, and “X” indicates that the plating layer is dark.
実施例１〜３の無電解メッキ形成材料は、触媒付着層が自己架橋性を有する親水性モノマーを構成モノマーとして含む親水性（メタ）アクリル系樹脂を含んでいることから、触媒付着性（上記結果の「均一性」および「接着性」）および触媒付着層の溶出防止性を満足しながらも、架橋を進行させることにより前記性能と相反する性能である絶縁性を良好にできるものであった（追加熱処理により表面抵抗率が１０の１１乗台から１０の１４乗台に上昇）。また、実施例１〜３の無電解メッキ形成材料は、メッキ層の触媒付着層との界面が変色することもなかった。 Since the electroless plating forming material of Examples 1 to 3 contains a hydrophilic (meth) acrylic resin containing a hydrophilic monomer having a self-crosslinking property as a constituent monomer, the catalyst adhesion layer (the above-described catalyst adhesion (described above)). The result was “uniformity” and “adhesiveness”) and anti-elution properties of the catalyst adhering layer, but it was possible to improve the insulation, which is a performance contrary to the above performance, by proceeding with the crosslinking. (Surface resistivity increased from 10 11 to 10 14 by additional heat treatment). Moreover, the electroless-plating formation material of Examples 1-3 did not discolor the interface with the catalyst adhesion layer of a plating layer.
比較例１、２の無電解メッキ形成材料は、触媒付着層が親水性（メタ）アクリル系樹脂を含んでいるものの、当該樹脂が自己架橋性を有する親水性モノマーを構成モノマーとして含んでいないことから、絶縁性を良好にできないものであった（追加熱処理しても表面抵抗率は１０の１２乗台のまま）。 In the electroless plating material of Comparative Examples 1 and 2, the catalyst adhesion layer contains a hydrophilic (meth) acrylic resin, but the resin does not contain a hydrophilic monomer having self-crosslinking property as a constituent monomer. Therefore, the insulating property could not be improved (the surface resistivity remained at the 10 12th power level even after the additional heat treatment).
比較例３、４の無電解メッキ形成材料は、触媒付着層が、自己架橋性を有する親水性モノマーを構成モノマーとして含む親水性（メタ）アクリル系樹脂を含んでいないことから、絶縁性を良好にできないものであった（追加熱処理しても表面抵抗率は１０の１０乗台のまま）。また、比較例３、４の無電解メッキ形成材料は、メッキ層の触媒付着層との界面が変色してしまうものであった。 The electroless plating material of Comparative Examples 3 and 4 has good insulation properties because the catalyst adhesion layer does not contain a hydrophilic (meth) acrylic resin containing a hydrophilic monomer having a self-crosslinking property as a constituent monomer. (The surface resistivity remained at the 10th power range even after additional heat treatment). Moreover, the electroless-plating formation material of the comparative examples 3 and 4 discolored the interface with the catalyst adhesion layer of a plating layer.
［メッキ層のひび割れの考察］
上記（４）のように追加熱処理後に電解メッキが形成された実施例１〜３および比較例１〜４の無電解メッキ形成材料の電解メッキ面表面のひび割れを観察した。その結果、自己架橋が進行した実施例１〜３の無電解メッキ形成材料は殆どひび割れることなく、自己架橋を起こさない比較例１〜４の無電解メッキ形成材料に対する優位性が確認された。
また、実施例１〜３の無電解メッキ形成材料の触媒付着層の厚み（１．０μｍ）を、０．７μｍ、０．５μｍ、０．２μｍ、０．０５μｍに変更したものを作製し、電解メッキ面のひび割れを観察した。その結果、触媒付着層の厚みが薄くなるほどひび割れを起こしにくいことが確認された。
[Consideration of cracks in plating layer]
Cracks on the surface of the electroplating surface of the electroless plating materials of Examples 1 to 3 and Comparative Examples 1 to 4 in which the electroplating was formed after the additional heat treatment as in (4) above were observed. As a result, the electroless plating forming materials of Examples 1 to 3 in which self-crosslinking progressed were hardly cracked, and the superiority to the electroless plating forming materials of Comparative Examples 1 to 4 that did not cause self-crosslinking was confirmed.
Moreover, what changed the thickness (1.0 micrometer) of the catalyst adhesion layer of the electroless-plating formation material of Examples 1-3 into 0.7 micrometer, 0.5 micrometer, 0.2 micrometer, and 0.05 micrometer was produced, and electrolysis was carried out. The plated surface was observed for cracks. As a result, it was confirmed that cracks are less likely to occur as the thickness of the catalyst adhesion layer becomes thinner.
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