JP4640583B2 - Pretreatment liquid for electroless plating and electroless plating method using the same - Google Patents

Pretreatment liquid for electroless plating and electroless plating method using the same Download PDF

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JP4640583B2
JP4640583B2 JP2005069059A JP2005069059A JP4640583B2 JP 4640583 B2 JP4640583 B2 JP 4640583B2 JP 2005069059 A JP2005069059 A JP 2005069059A JP 2005069059 A JP2005069059 A JP 2005069059A JP 4640583 B2 JP4640583 B2 JP 4640583B2
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electroless plating
plated
plating
pretreatment liquid
electroless
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高明 納堂
澄子 中島
諭 赤沢
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Showa Denko Materials Co Ltd
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Hitachi Chemical Co Ltd
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本発明は、無電解めっき用前処理液、およびこれを用いた無電解めっき方法に関する。   The present invention relates to a pretreatment liquid for electroless plating and an electroless plating method using the same.

プラスティック、ガラス等の非導電性物質からなる被めっき物へ無電解めっきを行なう場合、無電解めっき反応を速やかに開始させるための当該反応に活性な触媒を反応場に付与する必要がある。そのため、従来より、無電解めっきを行なう場合、被めっき物をめっき液に投入する前の前処理として、脱脂洗浄およびコンディショニングの後、上記触媒の前駆体(例えば、触媒が金属パラジウムの場合にはパラジウム塩等)を含む液中に被めっき物を浸漬し、次いで、活性化処理などの処理を施して、被めっき物の表面に上記触媒を付与するための処理が行われている。   When electroless plating is performed on an object to be plated made of a non-conductive material such as plastic or glass, it is necessary to provide a reaction field with a catalyst active in the reaction for promptly starting the electroless plating reaction. Therefore, conventionally, when performing electroless plating, as a pretreatment before putting the object to be plated into the plating solution, after degreasing and conditioning, the precursor of the catalyst (for example, when the catalyst is metallic palladium) The object to be plated is immersed in a liquid containing a palladium salt, etc., and then subjected to a treatment such as an activation treatment to give the catalyst to the surface of the object to be plated.

例えば、触媒溶液として強酸性のパラジウム−錫触媒液を使用し、この液に被めっき物を浸漬して触媒核を付与し、次いで、酸又はアルカリ処理を行い、触媒活性を発現させた後、得られる被めっき物を自己触媒型の無電解めっき液に浸漬してめっき皮膜(めっき層)を生成する方法が提案されている(例えば、下記特許文献1参照)。   For example, using a strongly acidic palladium-tin catalyst solution as a catalyst solution, immersing an object to be plated in this solution to give a catalyst nucleus, then performing an acid or alkali treatment to express the catalytic activity, There has been proposed a method in which an object to be plated is immersed in an autocatalytic electroless plating solution to generate a plating film (plating layer) (for example, see Patent Document 1 below).

なお、本明細書において、「自己触媒型の無電解めっき液」とは、無電解めっきのうち、めっき反応に還元剤を利用する「化学還元めっき」に使用される液であって、以下の触媒作用を有する金属(めっき層を形成する金属)の原料となる金属イオンが含有されているものを示す。すなわち、上記の金属とは、還元剤により原料の金属イオンが還元されることにより被めっき物の表面に金属として析出した際に、還元剤と金属イオンとの反応に対して触媒作用(自己触媒作用)を有するものである。   In the present specification, the “self-catalyzed electroless plating solution” is a solution used for “chemical reduction plating” using a reducing agent in a plating reaction in electroless plating, The metal ion which becomes a raw material of the metal (metal which forms a plating layer) which has a catalytic action is shown. That is, the above metal is a catalyst (autocatalyst) for the reaction between the reducing agent and the metal ion when the raw material metal ion is reduced by the reducing agent and deposited as a metal on the surface of the object to be plated. It has an action).

無電解めっきの代表的な適用事例に、電子機器に搭載するプリント配線板の製造工程で、スルーホールやビアホールの電気的接続を行なうための層間接続技術として、無電解めっきが行なわれている。近年の電子機器の小型化、軽量化に伴い、スルーホールやビアホールの小径化が進み、特にドリルやレーザーによって開けられた穴へ無電解めっきを行なう際、孔内の有機樹脂や無機材料(特にガラス繊維の破断面)でめっきが未析出となり、被めっき物の表面の一部が外部に露出する現象が多発した。この現象は層間の電気接続部の信頼性が低下することが懸念される。この原因の一つとして、前記パラジウム−錫触媒が有機樹脂や無機材料に吸着していないことが挙げられる。   As a typical application example of electroless plating, electroless plating is performed as an interlayer connection technique for electrically connecting through holes and via holes in a manufacturing process of a printed wiring board mounted on an electronic device. As electronic devices have become smaller and lighter in recent years, through holes and via holes have become smaller in diameter, especially when electroless plating is performed on holes opened by drills or lasers. Plating did not precipitate at the fracture surface of the glass fiber), and a phenomenon in which part of the surface of the object to be plated was exposed to the outside occurred frequently. This phenomenon is a concern that the reliability of the electrical connection between the layers is reduced. One reason for this is that the palladium-tin catalyst is not adsorbed on organic resins or inorganic materials.

この現象を防ぐための手法として、例えば、親水性を有し、且つキレートを形成しやすい活性官能基を分子中に有するシランカップリング剤を被めっき物の表面に存在させ、然る後に無電解めっきを施す方法が提案されている(例えば、下記特許文献2参照)。また、被めっき物を、アクリルアミドと第4アンモニウム化合物または第4フォスフォニウム化合物との共重合水溶液に接触させ、然るのち、前記パラジウム−錫触媒液に接触させる方法が提案されている(例えば、下記特許文献3参照)。   As a method for preventing this phenomenon, for example, a silane coupling agent having an active functional group that has hydrophilicity and easily forms a chelate in the molecule is present on the surface of the object to be plated, and then electroless A method of performing plating has been proposed (see, for example, Patent Document 2 below). Further, a method has been proposed in which an object to be plated is brought into contact with a copolymer aqueous solution of acrylamide and a quaternary ammonium compound or a fourth phosphonium compound, and then contacted with the palladium-tin catalyst solution (for example, , See Patent Document 3 below).

また、被めっき物の洗浄力を高め、且つ、めっき皮膜の密着力を向上させるためのめっき前処理として、シランカップリング剤、非イオン性界面活性剤、エチレンジアミンテトラ酢酸又はその塩又はその誘導体、および第4アンモニウム塩を含む水溶液よりなる無電解めっき用の前処理液を用いる方法が提案されている(下記特許文献4参照)。   In addition, as a plating pretreatment for increasing the cleaning power of an object to be plated and improving the adhesion of a plating film, a silane coupling agent, a nonionic surfactant, ethylenediaminetetraacetic acid or a salt thereof or a derivative thereof, And a method using a pretreatment liquid for electroless plating comprising an aqueous solution containing a quaternary ammonium salt has been proposed (see Patent Document 4 below).

また、プリント配線板の製造工程において、スルーホール内のめっきつきまわり性を大きく向上させるためのめっき前処理として、非イオン性界面活性剤、フッ素を含む界面活性剤、金属錯化物、およびポリアクリルアミドを骨格に持つ界面活性剤を含むpH10以上の水溶液よりなる無電解めっき用の前処理液を用いる方法が提案されている(下記特許文献5参照)。
米国特許第3011920号明細書 特公昭59−52701号公報 特公昭63−21752号公報 特開平4−56776号公報 特開平4−198486号公報
In the printed wiring board manufacturing process, non-ionic surfactants, fluorine-containing surfactants, metal complexes, and polyacrylamide are used as pre-plating treatments to greatly improve the plating coverage in the through holes. There has been proposed a method using a pretreatment solution for electroless plating comprising an aqueous solution having a pH of 10 or more containing a surfactant having a skeleton (see Patent Document 5 below).
U.S. Pat. No. 3,119,920 Japanese Examined Patent Publication No.59-52701 Japanese Examined Patent Publication No. 63-21752 JP-A-4-56776 Japanese Patent Laid-Open No. 4-198486

しかしながら、上述の特許文献2〜5の前処理を使用する無電解めっき方法では、近年のプリント配線板の小径スルーホール、具体的には0.3mmφ以下、且つアスペクト比(スルーホール長さ/スルーホール径)が5.0以上のスルーホールや、小径ビアホール、具体的には0.2mmφ以下、且つアスペクト比(ビア長さ/ビア径)が2.0以上のビアホールへ無電解めっきを行なう際、孔内の有機樹脂や無機材料(特に、ガラス繊維の破断面)へのめっき析出が不十分であり、未だ十分な信頼性を得ることができていないなどの課題がある。   However, in the electroless plating method using the pretreatment described in Patent Documents 2 to 5, a small diameter through hole of a recent printed wiring board, specifically 0.3 mmφ or less, and an aspect ratio (through hole length / through hole) When electroless plating is performed on through-holes having a hole diameter of 5.0 or more or via holes having a small diameter, specifically 0.2 mmφ or less and an aspect ratio (via length / via diameter) of 2.0 or more. There are problems such as insufficient deposition of plating on organic resin and inorganic material (especially, the fracture surface of the glass fiber) in the holes, and sufficient reliability has not yet been obtained.

本発明は上記問題点に鑑みてなされたものであり、優れた脱脂・洗浄力を有し、且つ、めっき反応に活性な触媒を被めっき物の表面、特に有機樹脂や無機材料に容易かつ確実に付着させるため、該被めっき物の表面にコンディショニングを行なうための無電解めっき用前処理液を提供することを目的とする。また、本発明は、かかる無電解めっき用前処理液を用いた無電解めっき方法を提供することを目的とする。   The present invention has been made in view of the above-mentioned problems, and has an excellent degreasing and cleaning power and an active catalyst for plating reaction on the surface of an object to be plated, particularly an organic resin or an inorganic material, easily and reliably. An object of the present invention is to provide a pretreatment liquid for electroless plating for conditioning the surface of the object to be plated. Another object of the present invention is to provide an electroless plating method using such a pretreatment liquid for electroless plating.

本発明者らは、鋭意検討を重ねた結果、以下に示す特定の成分組成の条件を満たす前処理液を構成することにより、上記目的が達成可能であることを見出し、本発明に到達した。すなわち、本発明は以下の通りである。
(1)1種以上の非イオン性界面活性剤と、1種以上の陽イオン性樹脂と、1種以上の金属イオンの錯化剤を含む無電解めっき用前処理液であって、前記陽イオン性樹脂が、ポリアルキレンポリアミンであり、更に1種以上のアルカリ金属化合物を含むことを特徴とする無電解めっき用前処理液。
(2)更に1種以上のシランカップリング剤を含むことを特徴とする項(1)に記載の無電解めっき用前処理液。
(3)1種以上の非イオン性界面活性剤と、1種以上の陽イオン性樹脂と、1種以上の金属イオンの錯化剤を含む無電解めっき用前処理液であって、前記陽イオン性樹脂が、ポリアルキレンポリアミンであり、更に1種以上のシランカップリング剤を含むことを特徴とする無電解めっき用前処理液。
(4)項(1)から(3)いずれかに記載の無電解めっき用前処理液に被めっき物を浸漬する工程、被めっき物に触媒を付与する工程、被めっき物に付与した触媒を活性化する工程、被めっき物に無電解めっきを行う工程を有する無電解めっき方法。
As a result of intensive studies, the present inventors have found that the above object can be achieved by constituting a pretreatment liquid that satisfies the conditions of the specific component composition shown below, and have reached the present invention. That is, the present invention is as follows.
(1) A pretreatment liquid for electroless plating comprising at least one nonionic surfactant, at least one cationic resin, and at least one metal ion complexing agent, ionic resin, Ri Oh polyalkylene polyamine, further pre-treatment liquid electroless plating which comprises one or more alkali metal compounds.
(2) The pretreatment liquid for electroless plating according to item (1), further comprising one or more silane coupling agents .
(3) A pretreatment liquid for electroless plating comprising at least one nonionic surfactant, at least one cationic resin, and at least one metal ion complexing agent, The pretreatment liquid for electroless plating , wherein the ionic resin is a polyalkylene polyamine and further contains one or more silane coupling agents .
(4) The step of immersing the object to be plated in the pretreatment liquid for electroless plating according to any one of items (1) to (3) , the step of applying a catalyst to the object to be plated, the catalyst applied to the object of plating The electroless plating method which has the process of activating, and the process of electroless-plating to a to-be-plated object.

この前処理液を用いることにより、被めっき物を効率よく洗浄し、且つ、該被めっき物表面を、パラジウム−錫触媒が容易に吸着しやすい状態にすることができる。更に、無電解めっき後に形成しためっき皮膜の密着性が良好であるという特徴を有する。上記の陽イオン性樹脂(ポリアルキレンポリアミン)は、分子中の主鎖に陽イオンを形成する基を有し、且つその基に陽イオン性窒素原子を有するため、水溶液中において、正の電荷密度が高く、これが被めっき物に吸着すると、被めっき物へのパラジウム−錫触媒の吸着を促進させ、また無電解めっき後のめっき皮膜の密着力を向上させることができる。   By using this pretreatment liquid, the object to be plated can be efficiently washed, and the surface of the object to be plated can easily be adsorbed by the palladium-tin catalyst. Furthermore, it has the characteristic that the adhesiveness of the plating film formed after electroless plating is favorable. The above cationic resin (polyalkylene polyamine) has a group that forms a cation in the main chain in the molecule and has a cationic nitrogen atom in the group. When this is adsorbed to the object to be plated, the adsorption of the palladium-tin catalyst to the object to be plated can be promoted, and the adhesion of the plating film after electroless plating can be improved.

また、本発明は、上記前処理液に被めっき物を浸漬し、次いで触媒付与工程および触媒活性化工程を含む無電解めっきを行なうことを特徴とする無電解めっき方法を提供する。このめっき方法により、無電解めっき後の被めっき物の表面の一部が外部に露出したり、めっき皮膜が均一な厚さで形成されない、といった問題の発生が十分に防止され、該被めっき物の表面にめっき皮膜を均一に形成することができる。   Moreover, this invention provides the electroless-plating method characterized by immersing a to-be-plated object in the said pretreatment liquid, and performing electroless plating including a catalyst provision process and a catalyst activation process then. This plating method sufficiently prevents the occurrence of problems such as a part of the surface of the object to be plated after electroless plating being exposed to the outside or the formation of a plating film with a uniform thickness. A plating film can be uniformly formed on the surface of the film.

以下、本発明の好適な実施の形態について詳細に説明する。先ず、本発明の無電解めっき用前処理液の好適な一実施形態について説明する。   Hereinafter, preferred embodiments of the present invention will be described in detail. First, a preferred embodiment of the pretreatment liquid for electroless plating of the present invention will be described.

本実施形態の無電解めっき用前処理液は、1種以上の非イオン性界面活性剤と、1種以上の陽イオン性樹脂と、1種以上の金属イオンの錯化剤と、1種以上のアルカリ金属化合物とを含む水溶液であり、且つ陽イオン性樹脂が、ポリアルキレンポリアミンであることを特徴とする。
The pretreatment liquid for electroless plating according to the present embodiment includes at least one nonionic surfactant, at least one cationic resin, at least one metal ion complexing agent, and at least one type. An aqueous solution containing an alkali metal compound , and the cationic resin is a polyalkylene polyamine.

非イオン性界面活性剤は、液の表面張力を低下させ小径スルーホールや小径ビアホールへの液廻りを促すとともに、被めっき物表面の脱脂洗浄を行う。例として、脂肪酸モノグリセリンエステル、脂肪酸ポリグリコールエステル、脂肪酸ソルビタンエステル、脂肪酸モノエタノールアミド、脂肪酸ジエタノールアミド、脂肪酸ポリエチレングリコール縮合物、脂肪酸アミド・ポリエチレングリコール縮合物、脂肪族アルコール・ポリエチレングリコール縮合物、脂肪族アミン・ポリエチレングリコール縮合物、脂肪族メルカプタン・ポリエチレングリコール縮合物、アルキルフェノール・ポリエチレングリコール縮合物、ポリプロピレングリコール・ポリエチレングリコール縮合物などが挙げられるが、これらに限定されない。   The nonionic surfactant lowers the surface tension of the liquid and promotes liquid circulation to a small diameter through hole or small diameter via hole, and also performs degreasing cleaning of the surface of the object to be plated. Examples include fatty acid monoglycerin ester, fatty acid polyglycol ester, fatty acid sorbitan ester, fatty acid monoethanolamide, fatty acid diethanolamide, fatty acid polyethylene glycol condensate, fatty acid amide / polyethylene glycol condensate, fatty alcohol / polyethylene glycol condensate, fat An aliphatic amine / polyethylene glycol condensate, an aliphatic mercaptan / polyethylene glycol condensate, an alkylphenol / polyethylene glycol condensate, a polypropylene glycol / polyethylene glycol condensate, and the like, but are not limited thereto.

非イオン性界面活性剤の濃度は0.01〜100g/Lであることが好ましい。また、良好な洗浄効果および小径孔への液廻り効果、経済性および環境への負荷を考慮に入れると、0.1〜20g/Lがより好ましい。濃度が0.01g/L未満であると、洗浄効果および小径孔への液廻り効果が得られないため発明の効果が得られないため好ましくない。また、濃度が100g/Lを超えると経済性および環境への負荷が大きいため好ましくない。   The concentration of the nonionic surfactant is preferably 0.01 to 100 g / L. Moreover, if considering the good cleaning effect, the effect of the liquid around the small-diameter hole, the economy and the load on the environment, 0.1 to 20 g / L is more preferable. If the concentration is less than 0.01 g / L, it is not preferable because the cleaning effect and the effect of flowing around the small-diameter hole cannot be obtained, and the effect of the invention cannot be obtained. In addition, if the concentration exceeds 100 g / L, it is not preferable because the economy and the load on the environment are large.

陽イオン性樹脂は、被めっき物へのパラジウム−錫の吸着を促進させ、また無電解めっき後のめっき皮膜の密着力を向上させる。陽イオン性樹脂は、ポリアルキレンポリアミンであり、具体的には、ポリエチレンイミン、ポリプロピレンイミン、ポリアルキレンイミン等が挙げられる。   The cationic resin promotes the adsorption of palladium-tin to the object to be plated and improves the adhesion of the plating film after electroless plating. The cationic resin is a polyalkylene polyamine, and specific examples thereof include polyethylene imine, polypropylene imine, polyalkylene imine and the like.

陽イオン性樹脂の分子量は300〜300000であることが好ましい。分子量が300未満であると、被めっき物への吸着が起こりにくくなり、それに伴いパラジウム−錫触媒の吸着が起こりにくくなるため、めっき未析出部が発生し好ましくない。また、分子量が300000を超えると、前処理液の粘度が大きくなり、小径孔への液廻り効果が得られないため好ましくない。   The molecular weight of the cationic resin is preferably 300 to 300,000. When the molecular weight is less than 300, adsorption to the object to be plated is difficult to occur, and accordingly, adsorption of the palladium-tin catalyst is difficult to occur. On the other hand, if the molecular weight exceeds 300,000, the viscosity of the pretreatment liquid is increased, and the effect of liquid circulation to small-diameter holes cannot be obtained, which is not preferable.

陽イオン性樹脂の濃度は、0.05〜50g/Lが好ましい。また、経済性および環境への負荷を考慮に入れると、0.05〜10g/Lがより好ましい。濃度が0.05g/L未満であると、被めっき物への吸着量が小さくなり、それに伴いパラジウム−錫触媒の吸着が起こりにくくなるため、めっきの未析出部が発生し好ましくない。また、濃度が50g/L以上を超えると、経済性および環境への負荷が大きいため好ましくない。   The concentration of the cationic resin is preferably 0.05 to 50 g / L. Moreover, if economic efficiency and environmental load are taken into consideration, 0.05 to 10 g / L is more preferable. When the concentration is less than 0.05 g / L, the amount of adsorption to the object to be plated is reduced, and the adsorption of the palladium-tin catalyst is less likely to occur. On the other hand, if the concentration exceeds 50 g / L or more, the economical efficiency and the load on the environment are large, which is not preferable.

金属イオンの錯化剤は、洗浄過程で、被めっき物から溶出した金属イオン、例えばNi2+、Fe2+、Fe3+、Co2+、Sn2+、Pb2+、Pd2+、Cr3+、Zn2+、Cd2+、Cu2+、Ag等を捕捉することによって洗浄効果を向上させるとともに、液の安定性を向上させる。錯化剤は窒素含有の配位子が好ましく、例として、アンモニア、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、グリシン、アラニン、ジメチルアミン、アセトアミド、ホルムアミド、N,N−ジメチルホルムアミド、アセトニトリル、ピリジン、2−ヒドロキシピリジン、2−アミノピリジン、2−メチルピリジン、尿素、エチレンジアミン、エチレンジアミン四酢酸、エチレンジアミン四酢酸二ナトリウム塩、エチレンジアミン四酢酸四ナトリウム塩、ヒドロキシエチルエチレンジアミン三酢酸、シクロヘキサンジアミン四酢酸等が挙げられるが、これらに限定されない。 The metal ion complexing agent is a metal ion eluted from the object to be plated in the cleaning process, such as Ni 2+ , Fe 2+ , Fe 3+ , Co 2+ , Sn 2+ , Pb 2+ , Pd 2+ , Cr 3+ , Zn 2+ , Cd. By capturing 2+ , Cu 2+ , Ag + and the like, the cleaning effect is improved and the stability of the liquid is improved. The complexing agent is preferably a nitrogen-containing ligand, such as ammonia, monoethanolamine, diethanolamine, triethanolamine, glycine, alanine, dimethylamine, acetamide, formamide, N, N-dimethylformamide, acetonitrile, pyridine, 2-hydroxypyridine, 2-aminopyridine, 2-methylpyridine, urea, ethylenediamine, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid tetrasodium salt, hydroxyethylethylenediaminetriacetic acid, cyclohexanediaminetetraacetic acid, etc. However, it is not limited to these.

錯化剤の濃度は、0.01〜100g/Lが好ましい。また、経済性および環境への負荷を考慮に入れると、0.01〜20g/Lがより好ましい。濃度が0.01g/L未満であると、繰り返しの使用により液の安定性が悪くなるため好ましくない。また、濃度が100g/L以上を超えると、経済性および環境への負荷が大きいため好ましくない。   The concentration of the complexing agent is preferably 0.01 to 100 g / L. Moreover, if economic load and environmental load are taken into consideration, 0.01 to 20 g / L is more preferable. If the concentration is less than 0.01 g / L, the stability of the liquid deteriorates due to repeated use, which is not preferable. On the other hand, if the concentration exceeds 100 g / L or more, the economic efficiency and the load on the environment are large, which is not preferable.

ルカリ金属化合物は、これを加えることにより、被めっき物の脱脂および洗浄効果がより大きくなる。アルカリ金属化合物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、リン酸三リチウム、リン酸三ナトリウム、リン酸三カリウム、ケイ酸リチウム、ケイ酸ナトリウム、及びケイ酸カリウムなどが挙げられるが、これらに限定されない。
A alkali metal compounds, by adding this, degreasing and cleaning effects of the object to be plated becomes larger. Examples of alkali metal compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, lithium silicate, sodium silicate, And potassium silicate and the like, but are not limited thereto.

アルカリ金属化合物の濃度は、0.01〜200g/Lが好ましい。また、洗浄効果および経済性および環境への負荷を考慮に入れると、0.05〜50g/Lがより好ましい。濃度が200g/Lを超えると、安全性の問題から好ましくない。   The concentration of the alkali metal compound is preferably 0.01 to 200 g / L. Moreover, if considering the cleaning effect, economy, and environmental load, 0.05 to 50 g / L is more preferable. When the concentration exceeds 200 g / L, it is not preferable from the viewpoint of safety.

また、本実施形態の無電解めっき用前処理液は、1種以上の非イオン性界面活性剤と、1種以上の陽イオン性樹脂と、1種以上の金属イオンの錯化剤に加え、更に1種以上のシランカップリング剤を含み、且つ陽イオン性樹脂が、ポリアルキレンポリアミンであることを特徴とする。また、本実施形態の無電解めっき用前処理液は、1種以上の非イオン性界面活性剤と、1種以上の陽イオン性樹脂と、1種以上の金属イオンの錯化剤に加え、1種以上のアルカリ金属化合物と1種以上のシランカップリング剤を含むことがより好ましい。シランカップリング剤は、無電解めっき後、めっき皮膜と被めっき物、特に無機材料との密着力を増加させることができる。シランカップリング剤としては、アミノ系のシランカップリング剤が好ましく、例として、3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、N−フェニル−3−アミノプロピルトリメトキシシラン、N−2(アミノエチル)3−アミノプロピルトリメトキシシラン、N−2(アミノエチル)3−アミノプロピルメチルジエトキシシラン、N−2(アミノエチル)3−アミノプロピルメチルジメトキシシラン等が挙げられるが、これらに限定されない。 In addition, the pretreatment liquid for electroless plating of the present embodiment is in addition to one or more nonionic surfactants, one or more cationic resins, and one or more metal ion complexing agents, further seen contains one or more silane coupling agents, and cationic resin, characterized in that it is a polyalkylene polyamine. In addition, the pretreatment liquid for electroless plating of the present embodiment is in addition to one or more nonionic surfactants, one or more cationic resins, and one or more metal ion complexing agents, More preferably, it contains one or more alkali metal compounds and one or more silane coupling agents. The silane coupling agent can increase the adhesion between the plating film and the object to be plated, particularly an inorganic material, after electroless plating. As the silane coupling agent, an amino silane coupling agent is preferable, and examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- Examples include 2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldiethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, and the like. It is not limited to.

シランカップリング剤の濃度は、0.01〜100g/Lが好ましい。また、経済性および環境への負荷を考慮に入れると、0.01〜10g/Lがより好ましい。濃度が0.01g/L未満であると、めっき皮膜の密着力が小さく発明の効果が得られないため好ましくない。濃度が100g/Lを超えると、カップリング剤の凝集が起こり発明の効果が得られないため好ましくない。   The concentration of the silane coupling agent is preferably 0.01 to 100 g / L. Moreover, when economic efficiency and environmental load are taken into consideration, 0.01 to 10 g / L is more preferable. When the concentration is less than 0.01 g / L, the adhesion of the plating film is small and the effect of the invention cannot be obtained, which is not preferable. If the concentration exceeds 100 g / L, coupling agent aggregation occurs and the effects of the invention cannot be obtained.

また、本実施形態の無電解めっき方法は、上記本実施形態の無電解めっき用前処理液に被めっき物を浸漬する工程、被めっき物に触媒を付与する工程、被めっき物に付与した触媒を活性化する工程、被めっき物に無電解めっきを行う工程を有することを特徴とする。   The electroless plating method of the present embodiment includes a step of immersing the object to be plated in the pretreatment liquid for electroless plating of the present embodiment, a step of applying a catalyst to the object of plating, and a catalyst applied to the object of plating. And a step of performing electroless plating on an object to be plated.

無電解めっきを行なう際の、本発明の無電解めっき用前処理液の温度は、30〜90℃が好ましい。温度が30℃未満であると脱脂洗浄力およびコンディショニングの効果が得られなくなるため好ましくない。また、温度が90℃を超えると、水分が多量に蒸発し、濃度の変化が大きくなり、また安全性の問題から好ましくない。   The temperature of the pretreatment liquid for electroless plating of the present invention when performing electroless plating is preferably 30 to 90 ° C. If the temperature is less than 30 ° C., the degreasing power and conditioning effect cannot be obtained, which is not preferable. On the other hand, when the temperature exceeds 90 ° C., a large amount of water evaporates, the change in concentration becomes large, and it is not preferable from the viewpoint of safety.

また本発明の無電解めっき用前処理液に被めっき物を浸漬する時間は30秒〜30分が好ましい。また、本発明の効果を得つつ、作業効率を高めるためには、1分〜15分がより好ましい。浸漬する時間が30秒未満であると、本発明の効果が得られなくなるため好ましくない。また、浸漬時間が30分を超えると、作業効率が著しく悪くなるため好ましくない。   The time for immersing the object to be plated in the pretreatment liquid for electroless plating of the present invention is preferably 30 seconds to 30 minutes. Moreover, in order to improve work efficiency, obtaining the effect of this invention, 1 minute-15 minutes are more preferable. When the immersion time is less than 30 seconds, the effect of the present invention cannot be obtained, which is not preferable. Further, if the immersion time exceeds 30 minutes, the working efficiency is remarkably deteriorated, which is not preferable.

本発明の無電解めっき用前処理液に浸漬した後に得られる被めっき物を、更に水洗を行ってもよい。この操作は、被めっき物表面に付着した無電解めっき用前処理液のうちの余分な分量を除去するためのものであり、被めっき物表面に付着した無電解めっき用前処理液の液膜を完全に除去するものではない。洗浄条件を最適化することにより、最適量の被めっき物表面に付着した水溶液の液膜を残しつつ、余分な分量を除去することができる。また水洗に使用する水は、イオン交換水であることがより好ましい。   The object to be plated obtained after being immersed in the pretreatment liquid for electroless plating of the present invention may be further washed with water. This operation is for removing the excess amount of the pretreatment liquid for electroless plating adhering to the surface of the object to be plated, and the liquid film of the pretreatment liquid for electroless plating adhering to the surface of the object to be plated Is not completely removed. By optimizing the cleaning conditions, it is possible to remove an excessive amount while leaving a liquid film of an aqueous solution adhering to the surface of the object to be plated in an optimal amount. The water used for washing is more preferably ion exchange water.

本発明の無電解めっき用前処理液に被めっき物を浸漬した後、触媒付与工程および触媒活性化工程を行なう。触媒付与工程には、公知の酸性パラジウム−錫触媒液を、触媒活性化工程には酸性もしくはアルカリ性の活性化液をそれぞれ用いることができる。   After immersing the object to be plated in the pretreatment liquid for electroless plating of the present invention, a catalyst application step and a catalyst activation step are performed. A known acidic palladium-tin catalyst solution can be used in the catalyst application step, and an acidic or alkaline activation solution can be used in the catalyst activation step.

本発明では、触媒付与工程および触媒活性化工程後に得られる被めっき物を、自己触媒型の無電解めっき液に浸漬することが好ましい。使用する自己触媒型の無電解めっき液としては、公知の自己触媒型の無電解めっき液を用いることができる。例えば、無電解銅めっき液、無電解ニッケル−リンめっき液、無電解ニッケル−ホウ素めっき液、無電解パラジウムめっき液、無電解銀めっき液、無電解金めっき液等がある。   In this invention, it is preferable to immerse the to-be-plated object obtained after a catalyst provision process and a catalyst activation process in an autocatalytic electroless plating solution. As the autocatalytic electroless plating solution to be used, a known autocatalytic electroless plating solution can be used. For example, electroless copper plating solution, electroless nickel-phosphorous plating solution, electroless nickel-boron plating solution, electroless palladium plating solution, electroless silver plating solution, electroless gold plating solution and the like.

本発明の無電解めっき方法でめっきされる被めっき物は、PET樹脂、エポキシ樹脂、ポリイミド樹脂等のプラスティック、ガラス、セラミックス、プリント基板等の複合材料などが挙げられるが、これらに限定されない。なお、本発明の無電解めっき用前処理液及び無電解めっき方法は、スルーホールを有するプリント基板等に好適である。   Examples of the object to be plated by the electroless plating method of the present invention include, but are not limited to, plastic materials such as PET resin, epoxy resin, and polyimide resin, and composite materials such as glass, ceramics, and printed circuit boards. The pretreatment liquid for electroless plating and the electroless plating method of the present invention are suitable for printed boards having through holes.

以下、本発明の好適な実施例について更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
参考例1)
下記表1に示すように、イオン交換水に、非イオン性界面活性剤としてポリオキシエチレンオクチルフェニルエーテル(日本油脂株式会社製ノニオンHS−210)5.0g/L、金属イオンの錯化剤としてトリエタノールアミン(関東化学株式会社製)3.0g/L、陽イオン性樹脂としてポリエチレンイミン(和光純薬工業株式会社製、数平均分子量10000)0.05g/L、0.5g/Lおよび5.0g/Lの濃度で溶解した。この水溶液を「参考前処理」(無電解めっき用前処理液:参考−A〜参考−C)とした。
Hereinafter, preferred examples of the present invention will be described in more detail, but the present invention is not limited to these examples.
( Reference Example 1)
As shown in Table 1 below, in ion exchange water, 5.0 g / L of polyoxyethylene octyl phenyl ether (Nonion HS-210, manufactured by NOF Corporation) as a nonionic surfactant, as a complexing agent for metal ions Triethanolamine (manufactured by Kanto Chemical Co., Inc.) 3.0 g / L, polyethyleneimine as a cationic resin (manufactured by Wako Pure Chemical Industries, Ltd., number average molecular weight 10,000) 0.05 g / L, 0.5 g / L and 5 Dissolved at a concentration of 0.0 g / L. This aqueous solution was referred to as “ reference pretreatment liquid ” (pretreatment liquid for electroless plating: Reference- A to Reference- C).

被めっき物として、エポキシ系銅張積層板であるMCL−E−679(日立化成工業株式会社製、商品名、厚さ1.6mm)にドリルを用いて穴径0.2mmのスルーホールを形成し、デスミア処理を行なったものを使用した。そして、下記の工程で無電解銅めっきを行った。   Form a through-hole with a hole diameter of 0.2 mm using a drill on MCL-E-679 (trade name, thickness 1.6 mm, manufactured by Hitachi Chemical Co., Ltd.), which is an epoxy-based copper-clad laminate, as an object to be plated And what was desmeared was used. And the electroless copper plating was performed at the following process.

先ず、「参考前処理液」の液温を60℃に調整し、この液中に、上記被めっき物を5分間浸漬し、被めっき物の洗浄およびコンディショニングを行った。次に、室温(25℃)で2分間水洗した。次に、得られた被めっき物を、ソフトエッチング液である「HET−100」(日立化成工業株式会社製、商品名)に、室温(25℃)で2分間浸漬した。次に、得られた被めっき物を室温で2分間水洗した。次に、パラジウム−錫触媒の前処理液である「PD−301」(日立化成工業株式会社製、商品名)に室温(25℃)で2分間浸漬した。次に、得られた被めっき物をパラジウム−錫触媒液である「HS−202B」(日立化成工業株式会社製、商品名)に室温(25℃)で5分間浸漬した。次に、得られた被めっき物を室温(25℃)で2分間水洗した。
First, the liquid temperature of the “ reference pretreatment liquid” was adjusted to 60 ° C., and the object to be plated was immersed in this liquid for 5 minutes to wash and condition the object to be plated. Next, it was washed with water at room temperature (25 ° C.) for 2 minutes. Next, the obtained object to be plated was immersed in “HET-100” (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is a soft etching solution, at room temperature (25 ° C.) for 2 minutes. Next, the obtained object to be plated was washed with water at room temperature for 2 minutes. Next, it was immersed for 2 minutes at room temperature (25 ° C.) in “PD-301” (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is a pretreatment liquid for a palladium-tin catalyst. Next, the obtained object to be plated was immersed in “HS-202B” (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is a palladium-tin catalyst solution, at room temperature (25 ° C.) for 5 minutes. Next, the obtained object to be plated was washed with water at room temperature (25 ° C.) for 2 minutes.

次に、得られた被めっき物を、酸性の処理液である「ADP−601」(日立化成工業株式会社製、商品名)に室温(25℃)で5分間浸漬した。このようにして無電解めっきのためのパラジウム触媒を被めっき物のスルーホール内に析出させた。次に、得られた被めっき物を室温(25℃)で2分間水洗した。   Next, the obtained object to be plated was immersed in “ADP-601” (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an acidic treatment solution, at room temperature (25 ° C.) for 5 minutes. In this way, a palladium catalyst for electroless plating was deposited in the through hole of the object to be plated. Next, the obtained object to be plated was washed with water at room temperature (25 ° C.) for 2 minutes.

次に、得られた被めっき物を自己触媒型の無電解銅めっき液である「CUST−201」(日立化成工業株式会社製、商品名)に、液温25℃で15分間浸漬した(めっき工程)。次に、得られた被めっき物を室温(25℃)で5分間水洗した。次に、得られた被めっき物を80℃で10分間乾燥した。このようにして、被めっき物のスルーホール内に無電解銅めっき皮膜を形成した。   Next, the obtained object to be plated was immersed in “CUST-201” (trade name, manufactured by Hitachi Chemical Co., Ltd.) which is an autocatalytic electroless copper plating solution at a liquid temperature of 25 ° C. for 15 minutes (plating). Process). Next, the obtained object to be plated was washed with water at room temperature (25 ° C.) for 5 minutes. Next, the obtained object to be plated was dried at 80 ° C. for 10 minutes. In this way, an electroless copper plating film was formed in the through hole of the object to be plated.

次に、被めっき物のスルーホールへのめっきつきまわり性を評価するため、無電解銅めっき後の被めっき物を、図1に示すように切断し、めっき内壁面の下方から光をあてて光の透過の有無を調べるバックライトテストを行なった。無電解銅めっきの未析出部が存在した場合は、光が透過し、図2(a)に示すような像が観察され、また無電解銅めっきの未析出部が存在しない場合は、図2(b)に示すように、光の透過は観測されない。参考例1において、バックライトテストの結果、図2(b)に示すように、光の透過は観測されなかった。
Next, in order to evaluate the throwing power of the object to be plated to the through hole, the object to be plated after electroless copper plating is cut as shown in FIG. 1, and light is applied from below the inner wall surface of the plating. A backlight test was conducted to examine the presence or absence of light transmission. When there is an undeposited portion of electroless copper plating, light is transmitted, and an image as shown in FIG. 2A is observed, and when there is no undeposited portion of electroless copper plating, FIG. As shown in (b), no light transmission is observed. In Reference Example 1 , as a result of the backlight test, no light transmission was observed as shown in FIG.

(実施例
下記表1に示すように、イオン交換水に、非イオン性界面活性剤としてポリオキシエチレンオクチルフェニルエーテル5.0g/L、金属イオンの錯化剤としてトリエタノールアミン3.0g/L、陽イオン性樹脂としてポリエチレンイミン0.5g/L、アルカリ金属化合物として水酸化ナトリウム(関東化学株式会社製)1.0g/L、10g/Lおよび50g/Lの濃度で溶解した。この水溶液を「前処理液」(無電解めっき用前処理液:−A〜−C)とした。
(Example 1 )
As shown in Table 1 below, in ion-exchanged water, polyoxyethylene octylphenyl ether 5.0 g / L as a nonionic surfactant, triethanolamine 3.0 g / L as a metal ion complexing agent, cation Polyethyleneimine 0.5 g / L as a soluble resin, and sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) 1.0 g / L, 10 g / L and 50 g / L as an alkali metal compound were dissolved. This aqueous solution was designated as “pretreatment liquid 1 ” (pretreatment liquid for electroless plating: 1- A to 1- C).

被めっき物として、参考例1と同じくスルーホールを形成した銅張積層板を使用した。そして、「参考前処理液」を「前処理液」に変更した以外は、参考例1と同じ工程で無電解銅めっきを行なった。次に、被めっき物のスルーホールへのめっきつきまわり性を評価するため、参考例1と同じ方法でバックライトテストを行なった。バックライトテストの結果、図2(b)に示すように、光の透過は観測されなかった。
As the object to be plated, a copper-clad laminate having through holes formed as in Reference Example 1 was used. Then, electroless copper plating was performed in the same process as Reference Example 1 except that the “ reference pretreatment liquid” was changed to “pretreatment liquid 1 ”. Next, a backlight test was performed in the same manner as in Reference Example 1 in order to evaluate the throwing power of the object to be plated on the through hole. As a result of the backlight test, no light transmission was observed as shown in FIG.

(実施例
下記表1に示すように、イオン交換水に、非イオン性界面活性剤としてポリオキシエチレンオクチルフェニルエーテル5.0g/L、金属イオンの錯化剤としてトリエタノールアミン3.0g/L、陽イオン性樹脂としてポリエチレンイミン0.5g/L、アルカリ金属化合物として水酸化ナトリウム10g/L、シランカップリング剤として「KBE−903」(3−アミノプロピルトリエトキシシラン、信越化学工業株式会社製、商品名)0.05g/L、0.5g/Lおよび5.0g/Lの濃度で溶解した。この水溶液を「前処理液」(無電解めっき用前処理液:−A〜−C)とした。
(Example 2 )
As shown in Table 1 below, in ion-exchanged water, polyoxyethylene octylphenyl ether 5.0 g / L as a nonionic surfactant, triethanolamine 3.0 g / L as a metal ion complexing agent, cation Polyethyleneimine 0.5 g / L as a conductive resin, sodium hydroxide 10 g / L as an alkali metal compound, “KBE-903” (3-aminopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name as a silane coupling agent ) Dissolved at concentrations of 0.05 g / L, 0.5 g / L and 5.0 g / L. This aqueous solution was designated as “pretreatment liquid 2 ” (pretreatment liquid for electroless plating: 2- A to 2- C).

被めっき物として、参考例1と同じくスルーホールを形成した銅張積層板を使用した。そして、「参考前処理液」を「前処理液」に変更した以外は、参考例1と同じ工程で無電解銅めっきを行なった。次に、被めっき物のスルーホールへのめっきつきまわり性を評価するため、参考例1と同じ方法でバックライトテストを行なった。バックライトテストの結果、図2(b)に示すように、光の透過は観測されなかった。
As the object to be plated, a copper-clad laminate having through holes formed as in Reference Example 1 was used. Then, electroless copper plating was performed in the same process as Reference Example 1 except that the “ reference pretreatment liquid” was changed to “pretreatment liquid 2 ”. Next, a backlight test was performed in the same manner as in Reference Example 1 in order to evaluate the throwing power of the object to be plated on the through hole. As a result of the backlight test, no light transmission was observed as shown in FIG.

(比較例1)
下記表2に示すように、「参考前処理液」の陽イオン性樹脂であるポリエチレンイミン(和光純薬工業株式会社製、数平均分子量10000)の濃度を0g/L(無電解めっき用前処理液:1−D)にした以外は、参考例1と同様に行なった。バックライトテストの結果、図2(a)に示すように、光の透過が観測された。
(Comparative Example 1)
As shown in Table 2 below, the concentration of polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd., number average molecular weight 10,000), which is a cationic resin of the “ reference pretreatment liquid” , is 0 g / L (pretreatment for electroless plating). Solution: Performed in the same manner as in Reference Example 1 except that the solution was changed to 1-D). As a result of the backlight test, light transmission was observed as shown in FIG.

(比較例2)
下記表2に示すように、「前処理液」の陽イオン性樹脂であるポリエチレンイミン(和光純薬工業株式会社製、数平均分子量10000)の濃度を0g/L(無電解めっき用前処理液:2−D〜2−F)にした以外は、参考例1と同様に行なった。バックライトテストの結果、図2(a)に示すように、光の透過が観測された。
(Comparative Example 2)
As shown in Table 2 below, the concentration of polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd., number average molecular weight 10,000), which is a cationic resin of “pretreatment liquid 1 ”, is 0 g / L (pretreatment for electroless plating). liquid: except that the 2-D~2-F), was carried out in the same manner as in reference example 1. As a result of the backlight test, light transmission was observed as shown in FIG.

(比較例3)
下記表2に示すように、「前処理液」の陽イオン性樹脂であるポリエチレンイミン(和光純薬工業株式会社製、数平均分子量10000)の濃度を0g/L(無電解めっき用前処理液:3−D〜3−F)にした以外は、参考例1と同様に行なった。バックライトテストの結果、図2(a)に示すように、光の透過が観測された。
(Comparative Example 3)
As shown in the following Table 2, the concentration of polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd., number average molecular weight 10,000), which is a cationic resin of “pretreatment liquid 2 ”, is 0 g / L (pretreatment for electroless plating). liquid: except that the 3-D~3-F), was carried out in the same manner as in reference example 1. As a result of the backlight test, light transmission was observed as shown in FIG.

(比較例4)
下記表2に示すように、「参考前処理液」参考−B)の金属イオンの錯化剤であるトリエタノールアミン(関東化学株式会社製)の濃度を0g/L(無電解めっき用前処理液:1−E)にした以外は、参考例1と同様に行なった。バックライトテストの結果、図2(a)に示すように、光の透過が観測された。
(Comparative Example 4)
As shown in Table 2 below, the concentration of triethanolamine (manufactured by Kanto Chemical Co., Ltd.), which is a metal ion complexing agent in the “ reference pretreatment liquid” ( reference- B), is 0 g / L (before electroless plating). Treatment liquid: It was carried out in the same manner as in Reference Example 1 except that it was changed to 1-E). As a result of the backlight test, light transmission was observed as shown in FIG.

(比較例5)
下記表2に示すように、「参考前処理液」参考−B)の非イオン性界面活性剤であるポリオキシエチレンオクチルフェニルエーテル(日本油脂株式会社製ノニオンHS−210)の濃度を0g/L(無電解めっき用前処理液:1−F)にした以外は、参考例1と同様に行なった。バックライトテストの結果、図2(a)に示すように、光の透過が観測された。
(Comparative Example 5)
As shown in Table 2 below, the concentration of polyoxyethylene octylphenyl ether (Nonion HS-210, manufactured by NOF Corporation), which is a nonionic surfactant of “ Reference Pretreatment Solution” ( Reference- B), is 0 g / The same procedure as in Reference Example 1 was conducted except that L (pretreatment liquid for electroless plating: 1-F) was used. As a result of the backlight test, light transmission was observed as shown in FIG.

Figure 0004640583
Figure 0004640583

Figure 0004640583
Figure 0004640583

バックライトテストの結果から明らかなように、本発明の無電解めっき用前処理液1、2(1−A〜1−C、2−A〜2−C)は、陽イオン性樹脂の濃度が0g/Lである無電解めっき用前処理液:(1−D、2−D〜2−F、3−D〜3−F)と比較して、被めっき物のスルーホールへのめっきつきまわり性に優れることが確認された。また、比較例4及び比較例5に示されたように、本発明の効果を得るためには、非イオン性界面活性剤および錯化剤が必要であることが確認された。以上説明したとおり、本発明によれば、優れた脱脂・洗浄力を有しており、めっき反応に活性な触媒を被めっき物の表面に容易かつ確実に付着させることのできる無電解めっき用前処理液を提供することが可能となる。また、本発明によれば、かかる無電解めっき用前処理液を用いることにより、被めっき物とめっき皮膜との密着性が良好なめっきを行なうことが可能な無電解めっき方法を提供することができる。

As is clear from the results of the backlight test, the pretreatment liquids 1 and 2 (1-A to 1-C, 2-A to 2- C) for electroless plating of the present invention have a cationic resin concentration. Pretreatment solution for electroless plating that is 0 g / L: Compared with (1-D, 2-D to 2-F, 3-D to 3-F), plating around the through-hole of the object to be plated It was confirmed that it was excellent in performance. Further, as shown in Comparative Example 4 and Comparative Example 5, it was confirmed that a nonionic surfactant and a complexing agent are necessary to obtain the effects of the present invention. As described above, according to the present invention, before electroless plating, which has an excellent degreasing and cleaning power and can easily and reliably adhere a catalyst active in a plating reaction to the surface of an object to be plated. A treatment liquid can be provided. Moreover, according to the present invention, by using such a pretreatment liquid for electroless plating, it is possible to provide an electroless plating method capable of performing plating with good adhesion between an object to be plated and a plating film. it can.

(a)は、被めっき物の切断箇所を示す平面図であり、(b)は切断した被めっき物のバックライトテストを表す概略面である。(A) is a top view which shows the cut location of a to-be-plated thing, (b) is a schematic surface showing the backlight test of the to-be-plated thing. (a)及び(b)は、バックライトテストにおけるスルーホールの光の透過の有無を示す光学顕微鏡写真である。(A) And (b) is an optical microscope photograph which shows the presence or absence of light transmission of the through hole in a backlight test.

符号の説明Explanation of symbols

1:スルーホール
2:切断面A
3:切断面B
4:被めっき物(エポキシ系銅張積層板)
5:光学顕微鏡
6:光(バックライト)



1: Through hole 2: Cut surface A
3: Cut surface B
4: Object to be plated (epoxy copper-clad laminate)
5: Optical microscope 6: Light (backlight)



Claims (4)

1種以上の非イオン性界面活性剤と、1種以上の陽イオン性樹脂と、1種以上の金属イオンの錯化剤を含む無電解めっき用前処理液であって、前記陽イオン性樹脂が、ポリアルキレンポリアミンであり、更に1種以上のアルカリ金属化合物を含むことを特徴とする無電解めっき用前処理液。 A pretreatment liquid for electroless plating comprising one or more nonionic surfactants, one or more cationic resins, and one or more metal ion complexing agents, wherein the cationic resins but Ri Oh polyalkylene polyamine, further pre-treatment liquid electroless plating which comprises one or more alkali metal compounds. 更に1種以上のシランカップリング剤を含むことを特徴とする請求項1に記載の無電解めっき用前処理液。 The pretreatment liquid for electroless plating according to claim 1, further comprising one or more silane coupling agents . 1種以上の非イオン性界面活性剤と、1種以上の陽イオン性樹脂と、1種以上の金属イオンの錯化剤を含む無電解めっき用前処理液であって、前記陽イオン性樹脂が、ポリアルキレンポリアミンであり、更に1種以上のシランカップリング剤を含むことを特徴とする無電解めっき用前処理液。 A pretreatment liquid for electroless plating comprising one or more nonionic surfactants, one or more cationic resins, and one or more metal ion complexing agents, wherein the cationic resins Is a polyalkylene polyamine, and further contains one or more silane coupling agents . 請求項1から3いずれかに記載の無電解めっき用前処理液に被めっき物を浸漬する工程、被めっき物に触媒を付与する工程、被めっき物に付与した触媒を活性化する工程、被めっき物に無電解めっきを行う工程を有する無電解めっき方法。 A step of immersing the object to be plated in the pretreatment liquid for electroless plating according to any one of claims 1 to 3 , a step of imparting a catalyst to the object to be plated, a step of activating the catalyst imparted to the object of plating, An electroless plating method including a step of performing electroless plating on an object to be plated.
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