JP2018076560A - Electroless copper plating, removal liquid of catalyst used for deposition of electroless copper plating, and application thereof - Google Patents
Electroless copper plating, removal liquid of catalyst used for deposition of electroless copper plating, and application thereof Download PDFInfo
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Abstract
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本発明は、プリント配線板の製造に用いられる、無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒の除去液およびその用途に関する。 The present invention relates to an electroless copper plating used for the production of a printed wiring board and a catalyst removal solution used for the deposition of the electroless copper plating and its use.
プリント配線板の製造において、無電解銅めっきをシード層とした一般的なセミアディティブ法では、無電解銅めっき上に電解銅めっきを行った後、フラッシュエッチング（Ｆ／Ｅ）液により無電解銅めっきを除去し、次に無電解銅めっきの析出に用いられたパラジウム触媒を除去する、というこれらの２工程を通してパターンが形成されている。またパターンは電解銅めっきで形成されるのが一般的だが、特殊な工法では電解銅めっき上に電解錫または錫合金めっきを行ってパターンが形成される場合、電解錫または電解錫合金めっきのみでパターンが形成される場合がある。 In the production of printed wiring boards, in a general semi-additive method using electroless copper plating as a seed layer, electroless copper plating is performed on the electroless copper plating, and then electroless copper is used by a flash etching (F / E) solution. The pattern is formed through these two steps of removing the plating and then removing the palladium catalyst used to deposit the electroless copper plating. The pattern is generally formed by electrolytic copper plating. However, in a special method, when the pattern is formed by performing electrolytic tin or tin alloy plating on the electrolytic copper plating, only electrolytic tin or electrolytic tin alloy plating is used. A pattern may be formed.
これらの工程を１工程にすることはプリント配線板の製造において、有利ではあるが、従来より無電解銅めっきの除去に用いられている硫酸、過酸化水素系のＦ／Ｅ液（特許文献１）は、錫めっきや錫合金めっきを溶解してしまい、またパラジウム触媒の除去もできない。これ以外の技術としては、アルカリエッチング（特許文献２、３）が知られており、錫めっきや錫合金めっきを溶解せず無電解銅めっきを溶解可能なため適用が考えられるが、電解銅めっきもある程度溶解してしまい、またパラジウム触媒の除去もできない。 Although making these steps one step is advantageous in the production of printed wiring boards, sulfuric acid and hydrogen peroxide-based F / E solutions conventionally used for removing electroless copper plating (Patent Document 1) ) Dissolves tin plating and tin alloy plating, and the palladium catalyst cannot be removed. Alkaline etching (Patent Documents 2 and 3) is known as another technology, and it can be applied because it can dissolve electroless copper plating without dissolving tin plating or tin alloy plating. However, the palladium catalyst cannot be removed.
従って、本発明は無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を１工程で除去できる技術を提供することを課題とする。 Therefore, this invention makes it a subject to provide the technique which can remove the catalyst used for precipitation of electroless copper plating and electroless copper plating by 1 process.
本発明者らは、上記課題を解決するために鋭意研究した結果、酸およびチオ尿素化合物を組み合わせることにより、無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を１工程で除去できることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above-mentioned problems, the present inventors can remove the catalyst used for the electroless copper plating and the deposition of the electroless copper plating in one step by combining the acid and the thiourea compound. The present invention was completed.
すなわち、本発明は、酸およびチオ尿素化合物を含有することを特徴とする無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒の除去液である。 That is, the present invention is an electroless copper plating characterized by containing an acid and a thiourea compound and a catalyst removal solution used for the deposition of the electroless copper plating.
また、本発明は、基板に設けられた無電解銅めっき上に、電解銅めっき、電解錫めっきおよび電解錫合金めっきからなる群から選ばれる金属の１種または２種以上を用いてパターンを形成した後、上記除去液で無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を除去することを特徴とする基板上へのパターン形成方法である。 Moreover, this invention forms a pattern using the 1 type (s) or 2 or more types of the metal chosen from the group which consists of electrolytic copper plating, electrolytic tin plating, and electrolytic tin alloy plating on the electroless copper plating provided in the board | substrate. After that, the pattern forming method on the substrate is characterized by removing the electroless copper plating and the catalyst used for the deposition of the electroless copper plating with the above-mentioned removing solution.
更に、本発明は、無電解銅めっきを設けた基板を、上記除去液で処理することを特徴とする無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒の除去方法である。 Furthermore, this invention is the removal method of the catalyst used for precipitation of electroless copper plating and electroless copper plating characterized by processing the board | substrate provided with electroless copper plating with the said removal liquid.
本発明の除去液は、無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を除去することができ、また、電解銅めっき、電解錫めっきおよび電解錫合金めっきを除去しない。 The removing liquid of the present invention can remove the catalyst used for the deposition of electroless copper plating and electroless copper plating, and does not remove electrolytic copper plating, electrolytic tin plating, and electrolytic tin alloy plating.
本発明の基板上へのパターン形成方法は、上記性質を有する本発明の除去液を用いることにより、パターン形成において不要な無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を除去することができるため、正確なパターンを形成することができる。 The pattern formation method on the substrate of the present invention removes the electroless copper plating unnecessary for pattern formation and the catalyst used for the deposition of the electroless copper plating by using the removal liquid of the present invention having the above properties. Therefore, an accurate pattern can be formed.
本発明の無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒の除去方法は、上記性質を有する本発明の除去液を用いることにより、無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を除去することができる。 The removal method of the catalyst used for the electroless copper plating and electroless copper plating deposition of the present invention is suitable for the deposition of electroless copper plating and electroless copper plating by using the removal liquid of the present invention having the above properties. The catalyst used can be removed.
本発明の無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒の除去液（以下、「本発明の除去液」という）は、酸およびチオ尿素化合物を含有するものである。 The catalyst removing solution used for electroless copper plating and electroless copper plating deposition of the present invention (hereinafter referred to as “the removing solution of the present invention”) contains an acid and a thiourea compound.
本発明の除去液に用いられる酸は、特に限定されず、無機酸または有機酸の何れでもよい。無機酸としては、例えば、硫酸、塩酸、燐酸、ホウフッ化水素酸、ケイフッ化水素酸、スルファミン酸等が挙げられる。また、有機酸としては、例えば、メタンスルホン酸、エタンスルホン酸、１−プロパンスルホン酸、２−プロパンスルホン酸、１−ブタンスルホン酸、２−ブタンスルホン酸、ペンタンスルホン酸、イセチオン酸等のスルホン酸、ギ酸、酢酸、プロピオン酸、酪酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、フマル酸、マレイン酸、グリコール酸、グルコン酸、リンゴ酸、クエン酸、酒石酸等のカルボン酸等が挙げられる。これらの酸は１種または２種以上を組み合わせて用いることもできる。これらの酸の中でも硫酸、塩酸、メタンスルホン酸、エタンスルホン酸、イセチオン酸、ギ酸、酢酸、グルコン酸、リンゴ酸、クエン酸、酒石酸が好ましく、特に硫酸、塩酸、メタンスルホン酸、リンゴ酸、クエン酸、酒石酸が好ましい。 The acid used for the removal liquid of the present invention is not particularly limited, and may be either an inorganic acid or an organic acid. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, borohydrofluoric acid, silicohydrofluoric acid, sulfamic acid and the like. Examples of the organic acid include sulfones such as methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid, and isethionic acid. Acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, glycolic acid, gluconic acid, malic acid, citric acid, tartaric acid, etc. Is mentioned. These acids can be used alone or in combination of two or more. Among these acids, sulfuric acid, hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, isethionic acid, formic acid, acetic acid, gluconic acid, malic acid, citric acid, and tartaric acid are preferable, and sulfuric acid, hydrochloric acid, methanesulfonic acid, malic acid, citric acid are particularly preferable. Acid and tartaric acid are preferred.
本発明の除去液における酸の含有量は、特に限定されず、例えば、本発明の除去液の規定度が０.１〜１３Ｎ、好ましくは０.５〜１０Ｎとなるように含有させればよい。 The content of the acid in the removal liquid of the present invention is not particularly limited, and for example, it may be contained so that the normality of the removal liquid of the present invention is 0.1 to 13N, preferably 0.5 to 10N. .
本発明の除去液に用いられるチオ尿素化合物は、特に限定されないが、例えば、チオ尿素、Ｎ−メチルチオ尿素、１，３−ジメチルチオ尿素、トリメチルチオ尿素、テトラメチルチオ尿素、１，３−ジエチルチオ尿素、１，３−ジブチルチオ尿素、１，１，３−トリブチルチオ尿素、チオアセトアミド、４−メチルチオセミカブバジド、１−アリル２−チオ尿素、１−アセチル−２−チオ尿素、１−アリル−３−（２−ヒドロキシエチル）−２−チオ尿素、１，３−ビス（ジメチルアミノポロピル）−２−チオ尿素、１−フェニル−２−チオ尿素、１，３−ジフェニルチオ尿素、１−アセチル−２−チオ尿素、１−アリル−３−（２−ヒドロキシエチル）−２−チオ尿素、Ｎ−ベンゾイルチオ尿素、グアニルチオ尿素、２，５−ジチオビチオ尿素等が挙げられる。これらのチオ尿素化合物は１種または２種以上を組み合わせて用いることもできる。これらのチオ尿素化合物の中でもチオ尿素、Ｎ−メチルチオ尿素、１，３−ジメチルチオ尿素、トリメチルチオ尿素、テトラメチルチオ尿素、１，３−ジエチルチオ尿素が好ましく、特にチオ尿素、Ｎ−メチルチオ尿素、１，３−ジメチルチオ尿素、トリメチルチオ尿素が好ましい。 The thiourea compound used in the removing solution of the present invention is not particularly limited. For example, thiourea, N-methylthiourea, 1,3-dimethylthiourea, trimethylthiourea, tetramethylthiourea, 1,3-diethylthiourea, 1,3-dibutylthiourea, 1,1,3-tributylthiourea, thioacetamide, 4-methylthiosemicarbabazide, 1-allyl-2-thiourea, 1-acetyl-2-thiourea, 1-allyl-3 -(2-hydroxyethyl) -2-thiourea, 1,3-bis (dimethylaminopropyl) -2-thiourea, 1-phenyl-2-thiourea, 1,3-diphenylthiourea, 1-acetyl 2-thiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, N-benzoylthiourea, guanylthiourea, 2,5-dithiobithio Arsenide, and the like. These thiourea compounds can be used alone or in combination of two or more. Among these thiourea compounds, thiourea, N-methylthiourea, 1,3-dimethylthiourea, trimethylthiourea, tetramethylthiourea, 1,3-diethylthiourea are preferable, and thiourea, N-methylthiourea, 1, 3-dimethylthiourea and trimethylthiourea are preferred.
本発明の除去液におけるチオ尿素化合物の含有量は、特に限定されず、例えば、１〜２００ｇ／Ｌが好ましく、特に３０〜１５０ｇ／Ｌが好ましい。 The content of the thiourea compound in the removal liquid of the present invention is not particularly limited, and is preferably, for example, 1 to 200 g / L, particularly preferably 30 to 150 g / L.
本発明の除去液には、更に、電解銅めっきの溶解を抑制するために陰イオン界面活性剤を含有させることが好ましい。陰イオン界面活性剤は、特に限定されないが、例えば、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、ジアルキルスルホコハク酸塩、アルキルジフェニルエーテルジスルホン酸塩、アルファオレフィンスルホン酸塩、エーテルカルボン酸塩、アルキルリン酸塩等が挙げられる。塩の種類としては、例えば、カリウム塩、ナトリウム塩等が挙げられる。これらの陰イオン界面活性剤は１種または２種以上を組み合わせて用いることもできる。これらの陰イオン界面活性剤の中でもアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、ジアルキルスルホコハク酸塩、アルキルジフェニルエーテルジスルホン酸塩、アルファオレフィンスルホン酸塩が好ましく、特にアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩が好ましい。 The removing liquid of the present invention preferably further contains an anionic surfactant in order to suppress dissolution of electrolytic copper plating. The anionic surfactant is not particularly limited, and examples thereof include alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alpha olefin sulfonate, ether carboxylate, and alkyl phosphate. Examples include salts. Examples of the salt include potassium salt and sodium salt. These anionic surfactants can be used alone or in combination of two or more. Among these anionic surfactants, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl diphenyl ether disulfonates, and alpha olefin sulfonates are preferred, with alkylbenzene sulfonates and alkyl naphthalene sulfonates being particularly preferred. Alkyl diphenyl ether disulfonate is preferred.
本発明の除去液における陰イオン界面活性剤の含有量は、特に限定されず、例えば、０.００１〜５０ｇ／Ｌが好ましく、特に０.０１〜１０ｇ／Ｌが好ましい。 The content of the anionic surfactant in the removing solution of the present invention is not particularly limited, and is preferably 0.001 to 50 g / L, and particularly preferably 0.01 to 10 g / L.
本発明の除去液は、上記成分のみを含有するものでもよいが、上記成分の他に、本発明の効果を損なわない範囲で、更に、非イオン界面活性剤、還元剤等を含有させてもよい。 The removal liquid of the present invention may contain only the above components, but in addition to the above components, a nonionic surfactant, a reducing agent, etc. may be further contained within a range not impairing the effects of the present invention. Good.
本発明の除去液に用いられる非イオン界面活性剤としては、特に限定されないが、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキル（ステアリル）エーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル等が挙げられる。本発明の除去液に非イオン界面活性剤を含有させることにより浸透性を向上させることができる。 The nonionic surfactant used in the removing liquid of the present invention is not particularly limited. For example, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl (stearyl) ether, polyoxyethylene polyoxypropylene Examples thereof include alkyl ethers. By incorporating a nonionic surfactant into the removal liquid of the present invention, the permeability can be improved.
本発明の除去液に用いられる還元剤としては、特に限定されないが、例えば、レゾルシノール、ヒドロキノン、カテコール等が挙げられる。本発明の除去液に還元剤を含有させることにより沈殿を抑制することができる。 Although it does not specifically limit as a reducing agent used for the removal liquid of this invention, For example, a resorcinol, hydroquinone, catechol etc. are mentioned. Precipitation can be suppressed by including a reducing agent in the removal liquid of the present invention.
本発明の除去液は、上記した各成分を水と混合することにより調製することができる。 The removal liquid of the present invention can be prepared by mixing the above-described components with water.
以上説明した本発明の除去液は、無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を除去することができる。無電解銅めっきの析出に用いられる触媒は、通常公知であり、例えば、パラジウム触媒等が挙げられる。 The removal liquid of the present invention described above can remove the catalyst used for the electroless copper plating and the deposition of the electroless copper plating. The catalyst used for precipitation of electroless copper plating is generally known, and examples thereof include a palladium catalyst.
本明細書において、本発明の除去液が、無電解銅めっきを除去するとは、例えば、無電解銅めっきと他の金属を設けた試験片等で、無電解銅めっきが他の金属よりも優先して溶解することをいう。 In the present specification, the removal solution of the present invention removes electroless copper plating, for example, in a test piece provided with electroless copper plating and another metal, and the electroless copper plating has priority over other metals. To dissolve.
また、本発明の除去液が無電解銅めっきの析出に用いられた触媒を除去するとは、無電解銅めっきを設けた試験片に含まれる触媒量と、無電解銅めっきを設けた試験片を除去液中に浸漬した後に除去液中に溶出した触媒量をそれぞれ測定し、除去液中に溶出した触媒量が、浸漬前の触媒量の８０質量％（以下、単に「％」という）以上、好ましくは９０％以上であることをいう。 Further, the removal liquid of the present invention removes the catalyst used for the deposition of electroless copper plating, the amount of catalyst contained in the test piece provided with electroless copper plating, and the test piece provided with electroless copper plating. The amount of catalyst eluted in the removal liquid after being immersed in the removal liquid was measured, and the amount of catalyst eluted in the removal liquid was 80% by mass or more of the amount of catalyst before immersion (hereinafter simply referred to as “%”), Preferably it means 90% or more.
更に、本発明の除去液は電解銅めっき、電解錫めっきおよび電解錫合金めっきを除去しないものである。錫合金は、特に限定されず、例えば、錫銀合金、錫ビスマス合金、錫銅合金等が挙げられる。これらの錫合金の中でも錫銀合金が好ましい。 Furthermore, the removing liquid of the present invention does not remove electrolytic copper plating, electrolytic tin plating and electrolytic tin alloy plating. A tin alloy is not specifically limited, For example, a tin silver alloy, a tin bismuth alloy, a tin copper alloy etc. are mentioned. Of these tin alloys, tin silver alloys are preferred.
本発明の除去液が電解銅めっき、電解錫めっきおよび電解錫合金めっきを除去しないとは、例えば、無電解銅めっきを設けた試験片と、電解銅めっき、電解錫めっき、電解錫合金めっきからなる群から選ばれる金属の１種または２種以上を設けた試験片を、除去液中に同じ時間浸漬した後に測定される無電解銅めっきの溶解量が、前記金属の溶解量の２００％（２倍）以上、好ましくは５００％（５倍）以上であることをいう。 The removal liquid of the present invention does not remove electrolytic copper plating, electrolytic tin plating and electrolytic tin alloy plating, for example, from a test piece provided with electroless copper plating, and electrolytic copper plating, electrolytic tin plating, and electrolytic tin alloy plating The dissolution amount of electroless copper plating measured after immersing a test piece provided with one or more metals selected from the group consisting of the same in the removal solution for 200% of the dissolution amount of the metal ( 2 times) or more, preferably 500% (5 times) or more.
本発明の除去液は、上記性質を有するため、これで無電解銅めっきを設けた基板を処理することにより、無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を除去することができる。ここで基板の材料は特に限定されず、例えば、電子回路基板で絶縁層やソルダーレジストに使用されるエポキシ樹脂等が挙げられる。前記基板に無電解銅めっきを設ける方法は触媒を用いる公知の無電解銅めっき等でよい。また、本発明の除去液を用いた処理の方法や条件は特に限定されず、例えば、本発明の除去液を１０〜５５℃の液温にし、それを１０秒〜３０分間、浸漬、噴霧、塗布等で基板へ接触させればよい。 Since the removing liquid of the present invention has the above properties, the catalyst used for the deposition of electroless copper plating and electroless copper plating can be removed by treating the substrate provided with electroless copper plating. it can. Here, the material of the substrate is not particularly limited, and examples thereof include an epoxy resin used for an insulating layer and a solder resist in an electronic circuit substrate. A method of providing electroless copper plating on the substrate may be known electroless copper plating using a catalyst. Moreover, the method and conditions of the treatment using the removal liquid of the present invention are not particularly limited. For example, the removal liquid of the present invention is set to a liquid temperature of 10 to 55 ° C., and is immersed, sprayed, for 10 seconds to 30 minutes. What is necessary is just to contact a board | substrate by application | coating etc. FIG.
本発明の除去液は、上記のように無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を除去することができるため、特に、基板に設けた無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を除去する工程を含むプリント配線板等のパターン形成方法に用いることが好ましい。 Since the removal liquid of the present invention can remove the catalyst used for the deposition of electroless copper plating and electroless copper plating as described above, in particular, the electroless copper plating and electroless copper plating provided on the substrate It is preferable to use it for a pattern formation method of a printed wiring board or the like including a step of removing the catalyst used for the deposition.
具体的には、基板に設けられた無電解銅めっき上に、電解銅めっき、電解錫めっきおよび電解錫合金めっきからなる群から選ばれる金属の１種または２種以上を用いてパターンを形成した後、本発明の除去液で無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を除去すればよい。パターンのめっきは電解銅めっき、電解錫めっきまたは電解錫合金めっきの１種類、または電解銅めっきに次いで電解錫めっきまたは電解錫合金めっきの２種類が好ましい。なお、電解銅めっきと、電解錫めっきまたは電解錫合金めっきとの間には、錫と銅が拡散しないように、電解ニッケルめっき、電解ニッケルリンめっき等の拡散防止層を設けてもよい。これらの拡散防止層があっても、本発明の除去液の効果は変わらない。パターンの形成方法は、基板に設けた無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を除去する工程を含むものであれば特に限定されないが、セミアディティブ法が好ましい。また、形成されるパターンとしては特に限定されず、ライン、ピラー等が挙げられる。 Specifically, a pattern was formed on the electroless copper plating provided on the substrate using one or more metals selected from the group consisting of electrolytic copper plating, electrolytic tin plating, and electrolytic tin alloy plating. Then, the catalyst used for the electroless copper plating and the deposition of the electroless copper plating may be removed with the removing solution of the present invention. The pattern plating is preferably one type of electrolytic copper plating, electrolytic tin plating or electrolytic tin alloy plating, or two types of electrolytic tin plating or electrolytic tin alloy plating after electrolytic copper plating. A diffusion preventing layer such as electrolytic nickel plating or electrolytic nickel phosphorus plating may be provided between the electrolytic copper plating and the electrolytic tin plating or the electrolytic tin alloy plating so that tin and copper do not diffuse. Even if these diffusion preventing layers are present, the effect of the removing liquid of the present invention does not change. The pattern forming method is not particularly limited as long as it includes a step of removing the electroless copper plating provided on the substrate and the catalyst used for the deposition of the electroless copper plating, but a semi-additive method is preferable. Moreover, it does not specifically limit as a pattern formed, A line, a pillar, etc. are mentioned.
以上説明した本発明のパターン形成方法は、パターン形成において不要な無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を除去することができるため、正確なパターンを形成することができる。 Since the pattern forming method of the present invention described above can remove the electroless copper plating unnecessary for pattern formation and the catalyst used for the deposition of the electroless copper plating, an accurate pattern can be formed.
以下、本発明を実施例を挙げて詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples at all.
実 施 例 １
試験液の調製：
下記表１に示す成分を水に混合して各試験液を調製した。
Example 1
Test solution preparation:
Components shown in Table 1 below were mixed with water to prepare each test solution.
試 験 例 １
性能評価：
実施例１で調製した各試験液を表２に記載の所定の液温に加温し、これに各試験片を表２に記載の所定の時間浸漬し、下記の方法により無電解銅めっき、電解銅めっき、電解錫めっき、電解錫銀めっきのエッチング量、触媒除去性を評価した。結果を表３に示した。
Test example 1
Performance evaluation:
Each test solution prepared in Example 1 is heated to a predetermined liquid temperature described in Table 2, and each test piece is immersed in the predetermined time described in Table 2, and electroless copper plating is performed by the following method. The etching amount and catalyst removability of electrolytic copper plating, electrolytic tin plating, and electrolytic tin silver plating were evaluated. The results are shown in Table 3.
＜エッチング量＞
大きさ５×５ｃｍのエポキシ樹脂製の基材に、以下の工程で無電解銅めっきを約０.６μｍ形成し、これを無電解銅めっきのエッチング速度測定用試験片とした。この試験片を各試験液で１５秒間処理し、処理前後の重量変化より無電解銅めっきのエッチング速度を算出した。次に大きさ５×５ｃｍの銅張積層板上に電解銅めっき、電解錫めっき、電解錫銀めっきを約２０μｍ形成し、これを電解銅めっき、電解錫めっき、電解錫銀めっきのエッチング量測定用試験片とした。この試験片を先の無電解銅めっきエッチング速度よりそのエッチング量として１.２、２.４μｍとなる時間分処理し処理前後の重量変化より電解銅めっき、電解錫めっき、電解錫銀めっきエッチング量を算出した。
<Etching amount>
About 0.6 μm of electroless copper plating was formed on a 5 × 5 cm epoxy resin substrate by the following steps, and this was used as a test piece for measuring the etching rate of electroless copper plating. This test piece was treated with each test solution for 15 seconds, and the etching rate of electroless copper plating was calculated from the weight change before and after the treatment. Next, electrolytic copper plating, electrolytic tin plating, and electrolytic tin silver plating are formed on a copper clad laminate having a size of 5 × 5 cm, and an etching amount of electrolytic copper plating, electrolytic tin plating, and electrolytic tin silver plating is measured. A test piece was obtained. This test piece was treated for an amount of time of 1.2, 2.4 μm as the etching amount from the previous electroless copper plating etching rate, and the electrolytic copper plating, electrolytic tin plating, electrolytic tin silver plating etching amount from the weight change before and after the treatment. Was calculated.
＜試験片の無電解銅めっき処理工程＞
クリーナー／コンディショナー（ＰＢ−１１７Ｓ）５０℃、５分
↓
水洗
↓
ソフトエッチング（ＰＢ−２２８）３０℃、２分
↓
水洗
↓
プリディップ（塩酸）３０℃、１分
↓
触媒付与（ＰＢ−３１８）３０℃、５分
↓
水洗
↓
アクセラレーター（ＰＢ−４４５）３０℃、５分
↓
水洗
↓
無電解銅めっき（ＰＢ−５０３Ｆ）３０℃、１５分
（塩酸以外の薬品は何れも（株）ＪＣＵ製）
<Electroless copper plating process of test piece>
Cleaner / conditioner (PB-117S) 50 ° C, 5 minutes
↓
Flushing
↓
Soft etching (PB-228) 30 ° C, 2 minutes
↓
Flushing
↓
Pre-dip (hydrochloric acid) 30 ° C, 1 minute
↓
Catalyst application (PB-318) 30 ° C., 5 minutes
↓
Flushing
↓
Accelerator (PB-445) 30 ° C, 5 minutes
↓
Flushing
↓
Electroless copper plating (PB-503F) 30 ° C, 15 minutes
(All chemicals other than hydrochloric acid are manufactured by JCU)
＜触媒除去性＞
大きさ５×１０ｃｍのエポキシ樹脂製の基材に、無電解銅めっきを上記と同様の工程で約０.６μｍ形成し、これを試験片とした。この試験片を各試験液処理後、触媒残留量を測定し、未処理の試験片との触媒残留量の差を、触媒除去率として算出し評価した。触媒残留量の測定は、試験片を、３７質量％ＨＣｌと６８％ＨＮＯ３を３：１の容量比で混合し作成した王水約５０ｍＬに５分間浸漬して、その王水を１００ｍＬメスフラスコにサンプリングし、次に試験片をイオン交換水で洗浄し、その洗浄水も１００ｍＬメスフラスコにサンプリングして、最後に１００ｍＬに正確にメスアップした水溶液中のパラジウム濃度を、原子吸光分析装置（ＡＡ２４０ＦＳ；Ｖａｒｉａｎ社製）により分析した。
<Catalyst removability>
About 0.6 μm of electroless copper plating was formed on a 5 × 10 cm epoxy resin substrate in the same process as above, and this was used as a test piece. After the test pieces were treated with each test solution, the residual catalyst amount was measured, and the difference in the residual catalyst amount from the untreated test piece was calculated and evaluated as the catalyst removal rate. The amount of catalyst remaining was measured by immersing the test piece in about 50 mL of aqua regia prepared by mixing 37 mass% HCl and 68% HNO 3 at a volume ratio of 3: 1 for 5 minutes, and then adding the aqua regia to a 100 mL volumetric flask. Next, the test piece was washed with ion-exchanged water, and the washing water was also sampled into a 100 mL volumetric flask. Finally, the palladium concentration in the aqueous solution accurately measured up to 100 mL was measured by an atomic absorption spectrometer (AA240FS). Analysis by Varian).
実施例１〜５の試験液は、無電解銅めっきを、電解銅めっき、電解錫めっきおよび電解錫銀合金めっきよりも５倍以上溶解することが分かった。また、実施例１〜５の試験液は触媒を９０％以上除去できることが分かった。一方、比較例１、２の試験液は、電解銅めっきよりも無電解銅めっきを溶解するもののその差はあまりなく、電解錫めっき、電解錫銀合金めっきを無電解銅めっきよりも溶解してしまい、触媒は全く除去できないことが分かった。また、比較例３、４の試験液は、電解錫めっき、電解錫銀合金めっきを無電解銅めっきよりも溶解しないが、電解銅めっきと無電解銅めっきが同じくらい溶解し、触媒はほとんど除去できないことが分かった。 It turned out that the test liquid of Examples 1-5 melt | dissolves electroless copper plating 5 times or more than electrolytic copper plating, electrolytic tin plating, and electrolytic tin silver alloy plating. Moreover, it turned out that the test liquid of Examples 1-5 can remove a catalyst 90% or more. On the other hand, the test solutions of Comparative Examples 1 and 2 dissolve electroless copper plating more than electrolytic copper plating, but there is not much difference between them, and electrolytic tin plating and electrolytic tin silver alloy plating dissolve more than electroless copper plating. As a result, it was found that the catalyst could not be removed at all. In addition, the test solutions of Comparative Examples 3 and 4 do not dissolve electrolytic tin plating and electrolytic tin silver alloy plating more than electroless copper plating, but electrolytic copper plating and electroless copper plating dissolve as much, and the catalyst is almost removed. I found it impossible.
試 験 例 ２
性能評価：
実施例１で調製した各試験液を表２に記載の所定の液温に加温し、これに各試験片を表２に記載の所定の時間浸漬し、下記の方法によりＣｕ／Ｓｎ−Ａｇ、Ｓｎ、Ｃｕパターンの腐食性、無電解銅めっきの除去性を評価した。結果を表４に示した。
Test example 2
Performance evaluation:
Each test solution prepared in Example 1 was heated to the predetermined liquid temperature described in Table 2, and each test piece was immersed in the predetermined time described in Table 2 for Cu / Sn-Ag by the following method. , Sn, Cu pattern corrosivity, and electroless copper plating removability were evaluated. The results are shown in Table 4.
＜Ｃｕ／Ｓｎ−Ａｇ腐食性、無電解銅めっき除去性＞
大きさ５×５ｃｍのエポキシ樹脂製の基材に、無電解銅めっきを上記と同様の工程で約０．６μｍ形成した。その後セミアディティブ法によりエポキシ樹脂製の基材上に、Ｃｕ膜厚７０μｍ、Ｓｎ−Ａｇ膜厚１５μｍ、直径１００μｍの円柱形状のＣｕ／Ｓｎ−Ａｇパターンを電解銅めっきおよび電解錫銀合金めっきで形成し、これを試験片とした。この試験片を各試験液処理後、Ｃｕ／Ｓｎ−Ａｇパターン部の断面研磨によるＣｕの断面形状、Ｓｎ−Ａｇの表面状態、無電解銅めっき残留状態を走査型電子顕微鏡（ＳＥＭ）で観察し、処理前の試験片と比較して以下の評価基準で評価した。
<Cu / Sn-Ag corrosiveness, electroless copper plating removability>
About 0.6 μm of electroless copper plating was formed on a 5 × 5 cm epoxy resin substrate in the same process as above. Thereafter, a columnar Cu / Sn-Ag pattern having a Cu film thickness of 70 μm, a Sn—Ag film thickness of 15 μm, and a diameter of 100 μm is formed by electrolytic copper plating and electrolytic tin-silver alloy plating on a substrate made of epoxy resin by a semi-additive method. This was used as a test piece. After this test piece was treated with each test solution, the cross-sectional shape of Cu by cross-sectional polishing of the Cu / Sn-Ag pattern part, the surface state of Sn-Ag, and the electroless copper plating residual state were observed with a scanning electron microscope (SEM). In comparison with the test piece before the treatment, the following evaluation criteria were used.
＜Ｃｕ／Ｓｎ−Ａｇ腐食性評価基準＞
（評 価） （状 態）
○ ： 変化なし
△ ： やや腐食あり
× ： 腐食あり
＜無電解銅めっき除去性評価基準＞
（評 価） （状 態）
○ ： 残渣なし
△ ： やや残渣あり
× ： 残渣あり
<Cu / Sn-Ag Corrosion Evaluation Criteria>
(Evaluation) (State)
○: No change
△: Some corrosion
×: Corrosion <Evaluation criteria for electroless copper plating removal>
(Evaluation) (State)
○: No residue
△: Some residue
×: Residual
＜Ｓｎ腐食性、無電解銅めっき除去性＞
大きさ５×５ｃｍのエポキシ樹脂製の基材に、無電解銅めっきを上記と同様の工程で約０.６μｍ形成した。その後セミアディティブ法によりエポキシ樹脂製の基材上に、Ｓｎ配線高さ約１５μｍ、ライン／スペース（Ｌ／Ｓ）＝２０／２０（μｍ）のＳｎパターンを電解錫めっきで形成し、これを試験片とした。この試験片を各試験液処理後、Ｓｎパターンの状態、無電解銅めっき残留状態を走査型電子顕微鏡（ＳＥＭ）で観察し、処理前の試験片と比較して以下の評価基準で評価した。
<Sn corrosion, electroless copper plating removability>
About 0.6 μm of electroless copper plating was formed on a 5 × 5 cm epoxy resin substrate in the same process as above. After that, Sn pattern with Sn wiring height of about 15μm and line / space (L / S) = 20/20 (μm) was formed on the substrate made of epoxy resin by semi-additive method by electrolytic tin plating, and this was tested A piece. After this test piece was treated with each test solution, the Sn pattern state and the electroless copper plating residual state were observed with a scanning electron microscope (SEM), and evaluated according to the following evaluation criteria in comparison with the test piece before treatment.
＜Ｓｎ腐食性評価基準＞
（評 価） （状 態）
○ ： 変化なし
△ ： やや腐食あり
× ： 腐食あり
＜無電解銅めっき除去性評価基準＞
（評 価） （状 態）
○ ： 残渣なし
△ ： やや残渣あり
× ： 残渣あり
<Sn corrosion evaluation criteria>
(Evaluation) (State)
○: No change
△: Some corrosion
×: Corrosion <Evaluation criteria for electroless copper plating removal>
(Evaluation) (State)
○: No residue
△: Some residue
×: Residual
＜Ｃｕ腐食性、無電解銅めっき除去性＞
大きさ５×５ｃｍのエポキシ樹脂製の基材に、無電解銅めっきを上記と同様の工程で約０.６μｍ形成した。その後セミアディティブ法によりエポキシ樹脂製の基材上に、Ｃｕ配線高さ約１５μｍ、ライン／スペース（Ｌ／Ｓ）＝２０／２０（μｍ）のＣｕパターンを電解銅めっきで形成し、これを試験片とした。この試験片を各試験液処理後、Ｃｕパターンの状態、無電解銅めっき残留状態を走査型電子顕微鏡（ＳＥＭ）で観察し、処理前の試験片と比較して以下の評価基準で評価した。
<Cu corrosiveness, electroless copper plating removability>
About 0.6 μm of electroless copper plating was formed on a 5 × 5 cm epoxy resin substrate in the same process as above. After that, a Cu pattern with a Cu wiring height of about 15 μm and a line / space (L / S) = 20/20 (μm) was formed by electrolytic copper plating on a substrate made of epoxy resin by a semi-additive method, and this was tested. It was a piece. After this test piece was treated with each test solution, the state of the Cu pattern and the remaining state of the electroless copper plating were observed with a scanning electron microscope (SEM), and evaluated according to the following evaluation criteria in comparison with the test piece before treatment.
＜Ｃｕ腐食性評価基準＞
（評 価） （状 態）
○ ： 変化なし
△ ： やや腐食あり
× ： 腐食あり
＜無電解銅めっき除去性評価基準＞
（評 価） （状 態）
○ ： 残渣なし
△ ： やや残渣あり
× ： 残渣あり
<Cu Corrosion Evaluation Criteria>
(Evaluation) (State)
○: No change
△: Some corrosion
×: Corrosion <Evaluation criteria for electroless copper plating removal>
(Evaluation) (State)
○: No residue
△: Some residue
×: Residual
実施例１〜５の試験液は、何れのパターンでも電解錫銀合金めっき、電解錫めっき、電解銅めっきを溶解せず、無電解銅めっきおよび触媒を除去可能であった。特に、試験液に陰イオン界面活性剤を含有させた実施例２〜５の試験液は電解銅めっきへのアタックが抑制されていた。
一方、比較例１、２の試験液は、Ｃｕ／Ｓｎ−Ａｇパターン、Ｓｎパターンでは電解錫銀合金めっき、電解錫めっきへのアタックが強く、且つ溶解した電解錫銀合金めっき、電解錫めっきがパターン間に付着し無電解銅めっきの除去も阻害していた。また、Ｃｕパターンに対してはややアタックが強かった。更に、何れのパターンでも触媒除去性がなかった。
また、比較例３、４の試験液は、Ｃｕ／Ｓｎ−Ａｇパターンでは電解錫銀合金めっきを溶解せず、無電解銅めっきが除去されたが電解銅めっきへのアタックが強かった。Ｓｎパターンでは電解錫めっきは溶解しないが、無電解銅めっきの除去性が悪かった。Ｃｕパターンでは電解銅めっきのアタックが強く、無電解銅めっきの除去性も悪かった。また何れのパターンでも触媒除去性がほぼなかった。
The test solutions of Examples 1 to 5 did not dissolve the electrolytic tin silver alloy plating, the electrolytic tin plating, and the electrolytic copper plating in any pattern, and could remove the electroless copper plating and the catalyst. In particular, in the test solutions of Examples 2 to 5 containing an anionic surfactant in the test solution, the attack on the electrolytic copper plating was suppressed.
On the other hand, the test solutions of Comparative Examples 1 and 2 are Cu / Sn-Ag pattern, Sn pattern has strong attack on electrolytic tin silver alloy plating and electrolytic tin plating, and dissolved electrolytic tin silver alloy plating and electrolytic tin plating. Removal of electroless copper plating adhered between the patterns was also hindered. Further, the attack was slightly strong against the Cu pattern. Furthermore, there was no catalyst removability in any pattern.
Further, the test solutions of Comparative Examples 3 and 4 did not dissolve the electrolytic tin-silver alloy plating in the Cu / Sn-Ag pattern, and the electroless copper plating was removed, but the attack on the electrolytic copper plating was strong. In the Sn pattern, the electrolytic tin plating was not dissolved, but the removability of the electroless copper plating was poor. In the Cu pattern, the attack of electrolytic copper plating was strong, and the removability of electroless copper plating was also poor. Moreover, there was almost no catalyst removal property in any pattern.
実 施 例 ６
除去液１：
メタンスルホン酸７０ｇ／Ｌ、チオ尿素１００ｇ／Ｌ、ドデシルベンゼンスルホン酸Na０．１５ｇ／Ｌの組成の除去液１を調製した。この除去液１を５０℃にしたものに、試験例２で使用したのと同じＣｕ／Ｓｎ−Ａｇパターン、Ｓｎパターン、Ｃｕパターンを２５０秒浸漬したところ、何れのパターンでも電解錫銀合金めっき、電解錫めっき、電解銅めっきを溶解せず、無電解銅めっきおよび触媒を除去可能であった。
Example 6
Removal liquid 1:
A removal liquid 1 having a composition of methanesulfonic acid 70 g / L, thiourea 100 g / L, and dodecylbenzenesulfonic acid Na 0.15 g / L was prepared. When the same Cu / Sn-Ag pattern, Sn pattern, and Cu pattern used in Test Example 2 were immersed in this removing liquid 1 at 50 ° C. for 250 seconds, electrolytic tin silver alloy plating was performed in any pattern. The electrolytic tin plating and the electrolytic copper plating were not dissolved, and the electroless copper plating and the catalyst could be removed.
実 施 例 ７
除去液２：
メタンスルホン酸１６０ｇ／Ｌ、チオ尿素６０ｇ／Ｌ、トリメチルチオ尿素３０ｇ／Ｌ、ドデシルベンゼンスルホン酸Na０．１５ｇ／Ｌの組成の除去液２を調製した。この除去液２を５０℃にしたものに、試験例２で使用したのと同じＣｕ／Ｓｎ−Ａｇパターン、Ｓｎパターン、Ｃｕパターンを２５０秒浸漬したところ、何れのパターンでも電解錫銀合金めっき、電解錫めっき、電解銅めっきを溶解せず、無電解銅めっきおよび触媒を除去可能であった。
Example 7
Remover 2:
A removal liquid 2 having a composition of methanesulfonic acid 160 g / L, thiourea 60 g / L, trimethylthiourea 30 g / L, and dodecylbenzenesulfonic acid Na 0.15 g / L was prepared. When the same Cu / Sn-Ag pattern, Sn pattern, and Cu pattern as used in Test Example 2 were immersed in this removing liquid 2 at 50 ° C. for 250 seconds, electrolytic tin-silver alloy plating in any pattern, The electrolytic tin plating and the electrolytic copper plating were not dissolved, and the electroless copper plating and the catalyst could be removed.
実 施 例 ８
除去液３：
メタンスルホン酸１６０ｇ／Ｌ、チオ尿素９０ｇ／Ｌ、ドデシルベンゼンスルホン酸Na０．１５ｇ／Ｌの組成の除去液３を調製した。この除去液２を４０℃にしたものに、試験例２で使用したのと同じＣｕ／Ｓｎ−Ａｇパターン、Ｓｎパターン、Ｃｕパターンを３００秒浸漬したところ、何れのパターンでも電解錫銀合金めっき、電解錫めっき、電解銅めっきを溶解せず、無電解銅めっきおよび触媒を除去可能であった。
Example 8
Remover 3:
A removal liquid 3 having a composition of 160 g / L of methanesulfonic acid, 90 g / L of thiourea, and 0.15 g / L of sodium dodecylbenzenesulfonate was prepared. When the same Cu / Sn-Ag pattern, Sn pattern, and Cu pattern used in Test Example 2 were immersed for 300 seconds in this removing liquid 2 at 40 ° C., electrolytic tin-silver alloy plating in any pattern, The electrolytic tin plating and the electrolytic copper plating were not dissolved, and the electroless copper plating and the catalyst could be removed.
本発明の除去液は、プリント配線板の製造に利用できる。
以 上
The removing liquid of the present invention can be used for the production of a printed wiring board.
that's all
Claims (12)
請求項１〜９の何れかに記載の除去液で無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒を除去することを特徴とする基板上へのパターン形成方法。 After forming a pattern on the electroless copper plating provided on the substrate using one or more metals selected from the group consisting of electrolytic copper plating, electrolytic tin plating, and electrolytic tin alloy plating,
A method for forming a pattern on a substrate, comprising removing the electroless copper plating and the catalyst used for the deposition of the electroless copper plating with the removing liquid according to claim 1.
請求項１〜９の何れかに記載の除去液で処理することを特徴とする無電解銅めっきおよび無電解銅めっきの析出に用いられた触媒の除去方法。 A substrate provided with electroless copper plating
The removal method of the catalyst used for precipitation of electroless copper plating and electroless copper plating characterized by processing with the removal liquid in any one of Claims 1-9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110106505A (en) * | 2019-05-27 | 2019-08-09 | 江门职业技术学院 | It is a kind of remove gold coating composition and its application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003138389A (en) * | 2001-10-30 | 2003-05-14 | Asahi Denka Kogyo Kk | Etchant composition and pattern forming method |
| JP2004063643A (en) * | 2002-07-26 | 2004-02-26 | Toppan Printing Co Ltd | Method for producing printed circuit board |
| JP2005154899A (en) * | 2003-11-07 | 2005-06-16 | Mec Kk | Etchant and replenishment solution therefor, and etching method and method for producing wiring board using the same |
| JP2008106354A (en) * | 2006-09-25 | 2008-05-08 | Mec Kk | Metal removing solution and metal removing method using the same |
| WO2014203649A1 (en) * | 2013-06-18 | 2014-12-24 | 株式会社Ｊｃｕ | Solution for preventing bridging of electroless metal coat, and method for manufacturing printed wiring board using same |
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2016
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003138389A (en) * | 2001-10-30 | 2003-05-14 | Asahi Denka Kogyo Kk | Etchant composition and pattern forming method |
| JP2004063643A (en) * | 2002-07-26 | 2004-02-26 | Toppan Printing Co Ltd | Method for producing printed circuit board |
| JP2005154899A (en) * | 2003-11-07 | 2005-06-16 | Mec Kk | Etchant and replenishment solution therefor, and etching method and method for producing wiring board using the same |
| JP2008106354A (en) * | 2006-09-25 | 2008-05-08 | Mec Kk | Metal removing solution and metal removing method using the same |
| WO2014203649A1 (en) * | 2013-06-18 | 2014-12-24 | 株式会社Ｊｃｕ | Solution for preventing bridging of electroless metal coat, and method for manufacturing printed wiring board using same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110106505A (en) * | 2019-05-27 | 2019-08-09 | 江门职业技术学院 | It is a kind of remove gold coating composition and its application |
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