JP2021042434A - Electroless plating inhibitory composition and method for producing plated part - Google Patents
Electroless plating inhibitory composition and method for producing plated part Download PDFInfo
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Abstract
Description
本発明は、無電解メッキ抑制組成物及びメッキ部品の製造方法に関する。 The present invention relates to an electroless plating suppressing composition and a method for producing a plated part.
近年、三次元成形回路部品（ＭＩＤ：Ｍｏｌｄｅｄ Ｉｎｔｅｒｃｏｎｎｅｃｔｅｄ Ｄｅｖｉｃｅ）が、スマートフォン等で実用化されており、今後、自動車分野での応用拡大が期待されている。ＭＩＤは、樹脂成形体の表面に金属膜で回路を形成したデバイスであり、製品の軽量化、薄肉化及び部品点数削減に貢献できる。 In recent years, three-dimensional molded circuit parts (MID: Molded Integrated Devices) have been put into practical use in smartphones and the like, and their applications in the automobile field are expected to expand in the future. The MID is a device in which a circuit is formed of a metal film on the surface of a resin molded product, and can contribute to weight reduction, thinning of the product, and reduction of the number of parts.
樹脂成形体等の絶縁性基材の表面に配線パターン（電気回路）を形成する方法として、レーザー光を使用する方法が提案されている（例えば、特許文献１）。まず、配線パターンを形成したい部分にレーザー光を照射して基材を粗化する。そして、基材全体に無電解メッキ触媒を付与すると、レーザー光照射部分には、他の部分と比較して無電解メッキ触媒が強固に付着する。次に、基材を洗浄すると、レーザー光照射部分のみに無電解メッキ触媒が残り、他の部分の触媒は容易に除去できる。レーザー光照射部分のみに無電解メッキ触媒が付着した基材に無電解メッキを施すことで、レーザー光照射部分、即ち、所定の配線パターンのみにメッキ膜を形成できる。レーザー光を利用した配線パターンの形成方法は、フォトマスク等を製造するコストや手間が省けるため、配線パターンの変更が容易である。 As a method of forming a wiring pattern (electric circuit) on the surface of an insulating base material such as a resin molded body, a method of using a laser beam has been proposed (for example, Patent Document 1). First, the base material is roughened by irradiating the portion where the wiring pattern is to be formed with laser light. Then, when the electroless plating catalyst is applied to the entire base material, the electroless plating catalyst adheres firmly to the laser beam irradiation portion as compared with other portions. Next, when the substrate is washed, the electroless plating catalyst remains only in the laser beam irradiated portion, and the catalyst in the other portion can be easily removed. By performing electroless plating on the base material to which the electroless plating catalyst is attached only to the laser light irradiation portion, a plating film can be formed only on the laser light irradiation portion, that is, a predetermined wiring pattern. The method of forming a wiring pattern using laser light saves the cost and labor of manufacturing a photomask or the like, so that the wiring pattern can be easily changed.
しかし、特許文献１で提案されているレーザー光を利用した配線パターン（電気回路）の形成方法では、基材の種類や表面状態によっては、無電解メッキ膜の形成を予定していない部分、即ち、配線パターン以外の部分にも無電解メッキ膜が生成する場合があった。例えば、無電解メッキ触媒が付着し易いフィラーを含有する基材、表面粗さが大きい基材、空隙を有する基材等は、無電解メッキ触媒が付着し易いため、洗浄しても無電解メッキ触媒が除去できずに残存し易い。また、無電解メッキ触媒の種類や基材の種類によっては、無電解メッキ触媒が基材の内部に浸透する場合があり、基材に浸透した無電解メッキ触媒を洗浄によって除去することは困難であった。このように所定の配線パターン以外の部分に無電解メッキ触媒が残存した基材に無電解メッキを施すと、当然に配線パターン以外の部分に無電解メッキ膜が生成してしまう。したがって、所定のパターン以外の部分において、より確実に、無電解メッキ膜の生成を抑制できる技術が求められていた。 However, in the method for forming a wiring pattern (electric circuit) using laser light proposed in Patent Document 1, a portion where an electroless plating film is not planned to be formed, that is, depending on the type and surface condition of the base material, that is, In some cases, an electroless plating film was formed on parts other than the wiring pattern. For example, an electroless plating catalyst easily adheres to a base material containing a filler, a base material having a large surface roughness, a base material having voids, etc. The catalyst cannot be removed and tends to remain. Further, depending on the type of the electroless plating catalyst and the type of the base material, the electroless plating catalyst may permeate into the base material, and it is difficult to remove the electroless plating catalyst that has permeated the base material by cleaning. there were. When electroless plating is applied to the base material in which the electroless plating catalyst remains in the portion other than the predetermined wiring pattern in this way, an electroless plating film is naturally formed in the portion other than the wiring pattern. Therefore, there has been a demand for a technique capable of more reliably suppressing the formation of an electroless plating film in a portion other than a predetermined pattern.
また、近年のＭＩＤ等のメッキ部品においては、ライン・アンド・スペース（Ｌ／Ｓ）が小さい配線パターン、アンテナパターン等の微細パターンが要求される。このような微細なパターンを無電解メッキで形成するために、メッキ膜を有する部分と、メッキ膜を有さない部分とのコントラストを明確にできる技術、即ち、高いメッキ選択性が求められている。また、ＭＩＤ等のメッキ部品は、様々な環境下、例えば、多湿環境下において製造される可能性がある。したがって、多湿環境下においても、同様に高いメッキ選択性が求められている。 Further, in recent years, plated parts such as MIDs are required to have fine patterns such as wiring patterns and antenna patterns having a small line and space (L / S). In order to form such a fine pattern by electroless plating, a technique capable of clarifying the contrast between a portion having a plating film and a portion having no plating film, that is, high plating selectivity is required. .. Further, plated parts such as MID may be manufactured in various environments, for example, in a humid environment. Therefore, even in a humid environment, high plating selectivity is similarly required.
本発明は、これらの課題を解決するものであり、基材の種類、形状及び状態に依存せずに、無電解メッキ膜の形成を予定していない部分での無電解メッキ膜の生成を抑制し、多湿環境下においても高いメッキ選択性を示す無電解メッキ抑制組成物を提供する。 The present invention solves these problems and suppresses the formation of an electroless plating film in a portion where the formation of an electroless plating film is not planned, regardless of the type, shape and state of the base material. However, an electroless plating suppressing composition showing high plating selectivity even in a humid environment is provided.
本発明の第１の態様に従えば、無電解メッキ抑制組成物であって、アミド基及びアミノ基の少なくとも一方を有する化合物である触媒活性妨害剤と、蒸気圧が、０．３ｋＰａ〜５ｋＰａの第１溶媒と、蒸気圧が５ｋＰａより大きい第２溶媒と、を含む、無電解メッキ抑制組成物が提供される。 According to the first aspect of the present invention, an electroless plating suppressing composition, which is a compound having at least one of an amide group and an amino group, has a catalytic activity interfering agent and a vapor pressure of 0.3 kPa to 5 kPa. An electroless plating suppressing composition containing a first solvent and a second solvent having a vapor pressure greater than 5 kPa is provided.
前記無電解メッキ抑制組成物中において、第２溶媒の配合量（Ｂ）が第１溶媒の配合量（Ａ）より多くてもよい。前記無電解メッキ抑制組成物中において、第１溶媒の配合量（Ａ）の、第２溶媒の配合量（Ｂ）に対する質量比（Ａ／Ｂ）が、（Ａ／Ｂ）＝３／９７〜３０／７０であってもよい。 In the electroless plating suppressing composition, the blending amount (B) of the second solvent may be larger than the blending amount (A) of the first solvent. In the electroless plating suppressing composition, the mass ratio (A / B) of the blending amount (A) of the first solvent to the blending amount (B) of the second solvent is (A / B) = 3/97 to It may be 30/70.
前記触媒活性妨害剤が第２溶媒に溶解可能であってもよく、前記触媒活性妨害剤の第２溶媒に対する溶解度が１以上であってもよい。前記触媒活性妨害剤の第２溶媒に対する溶解度が、第１溶媒に対する溶解度以上であってもよい。 The catalytic activity interfering agent may be soluble in a second solvent, and the catalytic activity interfering agent may have a solubility of 1 or more in the second solvent. The solubility of the catalytic activity interfering agent in the second solvent may be greater than or equal to the solubility in the first solvent.
第１溶媒がトルエン、シクロヘキサノン及びメチルイソブチルケトンからなる群から選択される少なくとも一つであってもよい。第２溶媒がメチルエチルケトン及びテトラヒドロフランの少なくとも一方であってもよい。第１溶媒がトルエンであり、第２溶媒がメチルエチルケトンであってもよい。 The first solvent may be at least one selected from the group consisting of toluene, cyclohexanone and methyl isobutyl ketone. The second solvent may be at least one of methyl ethyl ketone and tetrahydrofuran. The first solvent may be toluene and the second solvent may be methyl ethyl ketone.
前記触媒活性妨害剤がポリマーであってもよい。前記触媒活性妨害剤の重量平均分子量が１，０００〜１，０００，０００であってもよい。前記触媒活性妨害剤が、ハイパーブランチポリマーであってもよく、前記ハイパーブランチポリマーがジチオカルバメート基を有してもよい。前記無電解メッキ抑制組成物中において、前記触媒活性妨害剤の配合量が、０．２質量％〜５．０質量％であってもよく、０．３質量％〜２．０質量％であってもよい。 The catalytic activity interfering agent may be a polymer. The weight average molecular weight of the catalytic activity interfering agent may be 1,000 to 1,000,000. The catalytic activity interfering agent may be a hyperbranched polymer, and the hyperbranched polymer may have a dithiocarbamate group. In the electroless plating suppressing composition, the blending amount of the catalytic activity interfering agent may be 0.2% by mass to 5.0% by mass, and is 0.3% by mass to 2.0% by mass. You may.
本発明の第２に態様に従えば、メッキ部品の製造方法であって、基材の表面に、第１の態様の前記無電解メッキ抑制組成物を付与することと、前記基材の表面の一部を加熱又は光照射することと、加熱又は光照射した前記基材の表面に無電解メッキ触媒を付与することと、前記無電解メッキ触媒を付与した前記基材の表面に無電解メッキ液を接触させ、前記表面の加熱部分又は光照射部分に無電解メッキ膜を形成することとを含むメッキ部品の製造方法が提供される。 According to the second aspect of the present invention, in the method for producing a plated part, the electroless plating suppressing composition of the first aspect is applied to the surface of the base material, and the surface of the base material is subjected to the method. A part is heated or irradiated with light, an electroless plating catalyst is applied to the surface of the base material irradiated with heating or light, and an electroless plating solution is applied to the surface of the base material to which the electroless plating catalyst is applied. A method for manufacturing a plated component is provided, which comprises forming an electroless plating film on a heated portion or a light-irradiated portion of the surface.
本発明の無電解メッキ抑制組成物は、基材の種類、形状及び状態に依存せずに、無電解メッキ膜の形成を予定していない部分での無電解メッキ膜の生成を抑制できる。また、多湿環境下においても高いメッキ選択性を示す。 The electroless plating suppressing composition of the present invention can suppress the formation of the electroless plating film in a portion where the formation of the electroless plating film is not planned, regardless of the type, shape and state of the base material. It also exhibits high plating selectivity even in a humid environment.
［無電解メッキ抑制組成物］
無電解メッキ抑制組成物は、触媒活性妨害剤と、第１溶媒及び第２溶媒の混合溶媒とを含む。無電解メッキ抑制組成物は、メッキ部品の製造方法に用いられる。例えば、無電解メッキ抑制組成物は、メッキ部品の製造において、基材の無電解メッキ膜の形成を予定していない部分に付与され、無電解メッキ膜の生成を抑制する。
[Electroless plating suppression composition]
The electroless plating suppressing composition contains a catalytic activity interfering agent and a mixed solvent of a first solvent and a second solvent. The electroless plating suppressing composition is used in a method for manufacturing plated parts. For example, the electroless plating suppressing composition is applied to a portion of the base material where the formation of the electroless plating film is not planned in the production of the plated parts, and suppresses the formation of the electroless plating film.
触媒活性妨害剤（触媒失活剤）は、アミド基及びアミノ基の少なくとも一方を有する化合物である。触媒活性妨害剤は、アミド基及びアミノ基の少なくとも一方を有する化合物であれば特に限定されないが、ポリマーであることが好ましい。触媒活性妨害剤が、アミド基及びアミノ基の少なくとも一方を有するポリマー（以下、適宜「アミド基／アミノ基含有ポリマー」と記載する）である場合、その重量平均分子量は、例えば、１０００〜１，０００，０００であってもよい。アミド基／アミノ基含有ポリマーは、メッキ部品の製造方法において、様々な種類の基材の表面をポリマー層（以下適宜、「触媒活性妨害層」、又は「妨害層」と記載する）として均一に覆って、そこに留まることができる。これにより、基材の種類、形状及び状態に依存せずに、無電解メッキ膜の生成を抑制できる。この結果、基材の選択の幅が広がる。尚、触媒活性妨害剤の重量平均分子量は、例えば、ゲル浸透クロマトグラフィー（ＧＰＣ）によるポリスチレン換算で測定できる。 A catalytic activity interfering agent (catalytic inactivating agent) is a compound having at least one of an amide group and an amino group. The catalytic activity interfering agent is not particularly limited as long as it is a compound having at least one of an amide group and an amino group, but a polymer is preferable. When the catalytic activity interfering agent is a polymer having at least one of an amide group and an amino group (hereinafter, appropriately referred to as "amide group / amino group-containing polymer"), the weight average molecular weight thereof is, for example, 1000 to 1, It may be one million. The amide group / amino group-containing polymer uniformly forms the surface of various types of substrates as a polymer layer (hereinafter, appropriately referred to as “catalytically active interfering layer” or “interfering layer”) in the method for producing plated parts. You can cover it and stay there. Thereby, the formation of the electroless plating film can be suppressed regardless of the type, shape and state of the base material. As a result, the range of choices for the base material is widened. The weight average molecular weight of the catalytic activity interfering agent can be measured, for example, by gel permeation chromatography (GPC) in terms of polystyrene.
アミド基／アミノ基含有ポリマーは、アミド基のみを有するポリマーであってもよいし、アミノ基のみを有するポリマーであってもよいし、アミド基及びアミノ基の両方を有するポリマーであってもよい。アミド基／アミノ基含有ポリマーは、任意のものを用いることができるが、無電解メッキ触媒の触媒活性を妨げる観点からは、アミド基を有するポリマーが好ましく、また、側鎖を有する分岐ポリマーが好ましい。分岐ポリマーにおいては、側鎖がアミド基及びアミノ基の少なくとも一方を含むことが好ましく、側鎖がアミド基を含むことがより好ましい。 The amide group / amino group-containing polymer may be a polymer having only an amide group, a polymer having only an amino group, or a polymer having both an amide group and an amino group. .. Any amide group / amino group-containing polymer can be used, but a polymer having an amide group is preferable, and a branched polymer having a side chain is preferable from the viewpoint of hindering the catalytic activity of the electroless plating catalyst. .. In the branched polymer, the side chain preferably contains at least one of an amide group and an amino group, and more preferably the side chain contains an amide group.
アミド基／アミノ基含有ポリマーが無電解メッキ触媒の触媒活性を妨げるメカニズムは定かではないが、以下のように推測される。アミド基及び／又はアミノ基は、無電解メッキ触媒に吸着、配位、反応等して複合体を形成し、これにより無電解メッキ触媒は、アミド基／アミノ基含有ポリマーにトラップされる。特に、分岐ポリマーの側鎖に含まれるアミド基及び／又はアミノ基は自由度が高く、また、分岐ポリマー１分子中には、多数のアミド基及び／又はアミノ基を含むことができる。このため、分岐ポリマーは、複数のアミド基及び／又はアミノ基により、無電解メッキ触媒を効率的且つ強力にトラップできる。例えば、分岐ポリマーは多座配位子として作用し、複数のアミド基及び／又はアミノ基が無電解メッキ触媒に配位してキレート構造を形成できる。この様にトラップされた無電解メッキ触媒は、触媒活性を発揮できない。例えば、パラジウム等の金属が無電解メッキ触媒として妨害層上に付与されると、分岐ポリマーのアミド基及び／又はアミノ基がパラジウムをパラジウムイオンの状態でトラップする。パラジウムイオンは無電解メッキ液中に含まれる還元剤によって還元されて金属パラジウムとなり、無電解メッキ触媒活性を発揮する。しかし、分岐ポリマーにトラップされたパラジウムイオンは、無電解メッキ液中に含まれる還元剤によっても還元されず、触媒活性を発揮できない。これにより、触媒活性妨害層か形成された基材の表面では、無電解メッキ膜の形成が抑制される。ただし、このメカニズムは推定に過ぎず、本発明はこれに限定されない。 The mechanism by which the amide group / amino group-containing polymer interferes with the catalytic activity of the electroless plating catalyst is not clear, but it is presumed as follows. The amide group and / or amino group are adsorbed, coordinated, reacted, etc. on the electroless plating catalyst to form a complex, whereby the electroless plating catalyst is trapped in the amide group / amino group-containing polymer. In particular, the amide group and / or amino group contained in the side chain of the branched polymer has a high degree of freedom, and a large number of amide groups and / or amino groups can be contained in one molecule of the branched polymer. Therefore, the branched polymer can efficiently and strongly trap the electroless plating catalyst by a plurality of amide groups and / or amino groups. For example, the branched polymer can act as a polydentate ligand and multiple amide and / or amino groups can coordinate with the electroless plating catalyst to form a chelate structure. The electroless plating catalyst trapped in this way cannot exhibit catalytic activity. For example, when a metal such as palladium is applied onto the interfering layer as an electroless plating catalyst, the amide and / or amino groups of the branched polymer trap palladium in the form of palladium ions. Palladium ions are reduced by a reducing agent contained in the electroless plating solution to become metallic palladium, which exhibits electroless plating catalytic activity. However, the palladium ions trapped in the branched polymer are not reduced by the reducing agent contained in the electroless plating solution, and cannot exhibit catalytic activity. As a result, the formation of the electroless plating film is suppressed on the surface of the catalytically active interfering layer or the formed base material. However, this mechanism is only an estimation, and the present invention is not limited thereto.
アミド基／アミノ基含有ポリマーに含まれるアミド基は、特に限定されず、１級アミド基、２級アミド基、３級アミド基のいずれであってもよく、アミド基／アミノ基含有ポリマーに含まれるアミノ基は、特に限定されず、１級アミノ基、２級アミノ基、３級アミノ基のいずれであってもよい。これらのアミド基及びアミノ基は、ポリマー内に１種類のみが含まれてもよいし、２種類以上が含まれてもよい。 The amide group contained in the amide group / amino group-containing polymer is not particularly limited, and may be any of a primary amide group, a secondary amide group, and a tertiary amide group, and is contained in the amide group / amino group-containing polymer. The amino group is not particularly limited, and may be any of a primary amino group, a secondary amino group, and a tertiary amino group. Only one type of these amide groups and amino groups may be contained in the polymer, or two or more types may be contained.
アミド基／アミノ基含有ポリマーとして分岐ポリマーを用いる場合、無電解メッキ触媒の触媒活性を効率的に妨害する観点から、分岐ポリマーに含まれるアミド基は、２級アミド基であることが好ましく、また、アミド基の窒素には、イソプロピル基が結合していることが好ましい。また、分岐ポリマーに含まれるアミノ基は、１級アミノ基（‐ＮＨ２）又は２級アミノ基（‐ＮＨ‐）が好ましい。 When a branched polymer is used as the amide group / amino group-containing polymer, the amide group contained in the branched polymer is preferably a secondary amide group from the viewpoint of efficiently interfering with the catalytic activity of the electroless plating catalyst. , It is preferable that an isopropyl group is bonded to the nitrogen of the amide group. The amino group contained in the branched polymer is preferably a primary amino group (-NH 2 ) or a secondary amino group (-NH-).
分岐ポリマーの側鎖は、アミド基及びアミノ基の少なくとも一方を有し、更に硫黄を含む基を有してもよい。硫黄を含む基は、上述のアミド基及びアミノ基と同様に無電解メッキ触媒を吸着等する傾向がある。これにより、分岐ポリマーが無電解メッキ触媒の触媒活性を妨げる効果が促進される。硫黄を含む基は、特に限定されず、例えば、スルフィド基、ジチオカルバメート基、チオシアン基であり、好ましくは、ジチオカルバメート基である。これらの硫黄を含む基は、分岐ポリマーの側鎖に１種類のみが含まれてもよいし、２種類以上が含まれてもよい。 The side chain of the branched polymer may have at least one of an amide group and an amino group, and may further have a sulfur-containing group. Sulfur-containing groups tend to adsorb electroless plating catalysts, like the above-mentioned amide groups and amino groups. This promotes the effect of the branched polymer interfering with the catalytic activity of the electroless plating catalyst. The group containing sulfur is not particularly limited, and is, for example, a sulfide group, a dithiocarbamate group, a thiocyanate group, and preferably a dithiocarbamate group. Only one type of these sulfur-containing groups may be contained in the side chain of the branched polymer, or two or more types may be contained.
分岐ポリマーは、デンドリティックポリマーであることが好ましい。デンドリティックポリマーとは、頻繁に規則的な分岐を繰り返す分子構造で構成されたポリマーであり、デンドリマーとハイパーブランチポリマーに分類される。デンドリマーは、核となる分子を中心に、規則正しく完全に樹状分岐した構造をもつ、直径数ｎｍの球形のポリマーであり、ハイパーブランチポリマーは、完全な樹状構造をもつデンドリマーとは異なり、不完全な樹状分岐をもつポリマーである。デンドリティックポリマーの中でも、ハイパーブランチポリマーは、比較的合成が容易で且つ安価であるため、本実施形態の分岐ポリマーとして好ましい。 The branched polymer is preferably a dendritic polymer. A dendritic polymer is a polymer composed of a molecular structure that frequently repeats regular branching, and is classified into a dendrimer and a hyperbranched polymer. A dendrimer is a spherical polymer with a diameter of several nm that has a regular and completely dendritic structure centered on a core molecule, and a hyperbranched polymer is different from a dendrimer that has a complete dendritic structure. It is a polymer with complete dendritic branches. Among the dendritic polymers, the hyperbranched polymer is preferable as the branched polymer of the present embodiment because it is relatively easy to synthesize and inexpensive.
デンドリティックポリマーは、自由度の高い側鎖部分が多いため、無電解メッキ触媒に吸着し易く、効率的に無電解メッキ触媒の触媒活性を妨害できる。このため、デンドリティックポリマーは、薄膜化しても触媒活性妨害剤として効率よく作用する。また、デンドリティックポリマーの分散液は高濃度でも低粘度であるため、複雑形状の基材に対しても、均一な膜厚の妨害層を形成できる。更に、デンドリティックポリマーは耐熱性が高い。このため、ハンダリフロー耐性を要求されるメッキ部品に好適である。 Since the dendritic polymer has many side chain portions having a high degree of freedom, it is easily adsorbed on the electroless plating catalyst and can efficiently interfere with the catalytic activity of the electroless plating catalyst. Therefore, the dendritic polymer efficiently acts as a catalytic activity interfering agent even when it is thinned. Further, since the dispersion liquid of the dendritic polymer has a low viscosity even at a high concentration, it is possible to form an interfering layer having a uniform film thickness even on a base material having a complicated shape. Furthermore, dendritic polymers have high heat resistance. Therefore, it is suitable for plated parts that require solder reflow resistance.
デンドリティックポリマーは、アミド基及び／又はアミノ基に加えて、基材との親和性が高い官能基を含んでもよい。これにより、基材と触媒活性妨害層との密着性を強められる。基材との親和性が高い官能基は、基材の種類により適宜選択できる。例えば、基材がポリフェニレンサルファイド、液晶ポリマー等の芳香環を有する材料である場合、デンドリティックポリマーは芳香環を含むことが好ましい。基材がガラスである場合、デンドリティックポリマーは、ガラスと親和性の高いシラノール基を含むことが好ましい。 The dendritic polymer may contain a functional group having a high affinity with the substrate, in addition to the amide group and / or the amino group. As a result, the adhesion between the base material and the catalytic activity interfering layer can be strengthened. A functional group having a high affinity with the base material can be appropriately selected depending on the type of the base material. For example, when the base material is a material having an aromatic ring such as polyphenylene sulfide or a liquid crystal polymer, the dendritic polymer preferably contains an aromatic ring. When the base material is glass, the dendritic polymer preferably contains a silanol group having a high affinity for glass.
本実施形態のデンドリティックポリマーは、例えば、国際公開第２０１８／１３１４９２号に記載されている下記式（１）で表されるポリマーであることが好ましい。下記式（１）で表されるポリマーは、触媒活性妨害剤として効率よく作用する。 The dendritic polymer of the present embodiment is preferably, for example, a polymer represented by the following formula (1) described in International Publication No. 2018/131492. The polymer represented by the following formula (1) acts efficiently as a catalytic activity interfering agent.
Ａ１は、芳香環を含む基であれば、任意のものを用いることができるが、例えば、下記式（２）で表される基であることが好ましい。
Ａ１が、式（２）で表される基である場合、本実施形態のハイパーブランチポリマーのハイパーブランチ構造は、スチレン骨格を有する。ハイパーブランチ構造がスチレン骨格を有すると、ハイパーブランチポリマーの耐候性、耐熱性が向上する。 When A 1 is a group represented by the formula (2), the hyperbranched structure of the hyperbranched polymer of the present embodiment has a styrene skeleton. When the hyperbranched structure has a styrene skeleton, the weather resistance and heat resistance of the hyperbranched polymer are improved.
ハイパーブランチポリマーは、複数の末端基を有する。上記式（１）で表されるハイパーブランチポリマーの末端基において、Ａ２は、アミド基を含む基であり、Ａ３は、硫黄を含む基である。また、ｍ１は、各末端基におけるアミド基を含む基（Ａ２）の数（繰り返し数）ｍの平均値である。したがって、ｍ１は整数でなくてもよい。本実施形態のハイパーブランチポリマーは、平均値であるｍ１が０．５〜１１であればよく、アミド基を含む基（Ａ２）を有さない末端基を有してもよい。各末端基におけるアミド基を含む基（Ａ２）の数（繰り返し数）ｍは、例えば、０〜１１である。式（１）のｍ１は、分子内におけるアミド基を含む基（Ａ２）の総数（分子内におけるｍの合計）を末端基の数で除した商である。ｍ１の値は、ＮＭＲ法や元素分析法により定量できる。 Hyperbranched polymers have multiple end groups. In the terminal group of the hyperbranched polymer represented by the above formula (1), A 2 is a group containing an amide group, and A 3 is a group containing sulfur. Further, m1 is an average value of the number (repetition number) m of the groups (A 2 ) containing the amide group in each terminal group. Therefore, m1 does not have to be an integer. The hyperbranched polymer of the present embodiment may have an average value of m1 of 0.5 to 11, and may have a terminal group having no group (A 2) containing an amide group. The number (repetition number) m of the group (A 2 ) containing the amide group in each terminal group is, for example, 0 to 11. M1 in the formula (1) is a quotient obtained by dividing the total number of groups (A 2 ) containing an amide group in the molecule (total of m in the molecule) by the number of terminal groups. The value of m1 can be quantified by an NMR method or an elemental analysis method.
上記式（１）において、Ａ２はアミド基を含む基であれば特に限定されず、また、Ａ２に含まれるアミド基は、１級アミド基、２級アミド基、３級アミド基のいずれであってもよい。また、Ａ２は、アミド基を１個含む基であってもよいし、２個以上含む基であってもよい。Ａ２は下記式（３）で表される基であることが好ましい。Ａ２が下記式（３）で表される基であると、本実施形態のハイパーブランチポリマーは、金属捕捉能力がより向上する。これにより、無電解メッキ抑制効果がより高まる。 In the above formula (1), A 2 is not particularly limited as long as it is a group containing an amide group, and the amide group contained in A 2 is any of a primary amide group, a secondary amide group and a tertiary amide group. It may be. Further, A 2 may be a group containing one amide group or a group containing two or more amide groups. A 2 is preferably a group represented by the following formula (3). When A 2 is a group represented by the following formula (3), the hyperbranched polymer of the present embodiment has a higher metal trapping ability. As a result, the electroless plating suppressing effect is further enhanced.
上記式（１）において、Ａ３は、硫黄を含む基であれば特に限定されず、例えば、ジチオカルバメート基、トリチオカーボネート基、スルフィド基、チオシアン基等が挙げられ、中ででも、ジチオカルバメート基であることが好ましい。Ａ３がジチオカルバメート基であると、本実施形態のハイパーブランチポリマーは、合成が容易となり、また、金属捕捉能力が向上する。更に、Ａ３は、下記式（４）で表される基であることが好ましい。 In the above formula (1), A 3 is not particularly limited as long as it is a group containing sulfur, for example, dithiocarbamate group, trithiocarbonate group, a sulfide group, a thiocyanate group and the like, but being, dithiocarbamates It is preferably a group. When A 3 is a dithiocarbamate group, the hyperbranched polymer of the present embodiment, synthesis facilitated and also improves metal trapping capability. Moreover, A 3 is preferably a group represented by the following formula (4).
上記式（１）において、Ｒ０は、水素又は炭素数１〜１０個の置換若しくは無置換の炭化水素基であれば、任意の炭化水素基を用いることができる。上記炭化水素基は、鎖状若しくは環状の飽和脂肪族炭化水素基、鎖状若しくは環状の不飽和脂肪族炭化水素基、又は芳香族炭化水素基であってもよい。Ｒ０が、置換の炭化水素基である場合の置換基は、例えば、アルキル基、シクロアルキル基、ビニル基、アリル基、アリール基、アルコキシ基、ハロゲン基、ヒドロキシ基、アミノ基、イミノ基、ニトロ基、シリル基又はエステル基等であってもよい。また、Ｒ０は、無置換の炭化水素基であってもよく、例えば、ビニル基又はエチル基であってもよい。 In the above formula (1), R 0 is, if hydrogen or a hydrocarbon group of a substituted or unsubstituted 1 to 10 carbon atoms, can be any hydrocarbon group. The hydrocarbon group may be a chain or cyclic saturated aliphatic hydrocarbon group, a chain or cyclic unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group. When R 0 is a substituted hydrocarbon group, the substituents are, for example, an alkyl group, a cycloalkyl group, a vinyl group, an allyl group, an aryl group, an alkoxy group, a halogen group, a hydroxy group, an amino group, an imino group, and the like. It may be a nitro group, a silyl group, an ester group, or the like. Further, R 0 may be an unsubstituted hydrocarbon group, for example, a vinyl group or an ethyl group.
本実施形態のハイパーブランチポリマーは、式（１）において、Ｒ０が異なるハイパーブランチポリマーの混合物であってもよい。例えば、Ｒ０が不飽和結合を有する場合、ハイパーブランチポリマーの合成過程において、不飽和結合の一部に何らかの付加反応が生じて飽和結合となる場合がある。この場合、上記式（１）において、Ｒ０が不飽和炭化水素基のハイパーブランチポリマーと、Ｒ０が飽和炭化水素基のハイパーブランチポリマーとの混合物が得られる。本実施形態のハイパーブランチポリマーは、上記式（１）において、Ｒ０がビニル基のハイパーブランチポリマーと、Ｒ０がエチル基のハイパーブランチポリマーとの混合物であってもよい。 Hyperbranched polymer of the present embodiment, in Formula (1) may be a mixture of the hyperbranched polymer R 0 is different. For example, when R 0 has an unsaturated bond, some addition reaction may occur in a part of the unsaturated bond in the process of synthesizing the hyperbranched polymer, resulting in a saturated bond. In this case, in the above formula (1), a mixture of a hyperbranched polymer in which R 0 is an unsaturated hydrocarbon group and a hyperbranched polymer in which R 0 is a saturated hydrocarbon group is obtained. The hyperbranched polymer of the present embodiment may be a mixture of a hyperbranched polymer in which R 0 is a vinyl group and a hyperbranched polymer in which R 0 is an ethyl group in the above formula (1).
本実施形態のハイパーブランチポリマーは、数平均分子量が、３,０００〜３０,０００であり、重量平均分子量が、１０,０００〜３００,０００であることが好ましく、数平均分子量が、５，０００〜３０，０００であり、重量平均分子量が、１４,０００〜２００，０００であることがより好ましい。数平均分子量又は重量平均分子量が上記範囲内であれば、無電解メッキ抑制組成物の安定性と、メッキ抑制効果とを両立できる。尚、ハイパーブランチポリマーの重量平均分子量及び数平均分子量は、例えば、ゲル浸透クロマトグラフィー（ＧＰＣ）によるポリスチレン換算で測定できる。 The hyperbranched polymer of the present embodiment preferably has a number average molecular weight of 3,000 to 30,000, a weight average molecular weight of 10,000 to 300,000, and a number average molecular weight of 5,000. It is more preferably ~ 30,000 and the weight average molecular weight is 14,000 to 200,000. When the number average molecular weight or the weight average molecular weight is within the above range, both the stability of the electroless plating suppressing composition and the plating suppressing effect can be achieved. The weight average molecular weight and the number average molecular weight of the hyperbranched polymer can be measured, for example, by gel permeation chromatography (GPC) in terms of polystyrene.
本実施形態のハイパーブランチポリマーの合成方法は、特に限定されず、任意の方法により合成できる。例えば、市販のハイパーブランチポリマーを出発物質として、本実施形態のハイパーブランチポリマーを合成してもよい。また、モノマーの合成、モノマーの重合、末端基修飾等を順に行って、本実施形態のハイパーブランチポリマーを合成してもよい。尚、本実施形態のハイパーブランチポリマーの重量平均分子量及び数平均分子量、式（１）中のｍ１及びｎ１は、合成に用いる試薬の比率、合成条件等を任意の方法で調整することにより、所定の範囲内に調整できる。 The method for synthesizing the hyperbranched polymer of the present embodiment is not particularly limited, and the hyperbranched polymer can be synthesized by any method. For example, the hyperbranched polymer of the present embodiment may be synthesized using a commercially available hyperbranched polymer as a starting material. Further, the hyperbranched polymer of the present embodiment may be synthesized by sequentially performing the synthesis of the monomer, the polymerization of the monomer, the modification of the terminal group, and the like. The weight average molecular weight and number average molecular weight of the hyperbranched polymer of the present embodiment, m1 and n1 in the formula (1) are predetermined by adjusting the ratio of reagents used for synthesis, synthesis conditions, etc. by any method. Can be adjusted within the range of.
無電解メッキ抑制組成物中における、触媒活性妨害剤の配合量は、特に限定されないが、無電解メッキ抑制組成物の安定性とメッキ抑制効果とを両立する観点から、上記配合量は、０．２質量％〜５．０質量％が好ましく、０．３質量％〜２．０質量％がより好ましい。 The blending amount of the catalytic activity interfering agent in the electroless plating suppressing composition is not particularly limited, but from the viewpoint of achieving both the stability of the electroless plating suppressing composition and the plating suppressing effect, the blending amount is 0. 2% by mass to 5.0% by mass is preferable, and 0.3% by mass to 2.0% by mass is more preferable.
第１溶媒は、蒸気圧が、０．３ｋＰａ〜５ｋＰａであり、第２溶媒は、蒸発圧が５ｋＰａより大きい。 The vapor pressure of the first solvent is 0.3 kPa to 5 kPa, and the vapor pressure of the second solvent is larger than 5 kPa.
メッキ部品の製造において、本実施形態の無電解メッキ抑制組成物は基材上に付与され、溶媒が蒸発することにより基材上に触媒活性妨害層が形成される。このとき、溶媒が急激に蒸発すると周囲の空気が冷却され、空気中の水分が凝結して触媒活性妨害層に混入し、白濁が生じる（ブラッシング、白化）。ブラッシングが生じると、触媒活性妨害層が不均一となり、無電解メッキ膜の生成を十分に抑制できなくなる。この結果、メッキ選択性（メッキ膜有無のコントラスト）が低下する。この現象は、空気中の水蒸気量が多いとき、即ち、多湿環境下において顕著である。一方で、溶媒が蒸発し難いと触媒活性妨害層内に溶媒が残存し、乾燥が不十分となる。乾燥が不十分な場合も、触媒活性妨害層が不均一となりメッキ選択性が低下する。特に、ライン・アンド・スペース（Ｌ／Ｓ）が小さい微細な配線パターン、アンテナパターン等においてメッキ選択性が不十分となり、短絡が生じる虞がある。 In the production of plated parts, the electroless plating suppressing composition of the present embodiment is applied onto a base material, and the solvent evaporates to form a catalytic activity interfering layer on the base material. At this time, when the solvent evaporates rapidly, the surrounding air is cooled, and the moisture in the air condenses and mixes with the catalytic activity interfering layer, causing cloudiness (brushing, whitening). When brushing occurs, the catalytic activity interfering layer becomes non-uniform, and the formation of the electroless plating film cannot be sufficiently suppressed. As a result, the plating selectivity (contrast with or without the plating film) is lowered. This phenomenon is remarkable when the amount of water vapor in the air is large, that is, in a humid environment. On the other hand, if the solvent is difficult to evaporate, the solvent remains in the catalytic activity interfering layer, resulting in insufficient drying. Even when the drying is insufficient, the catalytic activity interfering layer becomes non-uniform and the plating selectivity is lowered. In particular, in a fine wiring pattern, antenna pattern, etc. with a small line and space (L / S), the plating selectivity becomes insufficient, and a short circuit may occur.
本実施形態では、蒸気圧の異なる第１溶媒及び第２溶媒を用いることで、全溶媒（第１溶媒と第２溶媒との混合溶媒）の蒸発速度を制御する。一般に、溶媒（溶剤）を含む組成物から形成される塗膜（湿潤塗膜）の乾燥プロセスは、次の3つの期間を経る。（Ｉ）溶剤が急激に蒸発し始める温度に達するまで塗膜の温度が上昇する湿潤塗膜の材料予熱期間、（ＩＩ）塗膜から溶剤が蒸発することによって塗膜から奪われる蒸発潜熱と、塗膜が周囲から受け取る熱量との釣合いがほぼ取れている恒率乾燥期間、（ＩＩＩ）塗膜中の溶剤がほぼ無くなった後、塗膜が固化し、塗膜の表面温度が上昇して周囲の温度（例えば、乾燥機内雰囲気の温度）に近づいていく減率乾燥期間。そして、塗膜中の溶媒は、（ＩＩ）恒率乾燥期間に主に蒸発する。一般に、蒸気圧が小さい溶媒は蒸発し難く、蒸気圧が大きい溶媒は蒸発し易い。蒸気圧が比較的小さく蒸発し難い第１溶媒と、蒸気圧が比較的大きく蒸発し易い第２溶媒とを混合することで、（ＩＩ）恒率乾燥期間において主に蒸気圧が大きい第２溶媒が蒸発し、その後の（ＩＩＩ）減率乾燥期間において、蒸気圧が小さい第１溶媒が蒸発する。これにより、ブラッシングを抑制しつつ、混合溶媒を十分に蒸発させることができる。この結果、メッキ抑制組成物は、高いメッキ選択性を示すことができる。本実施形態の無電解メッキ抑制組成物は、ブラッシングが発生し易い多湿環境下においても、同様に高いメッキ選択性を示すことができる。 In the present embodiment, the evaporation rate of all the solvents (mixed solvent of the first solvent and the second solvent) is controlled by using the first solvent and the second solvent having different vapor pressures. Generally, the drying process of a coating film (wet coating film) formed from a composition containing a solvent (solvent) goes through the following three periods. (I) The material preheating period of the wet coating film in which the temperature of the coating film rises until the temperature at which the solvent starts to evaporate rapidly is reached, and (II) the latent heat of evaporation taken from the coating film by the evaporation of the solvent from the coating film. During the constant drying period, when the coating film is almost balanced with the amount of heat received from the surroundings, (III) after the solvent in the coating film is almost eliminated, the coating film solidifies, the surface temperature of the coating film rises, and the surroundings The rate-reducing drying period that approaches the temperature of (for example, the temperature of the atmosphere inside the dryer). Then, the solvent in the coating film mainly evaporates during the (II) constant drying period. In general, a solvent having a low vapor pressure is difficult to evaporate, and a solvent having a high vapor pressure is easy to evaporate. By mixing the first solvent, which has a relatively low vapor pressure and is difficult to evaporate, and the second solvent, which has a relatively high vapor pressure and is easy to evaporate, (II) a second solvent having a large vapor pressure mainly during the constant drying period. Evaporates, and in the subsequent (III) rate-reducing drying period, the first solvent having a low vapor pressure evaporates. As a result, the mixed solvent can be sufficiently evaporated while suppressing brushing. As a result, the plating-suppressing composition can exhibit high plating selectivity. The electroless plating suppressing composition of the present embodiment can similarly exhibit high plating selectivity even in a humid environment where brushing is likely to occur.
第１溶媒は、第２溶媒よりも蒸気圧が低い。第１溶媒の蒸気圧は、０．３ｋＰａ〜５ｋＰａであり、好ましくは、０．５ｋＰａ〜５ｋＰａであってもよい。第１溶媒を含むことにより、ブラッシングを抑制できる。第２溶媒は、第１溶媒よりも蒸気圧が高い。第２溶媒の蒸気圧は、５ｋＰａより大きく、好ましくは、１０ｋＰａ以上であってもよい。また、第２溶媒の蒸気圧の上限値は特に限定されないが、例えば、２５ｋＰａ以下、又は２０ｋＰａ以下であってもよい。尚、本願明細書において、各溶媒の蒸気圧は、常温（例えば、２０〜２５℃）における平衡蒸気圧を意味する。 The first solvent has a lower vapor pressure than the second solvent. The vapor pressure of the first solvent is 0.3 kPa to 5 kPa, preferably 0.5 kPa to 5 kPa. Brushing can be suppressed by containing the first solvent. The second solvent has a higher vapor pressure than the first solvent. The vapor pressure of the second solvent may be larger than 5 kPa, preferably 10 kPa or more. The upper limit of the vapor pressure of the second solvent is not particularly limited, but may be, for example, 25 kPa or less, or 20 kPa or less. In the specification of the present application, the vapor pressure of each solvent means an equilibrium vapor pressure at room temperature (for example, 20 to 25 ° C.).
第１溶媒としては、例えば、トルエン（２．９ｋＰａ、２０℃）、シクロヘキサノン（０．６ｋＰａ、２５℃）、メチルイソブチルケトン（ＭＩＢＫ）（２．１ｋＰａ、２０℃）、グリコールエーテル、イソプロパノール（ＩＰＡ）（４．４ｋＰａ、２５℃）、酢酸ブチル（１．２ｋＰａ、２０℃）等が挙げられる。グリコールエーテルは、２価アルコールのモノエーテル、又はジエーテルであれば、特に限定されず、例えば、プロピレングリコールモノメチルエーテル（ＰＧＭ）（０．９ｋＰａ、２０℃）、エチレングリコールモノメチルエーテル（０．８ｋＰａ、２０℃）、エチレングリコールモノイソプロピルエーテル（０．３ｋＰａ、２０℃）等が挙げられる。中でも、第１溶媒としては、トルエン、シクロヘキサノン、ＭＩＢＫが好ましく、トルエンがより好ましい。これらの溶媒は、単独で用いても２種類以上を混合して用いてもよい。 Examples of the first solvent include toluene (2.9 kPa, 20 ° C.), cyclohexanone (0.6 kPa, 25 ° C.), methyl isobutyl ketone (MIBK) (2.1 kPa, 20 ° C.), glycol ether, isopropanol (IPA). (4.4 kPa, 25 ° C.), butyl acetate (1.2 kPa, 20 ° C.) and the like can be mentioned. The glycol ether is not particularly limited as long as it is a monoether of a dihydric alcohol or a diether, and is, for example, propylene glycol monomethyl ether (PGM) (0.9 kPa, 20 ° C.), ethylene glycol monomethyl ether (0.8 kPa, 20). ° C.), ethylene glycol monoisopropyl ether (0.3 kPa, 20 ° C.) and the like. Among them, toluene, cyclohexanone, and MIBK are preferable as the first solvent, and toluene is more preferable. These solvents may be used alone or in combination of two or more.
第２溶媒としては、例えば、メチルエチルケトン（ＭＥＫ）（１０．３ｋＰａ、２５℃）、テトラヒドロフラン（ＴＨＦ）（１８．９ｋＰａ、２０℃）、アセトン（２４．７ｋＰａ、２０℃）、１，２−ジメトキシエタン（ＤＭＧ）（６．４ｋＰａ、２０℃）等が挙げられ、中でも、ＭＥＫ、ＴＨＦが好ましく、ＭＥＫがより好ましい。これらの溶媒は、単独で用いても２種類以上を混合して用いてもよい。 Examples of the second solvent include methyl ethyl ketone (MEK) (10.3 kPa, 25 ° C.), tetrahydrofuran (THF) (18.9 kPa, 20 ° C.), acetone (24.7 kPa, 20 ° C.), 1,2-dimethoxyethane. (DMG) (6.4 kPa, 20 ° C.) and the like, among which MEK and THF are preferable, and MEK is more preferable. These solvents may be used alone or in combination of two or more.
第１溶媒の溶解性パラメータと、第２溶媒の溶解性パラメータとの差は、小さい方が好ましい。溶解性パラメータの差が小さければ、第１溶媒と第２溶媒とは相溶性が高まる。これにより、均一な触媒活性妨害層を形成でき、メッキ選択性がより向上する。例えば、第１溶媒の溶解性パラメータと、第２溶媒の溶解性パラメータとの差（差の絶対値）は、０．８以下が好ましく、０．４以下がより好ましい。例えば、第１溶媒が、トルエン、シクロヘキサノン、又はＭＩＢＫであり、第２溶媒が、ＭＥＫ又はＴＨＦであることが好ましい。また、第１溶媒がトルエンであり、第２溶媒がＭＥＫであることがより好ましい。 The difference between the solubility parameter of the first solvent and the solubility parameter of the second solvent is preferably small. If the difference in solubility parameters is small, the compatibility between the first solvent and the second solvent is increased. As a result, a uniform catalytic activity interfering layer can be formed, and the plating selectivity is further improved. For example, the difference (absolute value of the difference) between the solubility parameter of the first solvent and the solubility parameter of the second solvent is preferably 0.8 or less, more preferably 0.4 or less. For example, it is preferable that the first solvent is toluene, cyclohexanone, or MIBK, and the second solvent is MEK or THF. Further, it is more preferable that the first solvent is toluene and the second solvent is MEK.
表１に、主な第１及び第２溶媒の蒸気圧と、溶解性パラメータ（ＳＰ値）を示す。
無電解メッキ抑制組成物中において、第２溶媒の配合量（Ｂ）は第１溶媒の配合量（Ａ）より多いことが好ましい（Ｂ＞Ａ）。即ち、第２溶媒が無電解メッキ抑制組成物の主溶媒であることが好ましい。これにより、無電解メッキ抑制組成物の混合溶媒の蒸発を更に促進できる。また、無電解メッキ抑制組成物中において、第１溶媒の配合量（Ａ）の、第２溶媒の配合量（Ｂ）に対する質量比（Ａ／Ｂ）は、（Ａ／Ｂ）＝３／９７〜３５／６５であることが好ましく、３／９７〜３０／７０であることがより好ましい。質量比（Ａ／Ｂ）を上記範囲の下限値以上とすることでブラッシングをより抑制でき、上記範囲の上限値以下とすることで混合溶媒の蒸発をより促進できる。この結果、より高いメッキ選択性が得られる。 In the electroless plating suppressing composition, the blending amount (B) of the second solvent is preferably larger than the blending amount (A) of the first solvent (B> A). That is, it is preferable that the second solvent is the main solvent of the electroless plating suppressing composition. Thereby, the evaporation of the mixed solvent of the electroless plating suppressing composition can be further promoted. Further, in the electroless plating suppressing composition, the mass ratio (A / B) of the blending amount (A) of the first solvent to the blending amount (B) of the second solvent is (A / B) = 3/97. It is preferably ~ 35/65, and more preferably 3/97 to 30/70. Brushing can be further suppressed by setting the mass ratio (A / B) to the lower limit of the above range or more, and evaporation of the mixed solvent can be further promoted by setting the mass ratio (A / B) to the upper limit of the above range. As a result, higher plating selectivity can be obtained.
触媒活性妨害剤は、第２溶媒に溶解可能であることが好ましい。上述のように、第２溶媒は無電解メッキ抑制組成物の主溶媒であることが好ましい。触媒活性妨害剤が主溶媒である第２溶媒に溶解することで、均一な触媒活性妨害層を形成でき、この結果、メッキ選択性がより向上する。触媒活性妨害剤の第２溶媒に対する溶解度は高い方が好ましく、例えば、１（ｇ／１００ｇ）以上が好ましく、５（ｇ／１００ｇ）以上がより好ましい。尚、本願明細書において、溶解度とは、２５℃、常圧（例えば、１気圧）における溶媒１００gに溶ける溶質の質量（飽和溶解量）を意味する。触媒活性妨害剤の第２溶媒に対する溶解度を上記値以上とすることで、蒸発し易い第２溶媒が蒸発して触媒活性妨害剤の濃度が上昇しても、触媒活性妨害剤の凝集を抑制できる。この結果、均一な触媒活性妨害層が形成でき、メッキ選択性が更により向上する。 The catalytic activity interfering agent is preferably soluble in a second solvent. As described above, the second solvent is preferably the main solvent of the electroless plating suppressing composition. By dissolving the catalytic activity interfering agent in the second solvent which is the main solvent, a uniform catalytic activity interfering layer can be formed, and as a result, the plating selectivity is further improved. The solubility of the catalytic activity interfering agent in the second solvent is preferably high, for example, 1 (g / 100 g) or more is preferable, and 5 (g / 100 g) or more is more preferable. In the specification of the present application, the solubility means the mass (saturated dissolution amount) of a solute soluble in 100 g of a solvent at 25 ° C. and normal pressure (for example, 1 atm). By setting the solubility of the catalytic activity interfering agent in the second solvent to the above value or more, aggregation of the catalytic activity interfering agent can be suppressed even if the second solvent that easily evaporates evaporates and the concentration of the catalytic activity interfering agent increases. .. As a result, a uniform catalytic activity interfering layer can be formed, and the plating selectivity is further improved.
触媒活性妨害剤は、第１溶媒に溶解可能であるか、又は第１溶媒に分散可能であることが好ましい。主に恒率乾燥期間で蒸気圧が相対的大きい第２溶媒の蒸発が進むと、蒸気圧が相対的小さい蒸発し難い第１溶媒の比率が高まる。触媒活性妨害剤が、第１溶媒に溶解可能、又は分散可能であれば、第１溶媒の比率が高まった場合に触媒活性妨害剤の凝集を抑制でき、均一な触媒活性妨害層が形成できる。この結果、メッキ選択性がより向上する。ここで、分散とは、粒子が溶媒中に、一定時間、凝集、沈降等せずに安定に浮遊又は懸濁している状態をいう。例えば、第１溶媒中の触媒活性妨害剤の平均粒子径が２５０ｎｍ未満、好ましくは、１５０ｎｍ未満であるとき、触媒活性妨害剤は第１溶媒に分散していると判断してもよい。尚、第１溶媒中の触媒活性妨害剤の平均粒子径は、汎用の粒度分布測定装置を用いて室温において測定できる。平均粒子径は、例えば、レーザー回折・散乱粒子径分布測定法により求めた体積基準の平均粒子径（算術平均径）であってもよい。 The catalytic activity interfering agent is preferably soluble in the first solvent or dispersible in the first solvent. As the evaporation of the second solvent having a relatively large vapor pressure progresses mainly during the constant drying period, the ratio of the first solvent having a relatively small vapor pressure and being difficult to evaporate increases. If the catalytic activity interfering agent is soluble or dispersible in the first solvent, aggregation of the catalytic activity interfering agent can be suppressed when the ratio of the first solvent is increased, and a uniform catalytic activity interfering layer can be formed. As a result, the plating selectivity is further improved. Here, the term “dispersion” refers to a state in which particles are stably suspended or suspended in a solvent for a certain period of time without agglomeration, sedimentation, or the like. For example, when the average particle size of the catalytic activity interfering agent in the first solvent is less than 250 nm, preferably less than 150 nm, it may be determined that the catalytic activity interfering agent is dispersed in the first solvent. The average particle size of the catalytic activity interfering agent in the first solvent can be measured at room temperature using a general-purpose particle size distribution measuring device. The average particle size may be, for example, a volume-based average particle size (arithmetic mean size) obtained by a laser diffraction / scattered particle size distribution measurement method.
触媒活性妨害剤の第２溶媒に対する溶解度は、第１溶媒に対する溶解度以上であることが好ましく、第１溶媒に対する溶解度より高いことがより好ましい。触媒活性妨害剤の第２溶媒（主溶媒）に対する溶解度が高いことにより、均一な触媒活性妨害層を形成できる。一方で、触媒活性妨害剤の第１溶媒に対する溶解度は、第２溶媒に対する溶解度より低くてもよい。上述のように、第１溶媒の配合量（Ａ）は第２溶媒の配合量（Ｂ）より低くてもよい。このため、触媒活性妨害剤の第１溶媒に対する溶解度が低くとも、第２溶媒に対する溶解度が十分に高ければ、均一な触媒活性妨害層を形成できる。均一な触媒活性妨害層を形成する観点からは、触媒活性妨害剤は、第１溶媒と第２溶媒との混合溶媒（全溶媒）に溶解可能であることが好ましい。即ち、触媒活性妨害剤は、無電解メッキ抑制組成物中で溶解していることが好ましい。触媒活性妨害剤が溶解していることで、より均一な触媒活性妨害層が形成でき、メッキ選択性がより向上する。 The solubility of the catalytic activity interfering agent in the second solvent is preferably equal to or higher than the solubility in the first solvent, and more preferably higher than the solubility in the first solvent. Due to the high solubility of the catalytic activity interfering agent in the second solvent (main solvent), a uniform catalytic activity interfering layer can be formed. On the other hand, the solubility of the catalytic activity interfering agent in the first solvent may be lower than the solubility in the second solvent. As described above, the blending amount (A) of the first solvent may be lower than the blending amount (B) of the second solvent. Therefore, even if the solubility of the catalytic activity interfering agent in the first solvent is low, a uniform catalytic activity interfering layer can be formed if the solubility in the second solvent is sufficiently high. From the viewpoint of forming a uniform catalytic activity interfering layer, it is preferable that the catalytic activity interfering agent can be dissolved in a mixed solvent (all solvents) of the first solvent and the second solvent. That is, the catalytic activity interfering agent is preferably dissolved in the electroless plating suppressing composition. By dissolving the catalytic activity interfering agent, a more uniform catalytic activity interfering layer can be formed, and the plating selectivity is further improved.
例えば、上述した式（１）で表されるポリマーを触媒活性妨害剤として用いた場合、触媒活性妨害剤は、第１溶媒であるシクロヘキサノン、メチルイソブチルケトン（ＭＩＢＫ）、第２溶媒であるメチルエチルケトン（ＭＥＫ）、テトラヒドロフラン（ＴＨＦ）、１，２−ジメトキシエタン（ＤＭＧ）に溶解可能であり、これらの溶媒に対する触媒活性妨害剤の溶解度は、５．０以上である。一方、式（１）で表されるポリマーを触媒活性妨害剤として用いた場合、第１溶媒であるトルエン、プロピレングリコールモノメチルエーテル（ＰＧＭ）に対する触媒活性妨害剤の溶解度は、０．１以下と低いが、これらの溶媒に対して触媒活性妨害剤は分散可能である。 For example, when the polymer represented by the above formula (1) is used as a catalytic activity interfering agent, the catalytic activity interfering agent is cyclohexanone as the first solvent, methyl isobutyl ketone (MIBK), or methyl ethyl ketone as the second solvent (2). It is soluble in MEK), tetrahydrofuran (THF) and 1,2-dimethoxyethane (DMG), and the solubility of the catalytic activity interfering agent in these solvents is 5.0 or more. On the other hand, when the polymer represented by the formula (1) is used as the catalytic activity interfering agent, the solubility of the catalytic activity interfering agent in toluene and propylene glycol monomethyl ether (PGM) as the first solvent is as low as 0.1 or less. However, the catalytic activity interfering agent can be dispersed in these solvents.
無電解メッキ抑制組成物中における、第１溶媒と第２溶媒との混合溶媒（全溶媒）の配合量（Ａ＋Ｂ）は、特に限定されないが、例えば、９５質量％〜９９．８質量％、又は、９８質量％〜９９．７質量％である。 The blending amount (A + B) of the mixed solvent (total solvent) of the first solvent and the second solvent in the electroless plating suppressing composition is not particularly limited, but is, for example, 95% by mass to 99.8% by mass, or , 98% by mass to 99.7% by mass.
無電解メッキ抑制組成物は、触媒活性妨害剤と、第１溶媒と第２溶媒との混合溶媒（全溶媒）のみから構成されてもよい。また、本実施形態の無電解メッキ抑制組成物は、触媒活性妨害剤及び混合溶媒に加えて、界面活性剤、濡れ性調整剤等、汎用の添加剤を含んでもよい。また、本実施形態の効果を阻害しない範囲で、第１及び第２溶媒以外の有機溶剤等を含んでもよい。 The electroless plating suppressing composition may be composed only of a catalytic activity interfering agent and a mixed solvent (all solvents) of a first solvent and a second solvent. Further, the electroless plating suppressing composition of the present embodiment may contain general-purpose additives such as a surfactant and a wettability adjusting agent in addition to the catalytic activity interfering agent and the mixed solvent. Further, an organic solvent other than the first and second solvents may be contained as long as the effect of the present embodiment is not impaired.
本実施形態の無電解メッキ抑制組成物は、汎用の方法により調製できる。例えば、無電解メッキ抑制組成物は、撹拌機、超音波分散機、ミキサー等汎用の装置を用いて、触媒活性妨害剤と、第１溶媒と第２溶媒との混合溶媒と、必要により、その他の添加剤とを混合して調製できる。 The electroless plating suppression composition of the present embodiment can be prepared by a general-purpose method. For example, the electroless plating suppressing composition can be prepared by using a general-purpose device such as a stirrer, an ultrasonic disperser, or a mixer to obtain a catalytic activity interfering agent, a mixed solvent of a first solvent and a second solvent, and if necessary, other solvents. Can be prepared by mixing with the additives of.
本実施形態の無電解メッキ抑制組成物は、例えば、以下の効果を奏する。無電解メッキ抑制組成物は、触媒活性妨害剤を含む。メッキ部品の製造方法において、基材の無電解メッキ膜の形成を予定していない部分に、本実施形態の無電解メッキ抑制組成物を付与することにより、基材の種類、形状及び状態に依存せずに、無電解メッキ膜の形成を予定していない部分での無電解メッキ膜の生成を抑制できる。これにより、メッキ膜を有する部分と、メッキ膜を有さない部分とのコントラストが明確なメッキ部品を製造できる。 The electroless plating suppressing composition of the present embodiment has the following effects, for example. The electroless plating suppressing composition contains a catalytic activity interfering agent. In the method for manufacturing plated parts, by applying the electroless plating suppressing composition of the present embodiment to a portion where the electroless plating film of the base material is not planned to be formed, it depends on the type, shape and state of the base material. It is possible to suppress the formation of the electroless plating film in the portion where the formation of the electroless plating film is not planned. As a result, it is possible to manufacture a plated part having a clear contrast between the portion having the plating film and the portion having no plating film.
また、無電解メッキ抑制組成物は、第１溶媒と第２溶媒との混合溶媒を用いることで、ブラッシングを抑制しつつ、溶媒（混合溶媒）を十分に蒸発させることができる。この結果、高いメッキ選択性（メッキ膜有無のコントラスト）が得られる。本実施形態の無電解メッキ抑制組成物は、ブラッシングが発生し易い多湿環境下においても、同様に高いメッキ選択性を示す。 Further, in the electroless plating suppressing composition, by using a mixed solvent of the first solvent and the second solvent, the solvent (mixed solvent) can be sufficiently evaporated while suppressing brushing. As a result, high plating selectivity (contrast with or without plating film) can be obtained. The electroless plating suppressing composition of the present embodiment also exhibits high plating selectivity even in a humid environment where brushing is likely to occur.
［メッキ部品の製造方法］
図１に示すフローチャートに従って、本実施形態のメッキ部品の製造方法について説明する。本実施形態で製造するメッキ部品は、選択的にメッキ膜が形成されたメッキ部品であり、基材の表面の一部（所定パターン、所定部分）に無電解メッキ膜が形成されており、それ以外の部分には無電解メッキ膜が形成されていない。
[Manufacturing method of plated parts]
A method for manufacturing the plated parts of the present embodiment will be described with reference to the flowchart shown in FIG. The plated parts manufactured in the present embodiment are plated parts on which a plating film is selectively formed, and an electroless plating film is formed on a part of the surface of the base material (predetermined pattern, predetermined portion). The electroless plating film is not formed on the parts other than the above.
まず、基材の表面に、上述した本実施形態の無電解メッキ抑制組成物を付与する（図１のステップＳ１）。基材上に付与された無電解メッキ抑制組成物から溶媒（混合溶媒）が蒸発することにより、基材上に触媒活性妨害層が形成される。 First, the electroless plating suppressing composition of the present embodiment described above is applied to the surface of the base material (step S1 in FIG. 1). A catalytic activity interfering layer is formed on the base material by evaporating the solvent (mixed solvent) from the electroless plating suppressing composition applied on the base material.
基材の材料は特に限定されないが、表面に無電解メッキ膜を形成する観点から絶縁体が好ましく、例えば、熱可塑性樹脂、熱硬化性樹脂、光硬化性樹脂、セラミックス及びガラス等を用いることができる。中でも、成形の容易性から、基材は、樹脂から形成される樹脂基材が好ましい。 The material of the base material is not particularly limited, but an insulator is preferable from the viewpoint of forming an electroless plating film on the surface, and for example, a thermoplastic resin, a thermosetting resin, a photocurable resin, ceramics, glass or the like may be used. it can. Above all, a resin base material formed of a resin is preferable as the base material from the viewpoint of ease of molding.
熱可塑性樹脂としては、ナイロン６（ＰＡ６）、ナイロン６６（ＰＡ６６）、ナイロン１２（ＰＡ１２）、ナイロン１１（ＰＡ１１）、ナイロン６Ｔ（ＰＡ６Ｔ）、ナイロン９Ｔ（ＰＡ９Ｔ）、１０Ｔナイロン、１１Ｔナイロン、ナイロンＭＸＤ６（ＰＡＭＸＤ６）、ナイロン９Ｔ・６Ｔ共重合体、ナイロン６・６６共重合体等のポリアミドを用いることができる。ポリアミド以外の樹脂としては、ポリプロピレン、ポリメチルメタクリレート、ポリカーボネート（ＰＣ）、アモルファスポリオレフィン、ポリエーテルイミド、ポリエチレンテレフタレート、ポリエーテルエーテルケトン、ＡＢＳ樹脂、ポリフェニレンサルファイド（ＰＰＳ）、ポリアミドイミド、ポリ乳酸、ポリカプロラクトン、液晶ポリマー（ＬＣＰ）、シクロオレフィンポリマー等を用いることができる。中でも、ポリフェニレンサルファイド（ＰＰＳ）、ポリカーボネート（ＰＣ）、アクリロニトリル・ブタジエン・スチレン共重合体（ＡＢＳ樹脂）、液晶ポリマー（ＬＣＰ）、ナイロン６（ＰＡ６）は、汎用性が高いため、基材の材料として好ましい。尚、これらの熱可塑性樹脂は、単独で用いてもよいし、２種類以上を混合して用いてもよい。 Examples of the thermoplastic resin include nylon 6 (PA6), nylon 66 (PA66), nylon 12 (PA12), nylon 11 (PA11), nylon 6T (PA6T), nylon 9T (PA9T), 10T nylon, 11T nylon, and nylon MXD6. Polyamides such as (PAMXD6), nylon 9T / 6T copolymer, and nylon 6.66 copolymer can be used. Resins other than polyamide include polypropylene, polymethylmethacrylate, polycarbonate (PC), amorphous polyolefin, polyetherimide, polyethylene terephthalate, polyetheretherketone, ABS resin, polyphenylene sulfide (PPS), polyamideimide, polylactic acid, and polycaprolactone. , Liquid liquid polymer (LCP), cycloolefin polymer and the like can be used. Among them, polyphenylene sulfide (PPS), polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS resin), liquid crystal polymer (LCP), and nylon 6 (PA6) have high versatility and are therefore used as base material materials. preferable. These thermoplastic resins may be used alone or in combination of two or more.
熱硬化性樹脂としては、シリコーン樹脂、エポキシ樹脂等を用いることができる。透明な熱硬化性樹脂を用いることで、透明でハンダリフロー耐性を有するデバイス（メッキ部品）を製造できる。光硬化性樹脂としては、アクリル樹脂、シリコーン樹脂、エポキシ樹脂、ポリイミド等を用いることができる。また、セラミックスとしては、アルミナ、窒化アルミ、チタン酸ジルコン酸鉛（ＰＺＴ）、チタン酸バリウム、シリコンウエハ等を用いることができる。 As the thermosetting resin, a silicone resin, an epoxy resin, or the like can be used. By using a transparent thermosetting resin, a transparent device (plated part) having solder reflow resistance can be manufactured. As the photocurable resin, acrylic resin, silicone resin, epoxy resin, polyimide and the like can be used. Further, as the ceramics, alumina, aluminum nitride, lead zirconate titanate (PZT), barium titanate, silicon wafer and the like can be used.
本実施形態で用いる基材は、市販品であってもよいし、市販の材料から成形等により製造してもよい。また、本実施形態で用いる基材は、内部に発泡セルを有する発泡成形体であってもよい。 The base material used in this embodiment may be a commercially available product, or may be manufactured from a commercially available material by molding or the like. Further, the base material used in the present embodiment may be a foam molded product having a foam cell inside.
基材上に付与された無電解メッキ抑制組成物は、基材上で触媒活性妨害層（妨害層）を形成することが好ましい。妨害層は、基材の耐熱性等の物性や誘電率等の電気特性に影響を与えないように、薄い方が好ましい。妨害層の厚みは、例えば、５０００ｎｍ以下が好ましく、１０００ｎｍ以下がより好ましく、３００ｎｍ以下が更により好ましい。一方で、無電解メッキ触媒の触媒活性を妨害する観点からは、例えば、１０ｎｍ以上が好ましく、３０ｎｍ以上がより好ましく、５０ｎｍ以上が更により好ましい。尚、所定パターン以外での無電解メッキ膜の生成を抑制する観点から、妨害層は、後述する無電解メッキ工程において、少なくとも無電解メッキ液と接触する基材表面の領域に形成することが好ましく、基材の表面全面に形成することがより好ましい。 The electroless plating suppressing composition applied on the substrate preferably forms a catalytically active interfering layer (interfering layer) on the substrate. The interfering layer is preferably thin so as not to affect the physical properties such as heat resistance of the base material and the electrical characteristics such as the dielectric constant. The thickness of the interfering layer is, for example, preferably 5000 nm or less, more preferably 1000 nm or less, and even more preferably 300 nm or less. On the other hand, from the viewpoint of interfering with the catalytic activity of the electroless plating catalyst, for example, 10 nm or more is preferable, 30 nm or more is more preferable, and 50 nm or more is even more preferable. From the viewpoint of suppressing the formation of the electroless plating film other than the predetermined pattern, the interfering layer is preferably formed at least in the region of the substrate surface that comes into contact with the electroless plating solution in the electroless plating step described later. , It is more preferable to form it on the entire surface of the base material.
基材の表面に妨害層を形成する方法は、特に限定されない。例えば、無電解メッキ抑制組成物を基材に塗布してもよいし、無電解メッキ抑制組成物に基材を浸漬してもよい。具体的な形成方法としては、ディップコート、スクリーンコート、スプレーコート等が挙げられる。中でも、形成される妨害層の均一性と作業の簡便性の観点から、無電解メッキ抑制組成物に基材を浸漬する方法（ディップコート）が好ましい。 The method for forming the interfering layer on the surface of the base material is not particularly limited. For example, the electroless plating suppressing composition may be applied to the base material, or the base material may be immersed in the electroless plating suppressing composition. Specific examples of the forming method include dip coating, screen coating, spray coating and the like. Above all, a method (dip coating) of immersing the base material in the electroless plating suppressing composition is preferable from the viewpoint of the uniformity of the forming interfering layer and the convenience of work.
無電解メッキ抑制組成物に基材を浸漬するときの無電解メッキ抑制組成物の温度及び浸漬時間は特に限定されず、触媒活性妨害剤の種類、形成される妨害層の膜厚等を考慮して適宜決定できる。無電解メッキ抑制組成物の温度は、例えば、０℃〜１００℃、又は１０℃〜５０℃であり、浸漬時間は、例えば、１秒〜１０分、又は５秒〜２分である。 The temperature and immersion time of the electroless plating suppressing composition when the base material is immersed in the electroless plating suppressing composition are not particularly limited, and the type of catalytic activity interfering agent, the film thickness of the interfering layer to be formed, and the like are taken into consideration. Can be decided as appropriate. The temperature of the electroless plating suppressing composition is, for example, 0 ° C. to 100 ° C., or 10 ° C. to 50 ° C., and the immersion time is, for example, 1 second to 10 minutes, or 5 seconds to 2 minutes.
次に、無電解メッキ抑制組成物を付与した基材の表面の一部を加熱又は光照射する（図１のステップＳ２）。光を照射する方法は、特に限定されず、例えば、レーザー光を基材の表面に所定パターンに従って照射する方法（レーザー描画）や、光を照射しない部分をマスクした後に、基材の表面全体に光を照射する方法等が挙げられる。基材の表面の一部に光を照射することにより、光が熱に変換され、基材の表面は加熱されると推測される。また、基材の表面に光を照射せずに基材の表面を加熱する方法としては、凸部によりパターンが形成された簡易金型等で基材の表面を直接、熱プレスする方法が挙げられる。作業の簡便性及び加熱部分の選択性に優れていること、更に、パターンの変更及び微細化が容易であることから、レーザー描画により基材を加熱することが好ましい。 Next, a part of the surface of the base material to which the electroless plating suppressing composition is applied is heated or irradiated with light (step S2 in FIG. 1). The method of irradiating the light is not particularly limited, and for example, a method of irradiating the surface of the base material with laser light according to a predetermined pattern (laser drawing), or after masking a portion not irradiated with light, the entire surface of the base material is covered. Examples include a method of irradiating light. It is presumed that by irradiating a part of the surface of the base material with light, the light is converted into heat and the surface of the base material is heated. Further, as a method of heating the surface of the base material without irradiating the surface of the base material with light, a method of directly heat-pressing the surface of the base material with a simple mold or the like in which a pattern is formed by convex portions can be mentioned. Be done. It is preferable to heat the base material by laser drawing because the work is easy, the selectivity of the heated portion is excellent, and the pattern can be easily changed and miniaturized.
レーザー光は、例えば、ＣＯ２レーザー、ＹＶＯ４レーザー、ＹＡＧレーザー等のレーザー装置を用いて照射でき、これらのレーザー装置は、妨害層に用いる触媒活性妨害剤の種類に応じて適宜選択できる。 The laser light can be irradiated by using a laser device such as a CO 2 laser, a YVO 4 laser, or a YAG laser, and these laser devices can be appropriately selected according to the type of the catalytically active interfering agent used for the interfering layer.
加熱又は光照射された基材の表面の一部（加熱部分）において、妨害層は除去される。ここで、「妨害層の除去」とは、例えば、加熱部分の妨害層が、蒸発により消失することを意味する。妨害層が付与された基材の表面に、所定パターンのレーザー描画を行うことにより、所定パターンの妨害層除去部分と、妨害層が残存している妨害層残存部分とを形成できる。尚、加熱部分である妨害層除去部分では、妨害層と共に基材の表層部分が蒸発して消失してもよい。また、「妨害層の除去」とは、妨害層が完全に消失するだけでなく、後工程の無電解メッキ処理の進行に影響がない程度に妨害層が残存する場合も含む。妨害層が残存していても、後工程の無電解メッキ処理に影響なければ、無電解メッキ触媒の触媒活性を妨害する作用が消失したことになる。更に、本実施形態では、妨害層の加熱部分が変性又は変質して妨害層として作用しなくなる場合も、「妨害層の除去」に含める。例えば、触媒活性妨害剤がアミド基／アミノ基含有ポリマーである場合、アミド基及び／又はアミノ基が変性又は変質し、その結果、アミド基／アミノ基含有ポリマーが無電解メッキ触媒をトラップできない場合が挙げられる。この場合、妨害層の加熱部分は完全に消失するのではなく、変性物（変質物）が残存する。この変性物は、触媒活性を妨害しない。このため、妨害層が変性又は変質した部分も、妨害層が消失した妨害層除去部分と同様の作用を生じる。 The interfering layer is removed on a portion of the surface (heated portion) of the surface of the heated or light-irradiated substrate. Here, "removal of the interfering layer" means, for example, that the interfering layer in the heated portion disappears by evaporation. By performing a laser drawing of a predetermined pattern on the surface of the base material to which the disturbing layer is applied, a disturbing layer removing portion of the predetermined pattern and a disturbing layer remaining portion in which the disturbing layer remains can be formed. In the disturbing layer removing portion, which is the heating portion, the surface layer portion of the base material may evaporate and disappear together with the disturbing layer. Further, the “removal of the interfering layer” includes not only the case where the interfering layer completely disappears but also the case where the interfering layer remains to the extent that it does not affect the progress of the electroless plating treatment in the subsequent step. Even if the interfering layer remains, if it does not affect the electroless plating treatment in the subsequent step, the action of interfering with the catalytic activity of the electroless plating catalyst disappears. Further, in the present embodiment, the case where the heated portion of the disturbing layer is denatured or deteriorated so as not to act as the disturbing layer is also included in "removal of the disturbing layer". For example, if the catalytic activity interfering agent is an amide group / amino group-containing polymer, the amide group and / or the amino group is modified or altered, and as a result, the amide group / amino group-containing polymer cannot trap the electroless plating catalyst. Can be mentioned. In this case, the heated portion of the interfering layer does not completely disappear, but a modified product (altered product) remains. This modified product does not interfere with catalytic activity. Therefore, the portion where the disturbing layer is denatured or altered also has the same effect as the portion where the disturbing layer disappears.
次に、加熱又は光照射した基材の表面に無電解メッキ触媒を付与する（図１のステップＳ３）。無電解メッキ触媒を基材の表面に付与する方法は、特に限定されない。例えば、センシタイザー・アクチベータ法、キャタライザー・アクセラレータ法等、汎用の方法により、無電解メッキ触媒を基材に付与してもよい。また、例えば、特開２０１７−０３６４８６号公報に開示されている塩化パラジウム等の金属塩を含むメッキ触媒液を用いて、基材の表面に無電解メッキ触媒を付与してもよい。尚、金属塩を含むメッキ触媒液としては、市販のアクチベータ処理液を用いてもよい。 Next, an electroless plating catalyst is applied to the surface of the base material that has been heated or irradiated with light (step S3 in FIG. 1). The method of applying the electroless plating catalyst to the surface of the base material is not particularly limited. For example, the electroless plating catalyst may be applied to the substrate by a general-purpose method such as a sensitizer / activator method or a catalyzer / accelerator method. Further, for example, an electroless plating catalyst may be applied to the surface of the base material by using a plating catalyst solution containing a metal salt such as palladium chloride disclosed in JP-A-2017-036486. As the plating catalyst solution containing the metal salt, a commercially available activator treatment solution may be used.
次に、基材の表面に無電解メッキ液を接触させる（図１のステップＳ４）。基材表面には、妨害層が残存している妨害層残存部分と、加熱等により妨害層が除去された、所定パターンの妨害層除去部分が存在する。この基材表面に無電解メッキ触媒を付与して、無電解メッキ液を接触させることにより、所定パターンの妨害層除去部分のみに、無電解メッキ膜を形成できる。 Next, the electroless plating solution is brought into contact with the surface of the base material (step S4 in FIG. 1). On the surface of the base material, there are a remaining part of the disturbing layer in which the disturbing layer remains and a portion of removing the disturbing layer having a predetermined pattern in which the disturbing layer is removed by heating or the like. By applying an electroless plating catalyst to the surface of the base material and bringing it into contact with the electroless plating solution, an electroless plating film can be formed only on the part where the disturbing layer is removed in a predetermined pattern.
無電解メッキ液としては、目的に応じて任意の汎用の無電解メッキ液を使用しできるが、触媒活性が高く液が安定であるという点から、無電解ニッケルリンメッキ液、無電解銅メッキ液、無電解ニッケルメッキ液が好ましい。 As the electroless plating solution, any general-purpose electroless plating solution can be used depending on the purpose, but from the viewpoint of high catalytic activity and stable solution, electroless nickel phosphorus plating solution and electroless copper plating solution , Electroless nickel plating solution is preferable.
無電解メッキ膜上には、更に、異なる種類の無電解メッキ膜を形成してもよいし、電解メッキにより電解メッキ膜を形成してもよい。基材上のメッキ膜の総厚みを厚くすることにより、所定パターンのメッキ膜を電気回路として用いた場合に電気抵抗を小さくできる。メッキ膜の電気抵抗を下げる観点から、無電解メッキ膜上に積層するメッキ膜は、無電解銅メッキ膜、電解銅メッキ膜、電解ニッケルメッキ膜等が好ましい。また、電気的に孤立した回路には電解メッキを行えないため、このような場合は、無電解メッキにより、基材上のメッキ膜の総厚みを厚くすることが好ましい。また、ハンダリフローに対応できるようメッキ膜パターンのハンダ濡れ性を向上させるために、錫、金、銀等のメッキ膜をメッキ膜パターンの最表面に形成してもよい。 A different type of electroless plating film may be further formed on the electroless plating film, or an electroless plating film may be formed by electroplating. By increasing the total thickness of the plating film on the base material, the electric resistance can be reduced when the plating film having a predetermined pattern is used as an electric circuit. From the viewpoint of reducing the electrical resistance of the plating film, the plating film laminated on the electroless plating film is preferably an electroless copper plating film, an electrolytic copper plating film, an electroless nickel plating film or the like. Further, since electrolytic plating cannot be performed on an electrically isolated circuit, in such a case, it is preferable to increase the total thickness of the plating film on the base material by electroless plating. Further, in order to improve the solder wettability of the plating film pattern so as to correspond to solder reflow, a plating film of tin, gold, silver or the like may be formed on the outermost surface of the plating film pattern.
本実施形態のメッキ部品の製造方法は、無電解メッキ抑制組成物を用いることにより、基材の種類、形状及び状態に依存せずに、無電解メッキ膜の形成を予定していない部分での無電解メッキ膜の生成を抑制できる。本実施形態のメッキ部品の製造方法は、メッキ膜を有する部分と、メッキ膜を有さない部分とのコントラストが明確なメッキ部品を製造できる。 In the method for manufacturing the plated parts of the present embodiment, by using the electroless plating suppressing composition, the formation of the electroless plating film is not planned in the portion regardless of the type, shape and state of the base material. The formation of electroless plating film can be suppressed. The method for manufacturing a plated part of the present embodiment can manufacture a plated part having a clear contrast between a portion having a plating film and a portion having no plating film.
また、本実施形態のメッキ部品の製造方法は、無電解メッキ抑制組成物が第１溶媒と第２溶媒との混合溶媒を含むことで、溶媒の蒸発過程において、ブラッシングを抑制しつつ、溶媒（混合溶媒）を十分に蒸発させることができる。この結果、例えば、ブラッシングが発生し易い多湿環境下においても、高いメッキ選択性（メッキ膜有無のコントラスト）が得られる。 Further, in the method for producing a plated component of the present embodiment, the electroless plating suppressing composition contains a mixed solvent of a first solvent and a second solvent, so that in the process of vaporizing the solvent, brushing is suppressed while the solvent ( The mixed solvent) can be sufficiently evaporated. As a result, for example, high plating selectivity (contrast with or without plating film) can be obtained even in a humid environment where brushing is likely to occur.
尚、上述したメッキ部品の製造方法では、基材に無電解メッキ抑制組成物を付与し（図１のステップＳ１）、その後、基材の表面の一部を加熱又は光照射する（図１のステップＳ２）。しかし、本実施形態は、これに限定されず、基材の表面の一部を加熱又は光照射し（図１のステップＳ２）、その後、基材に無電解メッキ抑制組成物を付与してもよい。例えば、レーザー描画（光照射）した基材の表面は粗化されるため、その上に無電解メッキ抑制組成物を付与しても、無電解メッキを抑制するのに十分な妨害層が形成されない。このため、レーザー描画部分にのみ、選択的にメッキ膜を形成できる。 In the method for manufacturing plated parts described above, an electroless plating suppressing composition is applied to a base material (step S1 in FIG. 1), and then a part of the surface of the base material is heated or irradiated with light (FIG. 1). Step S2). However, the present embodiment is not limited to this, and a part of the surface of the base material may be heated or irradiated with light (step S2 in FIG. 1), and then the electroless plating suppressing composition may be applied to the base material. Good. For example, since the surface of the base material drawn by laser drawing (light irradiation) is roughened, even if an electroless plating suppressing composition is applied thereto, a sufficient interfering layer for suppressing electroless plating is not formed. .. Therefore, the plating film can be selectively formed only on the laser drawing portion.
以下、実施例及び比較例により本発明を具体的に説明するが、本発明は下記の実施例及び比較例により制限されない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples and Comparative Examples.
以下に説明する方法により、試料１〜１５（無電解メッキ抑制組成物）を調製した。試料１〜１５の組成を表２及び３に示す。尚、試料２〜９及び１１〜１５の無電解メッキ抑制組成物は本発明の実施例に相当し、試料１及び１０は本発明の比較例に相当する。 Samples 1 to 15 (electroless plating suppressing composition) were prepared by the method described below. The compositions of Samples 1 to 15 are shown in Tables 2 and 3. The electroless plating suppressing compositions of Samples 2 to 9 and 11 to 15 correspond to the examples of the present invention, and Samples 1 and 10 correspond to the comparative examples of the present invention.
［試料１］
触媒活性妨害剤として、下記式（５）で表されるハイパーブランチポリマーを、国際公開第２０１８／１３１４９２号に開示される方法により合成した。
[Sample 1]
As a catalytic activity interfering agent, a hyperbranched polymer represented by the following formula (5) was synthesized by the method disclosed in International Publication No. 2018/131492.
式（５）で表されるハイパーブランチポリマーは、式（１）で表されるポリマーであり、式（１）において、Ａ１が式（２）で表される基であり；Ａ２が式（３）で表される基であって、Ｒ1が単結合であり、Ｒ2が水素であり、Ｒ３がイソプロピル基であり；Ａ３が式（４）で表されるジチオカルバメート基であり、Ｒ４及びＲ５がエチル基であり、Ｒ０がビニル基又はエチル基である。 The hyperbranched polymer represented by the formula (5) is a polymer represented by the formula (1), and in the formula (1), A 1 is a group represented by the formula (2); A 2 is a formula. The group represented by (3), R 1 is a single bond, R 2 is hydrogen, R 3 is an isopropyl group; A 3 is a dithiocarbamate group represented by the formula (4). Yes, R 4 and R 5 are ethyl groups, and R 0 is a vinyl or ethyl group.
合成したハイパーブランチポリマーの分子量をＧＰＣ（ゲル浸透クロマトグラフィー）で測定した。分子量は、数平均分子量（Ｍｎ）＝９,９４６、重量平均分子量（Ｍｗ）＝２４,７９２であり、ハイパーブランチ構造独特の数平均分子量（Ｍｎ）と重量平均分子量（Ｍｗ）とが大きく異なった値であった。 The molecular weight of the synthesized hyperbranched polymer was measured by GPC (gel permeation chromatography). The molecular weights were number average molecular weight (Mn) = 9,946 and weight average molecular weight (Mw) = 24,792, and the number average molecular weight (Mn) and weight average molecular weight (Mw) peculiar to the hyperbranched structure were significantly different. It was a value.
合成した式（５）で表されるハイパーブランチポリマーと、第２溶媒（ＭＥＫ）とを表２に示す組成比率で混合し、試料１（無電解メッキ抑制組成物）を調製した。 The synthesized hyperbranched polymer represented by the formula (5) and the second solvent (MEK) were mixed at the composition ratio shown in Table 2 to prepare Sample 1 (electroless plating suppressing composition).
［試料２〜９］
試料２〜９は、第２溶媒（ＭＥＫ）に加えて第１溶媒（トルエン）を含むこと以外は、試料１と同様の方法により調製した。試料２〜９中において、第１溶媒の配合量（Ａ）の、第２溶媒の配合量（Ｂ）に対する質量比（Ａ／Ｂ）は、表２に示す値とした。
[Samples 2-9]
Samples 2 to 9 were prepared in the same manner as in Sample 1 except that the first solvent (toluene) was contained in addition to the second solvent (MEK). In Samples 2 to 9, the mass ratio (A / B) of the compounding amount (A) of the first solvent to the compounding amount (B) of the second solvent was set to the value shown in Table 2.
［試料１０］
試料１０は、第２溶媒（ＭＥＫ）を含まず、代わりに第１溶媒（トルエン）を含むこと以外は、試料１と同様の方法により調製した。
[Sample 10]
Sample 10 was prepared by the same method as Sample 1 except that it did not contain the second solvent (MEK) and instead contained the first solvent (toluene).
［試料１１〜１４］
試料１１〜１４は、第２溶媒（ＭＥＫ）に加えて第１溶媒を含むこと以外は、試料１と同様の方法により調製した。試料１１〜１４では、第１溶媒として表３に示す化合物を用い、第１溶媒の配合量（Ａ）の、第２溶媒の配合量（Ｂ）に対する質量比（Ａ／Ｂ）は表３に示す値とした。
[Samples 11-14]
Samples 11 to 14 were prepared in the same manner as in Sample 1 except that the first solvent was contained in addition to the second solvent (MEK). In Samples 11 to 14, the compounds shown in Table 3 were used as the first solvent, and the mass ratio (A / B) of the blending amount (A) of the first solvent to the blending amount (B) of the second solvent is shown in Table 3. The value is shown.
［試料１５］
試料１５は、第２溶媒としてＭＥＫに変えてＴＨＦを用い、更に第２溶媒に加えて第１溶媒（トルエン）を含むこと以外は、試料１と同様の方法により調製した。試料１５では、第１溶媒の配合量（Ａ）の、第２溶媒の配合量（Ｂ）に対する質量比（Ａ／Ｂ）は表３に示す値とした。
[Sample 15]
Sample 15 was prepared by the same method as that of Sample 1 except that THF was used instead of MEK as the second solvent and the first solvent (toluene) was further contained in addition to the second solvent. In Sample 15, the mass ratio (A / B) of the blended amount (A) of the first solvent to the blended amount (B) of the second solvent was set to the value shown in Table 3.
以上説明した試料１〜１５に用いた第１及び第２溶媒に対する、触媒活性妨害剤の溶解度を表２及び表３に併せて示す。第１溶媒として用いたシクロヘキサノン、ＭＩＢＫ、第２溶媒として用いたＭＥＫ及びＴＨＦに対して、触媒活性妨害剤は溶解可能であった。これらの溶媒に対する触媒活性妨害剤の溶解度は、５．０以上であった。一方、第１溶媒であるトルエン、ＰＧＭ、ＩＰＡに対する触媒活性妨害剤の溶解度は、０．１以下と低かったが、ＩＰＡ以外の溶媒、即ち、トルエン及びＰＧＭに対して触媒活性妨害剤は分散可能であった（第１溶媒中の触媒活性妨害剤の平均粒子径が２５０ｎｍ未満）。 Tables 2 and 3 also show the solubility of the catalytic activity interfering agent in the first and second solvents used in the samples 1 to 15 described above. The catalytic activity interfering agent was soluble in cyclohexanone and MIBK used as the first solvent, and MEK and THF used as the second solvent. The solubility of the catalytic activity interfering agent in these solvents was 5.0 or higher. On the other hand, the solubility of the catalytic activity interfering agent in the first solvent, toluene, PGM and IPA, was as low as 0.1 or less, but the catalytic activity interfering agent can be dispersed in a solvent other than IPA, that is, toluene and PGM. (The average particle size of the catalytic activity interfering agent in the first solvent is less than 250 nm).
［評価方法］
試料１〜１５について、以下の評価を行った。評価結果を表２及び３に示す。
[Evaluation methods]
The following evaluations were performed on Samples 1 to 15. The evaluation results are shown in Tables 2 and 3.
（１）ブラッシング（白化）評価
試料１〜１５それぞれをディップコーターにより板状のガラス基材（松浪硝子工業社製、大型スライド白縁磨Ｎｏ．２）に温度：２５℃、湿度：８０％の多湿環境下で塗布し（ディップコート）、温度：８０℃で５分間乾燥させ、膜厚約１００ｎｍの触媒活性妨害層をカラス基材上に形成した。触媒活性妨害層を目視により観察し、以下の価基準に基づいてブラッシングを評価した。
(1) Brushing (whitening) evaluation Samples 1 to 15 are each placed on a plate-shaped glass substrate (manufactured by Matsunami Glass Industry Co., Ltd., large slide white edge polishing No. 2) with a dip coater at a temperature of 25 ° C. and a humidity of 80%. It was applied in a humid environment (dip coating) and dried at a temperature of 80 ° C. for 5 minutes to form a catalytically active interfering layer having a film thickness of about 100 nm on the glass substrate. The catalytically active interfering layer was visually observed and brushing was evaluated based on the following valuation criteria.
＜ブラッシングの評価基準＞
○：目視でブラッシングが認められなかった。
×：目視でブラッシングが認められた。
<Evaluation criteria for brushing>
◯: No brushing was visually observed.
X: Brushing was visually observed.
（２）ヘイズ値の測定
ブラッシング評価で形成した、試料１〜１５の触媒活性妨害層それぞれのヘイズ値をヘイズメーター（日本電色工業社製、ＮＤＨ２０００）を用いて測定した。尚、ヘイズ値は、その値が小さい程、触媒活性妨害層において光散乱が生じていない（曇っていない）ことを示す。即ち、ヘイズ値が小さい程、触媒活性妨害層において、ブラッシング及び触媒活性妨害剤の凝集が生じておらず、均一な層が形成されていると判断できる。
(2) Measurement of haze value The haze value of each of the catalytically active interfering layers of Samples 1 to 15 formed by the brushing evaluation was measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). The smaller the haze value, the less light scattering (not cloudy) occurs in the catalytic activity interfering layer. That is, it can be determined that the smaller the haze value, the more uniform the layer is formed without brushing and aggregation of the catalytic activity interfering agent in the catalytic activity interfering layer.
（３）無電解メッキ選択性の評価
まず、汎用の射出成形機を用いてポリフェニレンサルファイド（帝人株式会社製、ガラス繊維強化ＰＰＳ １０４０Ｇ、黒色）を５ｃｍ×８ｃｍ×０．２ｃｍの板状体に成形した。この板状体を基材として用いた。試料１〜１５それぞれを、温度：２５℃、湿度：８０％の多湿環境下で基材に塗布し（ディップコート）、温度：８０℃で５分間乾燥させた。これにより、膜厚約１００ｎｍの触媒活性妨害層を基材上に形成した。
(3) Evaluation of electroless plating selectivity First, polyphenylene sulfide (manufactured by Teijin Limited, glass fiber reinforced PPS 1040G, black) is molded into a 5 cm x 8 cm x 0.2 cm plate using a general-purpose injection molding machine. did. This plate-like body was used as a base material. Each of the samples 1 to 15 was applied to a substrate (dip coat) in a humid environment with a temperature of 25 ° C. and a humidity of 80%, and dried at a temperature of 80 ° C. for 5 minutes. As a result, a catalytic activity interfering layer having a film thickness of about 100 nm was formed on the substrate.
触媒活性妨害層を形成した基材にＹＶＯ４レーザー（キーエンス製、ＭＤ−Ｖ９９２９ＷＡ、波長１０６４ｎｍ）を用いて、下記の配線パターンＡ及びＢをレーザー描画した。レーザー描画時のパワーは８０％、周波数は４０ｋＨｚ，線速度は６００ｍｍ／ｓとした。
配線パターンＡ（Ｌ／Ｓ＝０．５ｍｍ／０．５ｍｍ）：０．１ｍｍピッチの格子パターンによって形成されたライン（０．５ｍｍ×５ｍｍ）をスペース０．５ｍｍにて５本描画。
配線パターンＢ（Ｌ／Ｓ＝０．２ｍｍ／０．２ｍｍ）：０．０５ｍｍピッチの格子パターンによって形成されたライン（０．２ｍｍ×５ｍｍ）をスペース０．２ｍｍにて５本描画。
YVO 4 laser to a substrate to form a catalytically active interference layer (manufactured by Keyence, MD-V9929WA, wavelength 1064 nm) was used to laser writing the following wiring patterns A and B. The power at the time of laser drawing was 80%, the frequency was 40 kHz, and the linear velocity was 600 mm / s.
Wiring pattern A (L / S = 0.5 mm / 0.5 mm): Five lines (0.5 mm × 5 mm) formed by a grid pattern with a 0.1 mm pitch are drawn with a space of 0.5 mm.
Wiring pattern B (L / S = 0.2 mm / 0.2 mm): Five lines (0.2 mm × 5 mm) formed by a grid pattern with a pitch of 0.05 mm are drawn with a space of 0.2 mm.
レーザー描画した基材に、市販の無電解メッキ用触媒液（奥野製薬工業製、センシタイザー、アクチベータ）を用い汎用の方法により、無電解メッキ触媒を付与した（センシタイザー・アクチベータ法）。次に、無電解メッキ触媒を付与した基材を６０℃に調整した無電解ニッケルリンメッキ液（奥野製薬工業製、トップニコロンＬＰＨ−Ｌ、ｐＨ６．５）に１０分間浸漬した。これにより、試料１〜１５それぞれを用いて作製したメッキ部品を得た。 An electroless plating catalyst was applied to the laser-drawn substrate by a general-purpose method using a commercially available electroless plating catalyst solution (manufactured by Okuno Pharmaceutical Co., Ltd., sensitizer, activator) (sensitizer-activator method). Next, the base material to which the electroless plating catalyst was applied was immersed in an electroless nickel phosphorus plating solution (manufactured by Okuno Pharmaceutical Co., Ltd., Top Nicolon LPH-L, pH 6.5) adjusted to 60 ° C. for 10 minutes. As a result, plated parts prepared using each of the samples 1 to 15 were obtained.
作製したメッキ部品それぞれの表面を目視およびマイクロスコープ顕微鏡にて観察し、以下の評価基準に従って無電解メッキの選択性を評価した。 The surface of each of the produced plated parts was visually observed and observed with a microscope microscope, and the selectivity of electroless plating was evaluated according to the following evaluation criteria.
＜無電解メッキ選択性の評価基準＞
○：配線パターンＡ及びＢ両方において、隣接する配線間の短絡（繋がり）が無かった。
△：配線パターンＡ（Ｌ／Ｓ＝０．５ｍｍ／０．５ｍｍ）では、配線間の短絡（繋がり）が無いが、配線パターンＢ（Ｌ／Ｓ＝０．２ｍｍ／０．２ｍｍ）では、一部の隣接する配線間に短絡が認められた。
×：配線パターンＡ及びＢ両方において、一部の隣接する配線間に短絡（繋がり）が認められた。
<Evaluation criteria for electroless plating selectivity>
◯: In both wiring patterns A and B, there was no short circuit (connection) between adjacent wirings.
Δ: In the wiring pattern A (L / S = 0.5 mm / 0.5 mm), there is no short circuit (connection) between the wirings, but in the wiring pattern B (L / S = 0.2 mm / 0.2 mm), one A short circuit was observed between the wires adjacent to each other.
X: In both wiring patterns A and B, a short circuit (connection) was observed between some adjacent wirings.
表２及び３に示すように、試料２〜９及び１１〜１５（無電解メッキ抑制組成物）は、いずれも、多湿環境下での触媒活性妨害層の形成においてブラッシングが生じず、高いメッキ選択性（メッキ膜有無のコントラスト）を示した（評価結果：〇又は△）。また、試料２〜９及び１１〜１５の触媒活性妨害層のヘイズ値は、２．０％以下と低かった。これから、試料２〜９及び１１〜１５の触媒活性妨害層は、ブラッシング及び触媒活性妨害剤の凝集が生じておらず、均一であると判断できる。 As shown in Tables 2 and 3, samples 2 to 9 and 11 to 15 (electroless plating suppressing composition) do not cause brushing in the formation of the catalytic activity interfering layer in a humid environment, and high plating selection is performed. The property (contrast with or without plating film) was shown (evaluation result: 〇 or Δ). The haze value of the catalytically active interfering layers of Samples 2-9 and 11-15 was as low as 2.0% or less. From this, it can be determined that the catalytic activity interfering layers of Samples 2 to 9 and 11 to 15 are uniform without brushing and aggregation of the catalytic activity interfering agent.
中でも、質量比（Ａ／Ｂ）＝３／９７〜３０／７０を満たす試料２〜８及び１１〜１５は、より高いメッキ選択性を示した（評価結果：〇）。試料２〜８及び１１〜１５と比較して、試料９のメッキ選択性がやや低い（評価結果：△）原因は、質量比（Ａ／Ｂ）がやや高いため（（Ａ／Ｂ）＝３５／６５）、混合溶媒の乾燥が不十分となり触媒活性妨害層が不均一となったためと推測される。 Among them, the samples 2 to 8 and 11 to 15 satisfying the mass ratio (A / B) = 3/97 to 30/70 showed higher plating selectivity (evaluation result: 〇). The plating selectivity of sample 9 is slightly lower than that of samples 2 to 8 and 11 to 15 (evaluation result: Δ) because the mass ratio (A / B) is slightly higher ((A / B) = 35). / 65), it is presumed that the mixed solvent was not sufficiently dried and the catalytic activity interfering layer became non-uniform.
尚、試料２〜９及び１１〜１５では第２溶媒が主溶媒であり、第２溶媒に対する触媒活性妨害剤の溶解度は５．０（ｇ／１００ｇ）以上であった。試料２〜９及び１１〜１５において、触媒活性妨害剤は第１溶媒と第２溶媒との混合溶媒中に溶解していた。 In Samples 2-9 and 11-15, the second solvent was the main solvent, and the solubility of the catalytic activity interfering agent in the second solvent was 5.0 (g / 100 g) or more. In Samples 2-9 and 11-15, the catalytic activity interfering agent was dissolved in a mixed solvent of the first solvent and the second solvent.
一方、第１溶媒を含まない試料１では、ブラッシングが生じ、この結果、メッキ選択性が低下した。試料１の触媒活性妨害層のヘイズ値が高い原因は、ブラッシング（白化）である。また、第２溶媒を含まない試料１０では、ブラッシングは生じなかったが、メッキ選択性が低かった。この原因は、第２溶媒を含まないため溶媒の乾燥が不十分だったためと推測される。試料１０の触媒活性妨害層は、ブラッシングが生じていないがヘイズ値が高かった。この原因は、触媒活性妨害層中で触媒活性妨害剤が分散しているためである。 On the other hand, in the sample 1 containing no first solvent, brushing occurred, and as a result, the plating selectivity was lowered. The cause of the high haze value of the catalytic activity interfering layer of Sample 1 is brushing (whitening). Further, in the sample 10 containing no second solvent, brushing did not occur, but the plating selectivity was low. It is presumed that this is because the solvent was not sufficiently dried because it did not contain the second solvent. The catalytic activity interfering layer of Sample 10 had a high haze value although brushing did not occur. This is because the catalytic activity interfering agent is dispersed in the catalytic activity interfering layer.
本発明の無電解メッキ抑制組成物は、高いメッキ選択性を示す。このため、スマートフォン、自動車分野等で用いられるＭＩＤ等のメッキ部品の製造に利用可能である。 The electroless plating suppressing composition of the present invention exhibits high plating selectivity. Therefore, it can be used for manufacturing plated parts such as MID used in the fields of smartphones and automobiles.
Claims (16)
アミド基及びアミノ基の少なくとも一方を有する化合物である触媒活性妨害剤と、
蒸気圧が、０．３ｋＰａ〜５ｋＰａの第１溶媒と、
蒸発圧が５ｋＰａより大きい第２溶媒と、を含む無電解メッキ抑制組成物。 An electroless plating suppression composition
A catalytic activity interfering agent, which is a compound having at least one of an amide group and an amino group,
With a first solvent having a vapor pressure of 0.3 kPa to 5 kPa,
An electroless plating suppressing composition containing a second solvent having an evaporation pressure greater than 5 kPa.
基材の表面に、請求項１〜１５のいずれか一項に記載の前記無電解メッキ抑制組成物を付与することと、
前記基材の表面の一部を加熱又は光照射することと、
加熱又は光照射した前記基材の表面に無電解メッキ触媒を付与することと、
前記無電解メッキ触媒を付与した前記基材の表面に無電解メッキ液を接触させ、前記表面の加熱部分又は光照射部分に無電解メッキ膜を形成することと、を含むメッキ部品の製造方法。 It is a manufacturing method of plated parts.
To impart the electroless plating suppressing composition according to any one of claims 1 to 15 to the surface of the base material.
By heating or irradiating a part of the surface of the base material,
Applying an electroless plating catalyst to the surface of the base material that has been heated or irradiated with light,
A method for manufacturing an electroless plating component, comprising contacting an electroless plating solution with the surface of the base material to which the electroless plating catalyst is applied to form an electroless plating film on a heated portion or a light-irradiated portion of the surface.
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| JP2011214001A (en) * | 2010-03-19 | 2011-10-27 | Fujifilm Corp | Inkjet ink, surface metal film material and method for manufacturing the same, metal pattern material and method for manufacturing the same |
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| JP2017160518A (en) * | 2016-03-11 | 2017-09-14 | 日立マクセル株式会社 | Producing method of plating part, plating part, catalytic activity disturbing agent, and electroless plating compound material |
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| JP2011062674A (en) * | 2009-09-18 | 2011-03-31 | Fujifilm Corp | Method for forming polymer layer |
| JP2011214001A (en) * | 2010-03-19 | 2011-10-27 | Fujifilm Corp | Inkjet ink, surface metal film material and method for manufacturing the same, metal pattern material and method for manufacturing the same |
| JP2017031441A (en) * | 2015-07-29 | 2017-02-09 | 日立マクセル株式会社 | Manufacturing method of plated part and plated part |
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