JP4053369B2 - Organic acid soluble polyamide resin, method for producing the same, and method for producing three-dimensional injection molded circuit components - Google Patents

Description

【００２０】
〔式中、Ｒ¹は、それぞれ独立に水素原子または炭素原子数１〜６のアルキル基であり、Ｙは、水素原子、ＲＮＨ₂またはＲＯＨ（Ｒは、炭素原子数１〜６のアルキレン基）である。〕
で表されるピペラジン化合物、及び下記式(II)
【００２１】
【化６】

【００２２】
〔式中、Ｒ¹は、それぞれ独立に水素原子または炭素原子数１〜６のアルキル基であり、Ｒ²は、二価の脂肪族炭化水素基であり、Ｙは、水素原子、ＲＮＨ₂またはＲＯＨ（Ｒは、炭素原子数１〜６のアルキレン基）である。〕
で表されるジピペリジル化合物からなる群より選ばれる少なくとも一種の含窒素複素環化合物(b-1)を全アミノ基の２０当量％以上と、該含窒素複素環化合物以外のジアミン化合物(b-2)を全アミノ基の８０当量％以下とからなるジアミン成分とを、
全アミン当量の全カルボキシル当量に対する比が０．８：１〜１．３：１の範囲内で重縮合して得られるポリアミドであり、
（２）ポリアミドポリアミン（Ｂ）が、
ｃ）二量体脂肪酸含有量が６５重量％以上のダイマー酸またはそのアミド生成可能な誘導体(ｃ-1)を全カルボキシル基の２０当量％以上と、ダイマー酸以外のジカルボン酸化合物またはそのアミド生成可能な誘導体(ｃ-2)を全カルボキシル基の８０当量％以下とからなるジカルボン酸成分と、
ｄ）ポリアルキレンポリアミンとを、
全アミン当量の全カルボキシル当量に対する比が１．３：１〜３．０：１の範囲内で重縮合して得られるポリアミドポリアミンであり、かつ、
（４）アミド交換反応後に下記物性
ｉ）軟化点が８０〜１９０℃、
ii）酸価が０〜５ｍｇＫＯＨ/ｇ、
iii）アミン価が１０〜１００ｍｇＫＯＨ／ｇ、
iv）２００℃で測定した溶融粘度が３５０〜８０，０００ｍＰａ・ｓ、及び
v）濃度３０重量％の酢酸水溶液１００ｍｌに６０℃で３０分間浸漬して測定した溶解速度が０.２ｍｍ／３０分以上
を有する
ことを特徴とする有機酸可溶型ポリアミド樹脂が提供される。
【００２３】
また、本発明によれば、ポリアミド（Ａ）とポリアミドポリアミン（Ｂ）とをアミド交換反応させる新規な有機酸可溶型ポリアミド樹脂の製造方法であって、
（１）ポリアミド（Ａ）が、
ａ）二量体脂肪酸含有量が６５重量％以上のダイマー酸またはそのアミド生成可能な誘導体(a-1)を全カルボキシル基の２０当量％以上と、ダイマー酸以外のジカルボン酸化合物またはそのアミド生成可能な誘導体(a-2)を全カルボキシル基の８０当量％以下とからなるジカルボン酸成分と、
ｂ）下記式（Ｉ）
【００２４】
【化７】

【００２５】
〔式中、Ｒ¹は、それぞれ独立に水素原子または炭素原子数１〜６のアルキル基であり、Ｙは、水素原子、ＲＮＨ₂またはＲＯＨ（Ｒは、炭素原子数１〜６のアルキレン基）である。〕
で表されるピペラジン化合物、及び下記式(II)
【００２６】
【化８】

【００２７】
〔式中、Ｒ¹は、それぞれ独立に水素原子または炭素原子数１〜６のアルキル基であり、Ｒ²は、二価の脂肪族炭化水素基であり、Ｙは、水素原子、ＲＮＨ₂またはＲＯＨ（Ｒは、炭素原子数１〜６のアルキレン基）である。〕
で表されるジピペリジル化合物からなる群より選ばれる少なくとも一種の含窒素複素環化合物(b-1)を全アミノ基の２０当量％以上と、該含窒素複素環化合物以外のジアミン化合物(b-2)を全アミノ基の８０当量％以下とからなるジアミン成分とを、
全アミン当量の全カルボキシル当量に対する比が０．８：１〜１．３：１の範囲内で重縮合して得られるポリアミドであり、
（２）ポリアミドポリアミン（Ｂ）が、
ｃ）二量体脂肪酸含有量が６５重量％以上のダイマー酸またはそのアミド生成可能な誘導体(ｃ-1)を全カルボキシル基の２０当量％以上と、ダイマー酸以外のジカルボン酸化合物またはそのアミド生成可能な誘導体(ｃ-2)を全カルボキシル基の８０当量％以下とからなるジカルボン酸成分と、
ｄ）ポリアルキレンポリアミンとを、
全アミン当量の全カルボキシル当量に対する比が１．３：１〜３．０：１の範囲内で重縮合して得られるポリアミドポリアミンであり、そして、
（３）ポリアミド（Ａ）とポリアミドポリアミン（Ｂ）とを重量比（Ａ：Ｂ）９５：５〜４０：６０で、１５０〜３００の範囲内の温度で１時間以上溶融混合してアミド交換反応をさせることにより、
（４）アミド交換反応後に下記物性
ｉ）軟化点が８０〜１９０℃、
ii）酸価が０〜５ｍｇＫＯＨ/ｇ、
iii）アミン価が１０〜１００ｍｇＫＯＨ／ｇ、
iv）２００℃で測定した溶融粘度が３５０〜８０，０００ｍＰａ・ｓ、及び
v）濃度３０重量％の酢酸水溶液１００ｍｌに６０℃で３０分間浸漬して測定した溶解速度が０.２ｍｍ／３０分以上
を有するポリアミド樹脂を生成させる
ことを特徴とする有機酸可溶型ポリアミド樹脂の製造方法が提供される。
【００２８】
さらに、本発明によれば、（１）回路部品の基板を構成する一次成形品を合成樹脂の射出成形により形成する工程１、
（２）必要に応じて、１次成形品の表面を粗面化する工程２、
（３）一次成形品の回路を形成すべき部分を除く全表面に、前記の有機酸可溶型ポリアミド樹脂を射出成形して、有機酸可溶型ポリアミド樹脂被覆層を有する二次成形品を成形する工程３、
（４）二次成形品の有機酸可溶型ポリアミド樹脂被覆層部分を除く回路を形成すべき部分に、めっきにより導体回路層を形成する工程４、及び
（５）有機酸水溶液を用いて有機酸可溶型ポリアミド樹脂被覆層を溶解除去する工程５
からなる一連の工程を含む三次元射出成形回路部品の製造方法が提供される。
【００２９】
さらにまた、本発明によれば、(i）回路部品の基板を構成する一次成形品を合成樹脂の射出成形により形成する工程Ｉ、
（ii）必要に応じて、１次成形品の表面を粗面化する工程II、
（iii）一次成形品の回路を形成すべき部分を除く全表面に、前記の有機酸可溶型ポリアミド樹脂を射出成形して、有機酸可溶型ポリアミド樹脂被覆層を有する二次成形品を成形する工程III、
（iv）二次成形品の有機酸可溶型ポリアミド樹脂被覆層部分を除く回路を形成すべき部分に、触媒を賦与する工程IV、
（v）有機酸水溶液を用いて有機酸可溶型ポリアミド樹脂被覆層を溶解除去する工程V、及び
（vi）触媒賦与部分にめっきして導体回路層を形成する工程VI
からなる一連の工程を含む三次元射出成形回路部品の製造方法が提供される。
【００３０】
【発明の実施の形態】
本発明で使用するポリアミド（Ａ）は、二量体脂肪酸含有量が６５重量％以上のダイマー酸またはそのアミド生成可能な誘導体(a-1)を全カルボキシル基の２０当量％以上と、ダイマー酸以外のジカルボン酸化合物またはそのアミド生成可能な誘導体(a-2)を全カルボキシル基の８０当量％以下とからなるジカルボン酸成分と、下記式（Ｉ）
【００３１】
【化９】

【００３２】
〔式中、Ｒ¹は、それぞれ独立に水素原子または炭素原子数１〜６のアルキル基であり、Ｙは、水素原子、ＲＮＨ₂またはＲＯＨ（Ｒは、炭素原子数１〜６のアルキレン基）である。〕
で表されるピペラジン化合物、及び下記式(II)
【００３３】
【化１０】

【００３４】
〔式中、Ｒ¹は、それぞれ独立に水素原子または炭素原子数１〜６のアルキル基であり、Ｒ²は、二価の脂肪族炭化水素基であり、Ｙは、水素原子、ＲＮＨ₂またはＲＯＨ（Ｒは、炭素原子数１〜６のアルキレン基）である。〕
で表されるジピペリジル化合物からなる群より選ばれる少なくとも一種の含窒素複素環化合物(b-1)を全アミノ基の２０当量％以上と、該含窒素複素環化合物以外のジアミン化合物(b-2)を全アミノ基の８０当量％以下とからなるジアミン成分とを、全アミン当量の全カルボキシル当量に対する比が０．８：１〜１．３：１の範囲内で重縮合して得られるポリアミドである。本発明のポリアミド（Ａ）は、例えば、特公昭４５−６８２５号公報、特開昭４８−１４７９０号公報に記載されている製造方法により得ることができる。
【００３５】
本発明で使用するダイマー酸(Dimer acid)は、オレイン酸（Ｃ₁₈Ｈ₃₄Ｏ₂）、リノール酸（Ｃ₁₈Ｈ₃₂Ｏ₂）、リノレン酸（Ｃ₁₈Ｈ₃₀Ｏ₂）などの不飽和脂肪酸を粘土触媒により縮合させて二量体化した重合脂肪酸である。飽和脂肪酸を過酸化物触媒を用いて重合することによっても、ダイマー酸を得ることができる。ダイマー酸の主成分は二量体であり、その他に単量体や三量体などを含んでいる。ダイマー酸の代表的なものは、単量体（Ｃ₁₈）、二量体（Ｃ₃₆）及び三量体（Ｃ₅₄）の混合物である。
【００３６】
ダイマー酸の製法は、米国特許第３１５７６８１号明細書に記載されている。トール油脂肪酸などのオレイン酸、リノール酸を主成分とする脂肪酸から製造された市販のダイマー酸は、一般に、Ｃ₁₈単量体酸（単量体）５〜１５重量％、Ｃ₃₆二量体酸（二量体）６０〜８０重量％、及びＣ₅₄以上の高次重合体酸（三量体）１０〜３５重量％の組成を有している。
【００３７】
この未分別ダイマー酸中の単量体、二量体及び三量体の比率は、原料及びその重合条件に依存する。単量体脂肪酸とは、未重合の単量体酸を意味し、二量体脂肪酸とは、二量体脂肪酸を意味し、三量体脂肪酸とは、主として三量体酸よりなり更に高次のものも含有する重合体を意味する。ダイマー酸とは、脂肪酸から得られる重合酸の総称で、単量体、二量体、三量体の混合物である。ダイマー酸の原料となる脂肪酸とは、飽和、エチレン系不飽和、アセチレン系不飽和の天然及び合成の脂肪酸族のカルボン酸で、炭素原子数８乃至２４のものをいう。
【００３８】
飽和脂肪酸は、一般に、米国特許第３１５７６８１号明細書に記載の方法とは少し異なる方法で重合される。即ち、飽和脂肪酸は、中温で過酸化ジ−ｔ−ブチルのような過酸化物触媒を用いて重合される。一般に、重合体の収率が低いのでこれらの原料は工業的に重要ではない。飽和脂肪酸としては、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、イソパルミチン酸、ステアリン酸、アラキジン酸、ベヘン酸、及びリグノセリン酸のような直鎖及び側鎖の酸が挙げられる。重合されるエチレン系及びアセチレン系不飽和脂肪酸とその重合法に関しては、米国特許第３１５７６８１号明細書に記載されている。
【００３９】
ダイマー酸中に存在する単量体、二量体、及び三量体脂肪酸の含量は、ガスクロマトグラフィーにより、対応するメチルエステルとして定量される。他の定量法は、ミクロ分子蒸留分析法、液体クロマトグラフィー等がある。
【００４０】
本発明では、二量体脂肪酸含有量が６５重量％以上のダイマー酸またはそのアミド生成可能な誘導体(a-1)を使用する。二量体脂肪酸の含有量は、好ましくは８０重量％以上、特に好ましくは９０〜９５重量％である。二量体脂肪酸の含有量を高めるには、ダイマー酸を分留するか、溶剤抽出法により単量体を除去するなどの方法を採用することができる。二量体脂肪酸の含有量が低すぎると、溶融成形性などに優れたポリアミドを得ることができない。
【００４１】
ダイマー酸は、酸の形で使用することができるが、この他、アミド生成可能な誘導体とすることもできる。アミド生成可能な誘導体とは、ジアミン成分と反応してアミド結合を生成することが可能な誘導体を意味する。このような誘導体としては、エステル、ハロゲン化物、及び酸無水物がある。エステルは、ダイマー酸をアルコールと反応させることにより得ることができる。エステル残基としては、炭素原子数１〜８のアルキル基またはアリール基が好ましい。これらの中でも、メチル基やエチル基などの炭素原子数１〜４のアルキル基が特に好ましい。ハロゲンとしては、塩素原子、臭素原子、フッ素原子などがあるが、塩素原子が好ましい。
【００４２】
ジカルボン酸成分としては、ダイマー酸以外のジカルボン酸化合物またはそのアミド生成可能な誘導体(a-2)を使用することができる。このようなジカルボン酸化合物とその誘導体としては、下記式
Ｒ³ＯＯＣ−ＣＯＯＲ³
または下記式
Ｒ³ＯＯＣ−Ｒ⁴−ＣＯＯＲ³
で表される化合物を挙げることができる。これらの式において、Ｒ³は、炭素原子数１〜８のアルキル基またはアリール基であり、Ｒ⁴は、炭素原子数１〜２０の二価の炭化水素の脂肪族、脂環式または芳香族基である。また、これらの酸の無水物、ハロゲン化物（塩化物など）も使用することができる。エステルは、炭素原子数１〜４のアルキルエステルが好ましい。
【００４３】
このようなジカルボン酸化合物の例としては、シュウ酸、マロン酸、アジピン酸、コハク酸、スベリン酸、セバシン酸、アゼライン酸、ピメリン酸、テレフタル酸、イソフタル酸、フタル酸、ナフタリンジカルボン酸、１，４−または１，３−シクロヘキサンジカルボン酸などが挙げられる。
【００４４】
ジカルボン酸成分は、二量体脂肪酸含有量が６５重量％以上のダイマー酸またはそのアミド生成可能な誘導体(a-1)を全カルボキシル基の２０当量％以上、好ましくは５０当量％以上、より好ましくは５０〜９０当量％、最も好ましくは５５〜８５当量％と、ダイマー酸以外のジカルボン酸化合物またはそのアミド生成可能な誘導体(a-2)を全カルボキシル基の８０当量％以下、好ましくは５０当量％以下、より好ましくは１０〜５０当量％、最も好ましくは１５〜４５当量％とから構成される。ここで、全カルボキシル基は、カルボン酸のみならず、そのエステル、ハロゲン化物、酸無水物などに由来する官能基を意味する。溶融粘度調節等の目的で、モノカルボン酸化合物またはそのアミド形成可能な誘導体を少量成分として併用することができる。
【００４５】
ポリアミド（Ａ）を形成するジアミン成分としては、前記式（Ｉ）で表されるピペラジン化合物と前記式(II)で表されるジピペリジル化合物からなる群より選ばれる少なくとも一種の含窒素複素環化合物(b-1)、及び該含窒素複素環化合物以外のジアミン化合物(b-2)を使用する。
【００４６】
含窒素複素環化合物(b-1)を使用することにより、ポリアミド（Ａ）の接着性が向上し、さらには、合成樹脂成形品などに対して良好な接着性を示す有機酸可溶型ポリアミド樹脂を得ることができる。
【００４７】
含窒素複素環化合物(b-1)の具体例としては、ピペラジン、２，５−ジメチルピペラジン、２，５−ジエチルピペラジン、２−メチルピペラジン、２−エチルピペラジン、Ｎ−アミノエチル−ピペラジン、Ｎ−アミノプロピル−ピペラジン、１,３−ジ（４−ピペリジル）プロパン、１，２−ジ（４−ピペリジル）エタン、１，４−ジ（４−ピペリジル）ブタン、１−（Ｎ−ペンタヒドロキシエチル−４−ピペリジル）−３−（４−ピペリジル）プロパンなどが挙げられる。
【００４８】
該含窒素複素環化合物以外のジアミン化合物(b-2)は、下式
Ｈ₂ＮＲ⁵ＮＨ₂
で表されるものである。式中、Ｒ⁵は、脂肪族、脂環式または芳香族の二価の炭化水素基で炭素原子数２ないし３６のもの、あるいは、ポリオキシアルキレン基を持ったものである。このようなジアミン化合物の具体例は、エチレンジアミン、１，２−ジアミノプロパン、１，３−ジアミノプロパン、１，３−ジアミノブタン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、デカメチレンジアミン、オクタデカメチレンジアミン、メタキシリレンジアミン、パラキシレンジアミン、シクロへキシレンジアミン、ビス（アミノエチル）ベンゼン、シクロヘキシルビス（メチルアミン）、ジアミノ−ジシクロヘキシルメタン、メチレンジアニリン、ポリオキシプロピレンジアミン、ダイマージアミンなどが挙げられる。ジアミン化合物は、Ｒ⁵が炭素原子数２ないし６のアルキレン基であるものが好ましい。
【００４９】
ジアミン成分は、含窒素複素環化合物(b-1)を全アミノ基の２０当量％以上、好ましくは２０〜９０当量％、より好ましくは２５〜７５当量％と、該含窒素複素環化合物以外のジアミン化合物(b-2)を全アミノ基の８０当量％以下、好ましくは１０〜８０当量％、より好ましくは２５〜７５当量％とから構成される。含窒素複素環化合物の当量％が小さすぎると、接着性を十分に向上させることができない。
【００５０】
本発明で使用するポリアミド（Ａ）は、前述のジカルボン酸成分とジアミン成分とを、全アミン当量の全カルボキシル当量に対する比が０．８：１〜１．３：１、好ましくは０．９：１〜１．２：１の範囲内で重縮合して得られるポリアミドである。両成分を上記比率（モル当量比）で重縮合させることにより、酸価及びアミン価が共に３５ｍｇＫＯＨ／ｇ以下、好ましくは３０ｍｇＫＯＨ／ｇ以下で安定したポリアミド（Ａ）を得ることができる。
【００５１】
ポリアミド（Ａ）は、ジカルボン酸成分とジアミン成分とを加熱して重縮合させることにより得ることができる。加熱条件としては、例えば、１００〜３００℃で３〜１０時間程度加熱する方法が挙げられる。加熱は、減圧下に行ってもよい。
【００５２】
ポリアミド（Ａ）は、軟化点１００〜２００℃、酸価０〜１０ｍｇＫＯＨ／ｇ、アミン価５〜３０ｍｇＫＯＨ／ｇ、及び２１０℃で測定した溶融粘度５００〜１００，０００ｍＰａ・ｓの物性を有するものであることが望ましい。このポリアミド（Ａ）の軟化点及び溶融粘度が低すぎると、それを用いて得られる有機酸可溶型ポリアミド樹脂の軟化点及び溶融粘度が低下し、溶融成形性やその他の特性が悪化する。ポリアミド（Ａ）の軟化点は、好ましくは１２５〜１９０℃、より好ましくは１４０〜１８０℃である。ポリアミド（Ａ）の２１０℃で測定した溶融粘度は、好ましくは１，０００〜１０，０００ｍＰａ・ｓ、より好ましくは１，５００〜８，０００ｍＰａ・ｓである。
【００５３】
本発明で使用するポリアミドポリアミン（Ｂ）は、二量体脂肪酸含有量が６５重量％以上のダイマー酸またはそのアミド生成可能な誘導体(ｃ-1)を全カルボキシル基の２０当量％以上と、ダイマー酸以外のジカルボン酸化合物またはそのアミド生成可能な誘導体(ｃ-2）を全カルボキシル基の８０当量％以下とからなるジカルボン酸成分、及びポリアルキレンポリアミンとを、全アミン当量の全カルボキシル当量に対する比が１．３：１〜３．０：１の範囲内で重縮合して得られるポリアミドポリアミンである。
【００５４】
ダイマー酸またはそのアミド生成可能な誘導体(ｃ-1)、及びダイマー酸以外のジカルボン酸化合物またはそのアミド生成可能な誘導体(ｃ-2)としては、ポリアミド（Ａ）を合成するのに使用したのと同じものを使用することができる。ダイマー酸またはそのアミド生成可能な誘導体(ｃ-1)は、好ましくは全カルボキシル基の５０当量％以上、より好ましくは６０〜１００当量％の割合で使用される。ダイマー酸以外のジカルボン酸化合物またはそのアミド生成可能な誘導体(ｃ-2)は、好ましくは全カルボキシル基の５０当量％以下、より好ましくは０〜４０当量％の割合で使用される。溶融粘度調節等の目的で、モノカルボン酸化合物またはそのアミド形成可能な誘導体を少量成分として併用することができる。
【００５５】
ポリアルキレンポリアミンとしては、例えば、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミンなどが挙げられる。
【００５６】
ポリアミドポリアミン（Ｂ）は、ジカルボン酸成分とポリアルキレンポリアミンとを、全アミン当量の全カルボキシル当量に対する比が１．３：１〜３．０：１の範囲内で重縮合することにより合成されるアミン官能基を持ったポリアミドポリアミンである。ポリアミドポリアミン（Ｂ）は、例えば、特公昭３７−１８８９８号公報に記載されている合成法により製造することができる。
【００５７】
ポリアミドポリアミン（Ｂ）は、酸価０〜５ｍｇＫＯＨ／ｇ、アミン価５０〜３５０ｍｇＫＯＨ／ｇ、及び２００℃で測定した溶融粘度５０〜３，０００ｍＰａ・ｓの物性を有するものであることが望ましい。
【００５８】
有機酸可溶型ポリアミド樹脂を製造するには、ポリアミド（Ａ）とポリアミドポリアミン（Ｂ）とを重量比（Ａ：Ｂ）９５：５〜４０：６０、好ましくは９０：１０〜５０：５０、より好ましくは８５：１５〜６０：４０で溶融混合する。ポリアミド（Ａ）の混合比率が低すぎると、溶融成形性やその他の特性に優れた有機酸可溶型ポリアミド樹脂を得ることが困難になる。ポリアミド（Ａ）の割合が高すぎると、生成するポリアミド樹脂の有機酸に対する溶解性が低下し、低すぎると、生成するポリアミド樹脂の軟化点が低下して、射出成形時の固化に長時間を要したり、バリが発生し易くなる。
【００５９】
ポリアミド（Ａ）とポリアミドポリアミン（Ｂ）は、通常１５０〜３００℃、好ましくは２００〜２５０℃の高温下で、通常１時間以上、好ましくは５時間以上、より好ましくは１０時間以上、溶融混合することにより、アミド交換反応を起させる。アミド交換反応が生じていることは、溶融混合の結果、均一な物性を有する有機酸可溶型ポリアミド樹脂の得られることにより明らかである。溶融混合時に、アミド交換反応に加えて、更なる重縮合反応が進むこともある。
【００６０】
本発明の有機酸可溶型ポリアミド樹脂は、アミド交換反応後に下記物性
ｉ）軟化点が８０〜１９０℃、好ましくは１２０〜１８０℃、より好ましくは１３５〜１７０℃、
ii）酸価が０〜５ｍｇＫＯＨ/ｇ、
iii）アミン価が１０〜１００ｍｇＫＯＨ／ｇ、
iv）２００℃で測定した溶融粘度が３５０〜８０，０００ｍＰａ・ｓ、好ましくは５００〜１０，０００ｍＰａ・ｓ、より好ましくは１，０００〜８，０００ｍＰａ・ｓ、及び
v）濃度３０重量％の酢酸水溶液１００ｍｌに６０℃で３０分間浸漬して測定した溶解速度が０．２ｍｍ／３０分以上、好ましくは０．３ｍｍ／３０分以上
を有するものである。
【００６１】
有機酸可溶型ポリアミド樹脂の軟化点及び溶融粘度が低すぎると、射出成形性が低下し、その他の物性も悪化する。有機酸可溶型ポリアミド樹脂は、ギ酸や酢酸などの有機酸に可溶性であることが必須であり、有機酸に対する可溶性が低すぎると、ＭＩＤ製造時にレジスト樹脂として使用した場合、有機酸水溶液により溶解除去することが困難になる。有機酸に対する可溶性は、ポリアミド樹脂を用いて作製した試験片（１０ｍｍ×１０ｍｍ×１ｍｍ）を、濃度３０重量％の酢酸水溶液１００ｍｌに６０℃で３０分間浸漬して測定した溶解速度により評価することができる。この溶解速度の測定法は、有機酸可溶型ポリアミド樹脂をレジスト樹脂としての用途に使用する際に、実用的な溶解性の指標となる。測定法の詳細は、後記の実施例において説明する。
【００６２】
ポリアミド（Ａ）単独では、射出成形法による溶融成形が可能であり、他の合成樹脂成形品に対する優れた接着性が得られるが、有機酸水溶液に対する溶解性が不十分である。一方、ポリアミドポリアミン（Ｂ）単独では、有機酸水溶液に対する高い溶解性を示すが、軟化点を有していないため、射出成形法等の溶融成形法を適用することができない。また、ポリアミド（Ａ）とポリアミドポリアミン（Ｂ）とを単に混合しただけでは、有機酸水溶液に対する溶解性が不十分である。
【００６３】
本発明の有機酸可溶型ポリアミド樹脂は、溶融成形性、合成樹脂成形品に対する接着性、めっき処理液に対する耐性、有機酸に対する溶解性などに優れているため、ＭＩＤ製造時のレジスト樹脂として好適である。しかも、本発明の有機酸可溶型ポリアミド樹脂は、レジスト樹脂として使用した後、有機酸水溶液により容易に溶解除去することができるため、レジスト樹脂被覆層が残存しないＭＩＤの製造に好適である。
【００６４】
本発明の有機酸可溶型ポリアミド樹脂をレジスト樹脂として用いるＭＩＤ製造方法の好ましい具体例は、下記の一連の工程を有するものである。
（１）回路部品の基板を構成する一次成形品を合成樹脂の射出成形により形成する工程１、
（２）必要に応じて、１次成形品の表面を粗面化する工程２、
（３）一次成形品の回路を形成すべき部分を除く全表面に、前記の有機酸可溶型ポリアミド樹脂を射出成形して、有機酸可溶型ポリアミド樹脂被覆層を有する二次成形品を成形する工程３、
（４）二次成形品の有機酸可溶型ポリアミド樹脂被覆層部分を除く回路を形成すべき部分に、めっきにより導体回路層を形成する工程４、及び
（５）有機酸水溶液を用いて有機酸可溶型ポリアミド樹脂被覆層を溶解除去する工程５。
【００６５】
一次成形品に使用する合成樹脂としては、液晶ポリマー（ＬＣＰ）、ポリフェニレンスルフィド（ＰＰＳ）樹脂等のスーパーエンジニアリングプラスチック；ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンテレフタレート（ＰＥＴ）等の熱可塑性ポリエステル樹脂；ポリアミド６、ポリアミド６６、ポリアミド４６、ポリアミド６Ｔ、ポリアミド９Ｔなどのポリアミド樹脂；などが挙げられる。これらの合成樹脂は、めっきグレードであることが望ましい。
【００６６】
これらの合成樹脂を射出成形して一次成形品を成形し、必要に応じて表面を粗化する。粗面化する方法としては、例えば、水酸化ナトリウム、水酸化カリウムなどのアルカリ水溶液を５０〜９０℃に加熱し、その中に一次成形品を１〜６０分間程度浸漬する方法が挙げられるが、その他の方法も適用することができる。合成樹脂には、所望により、めっき賦与のための触媒を添加しておくことができる。
【００６７】
一次成形品の回路を形成すべき部分を除く全表面に、前記の有機酸可溶型ポリアミド樹脂を射出成形して、有機酸可溶型ポリアミド樹脂被覆層を有する二次成形品を成形するには、一次成形品を二次金型内にセットし、有機酸可溶型ポリアミド樹脂を射出インサート成形により、回路としない部分に被覆する。
【００６８】
二次成形品の有機酸可溶型ポリアミド樹脂被覆層部分を除く回路を形成すべき部分に、めっきにより導体回路層を形成するが、その際、常法に従って、触媒賦与、触媒活性化などの前処理を行う。めっきは、無電解めっき、それに引き続く電解めっき等の方法により行い、それによって、導体回路層を形成する。
【００６９】
その後、有機酸水溶液を用いて、二次成形品上の有機酸可溶型ポリアミド樹脂被覆層を溶解除去する。具体的には、４０〜６０℃の温度に設定した有機酸（例えば、ギ酸、酢酸）の濃度５〜５０重量％、好ましくは２０〜４０重量％水溶液に、めっきした二次成形品を１〜６０分間、好ましくは５〜３０分間浸漬する方法により、レジスト樹脂被覆層を容易に除去することができる。本発明で使用する有機酸可溶型ポリアミド樹脂は、めっき処理工程で使用する無機酸を含有する各種処理液に対して安定であるため、所望の回路パターンを精度良く得ることができ、回路ピッチの微細化にも対応が可能となる。
【００７０】
また、本発明の有機酸可溶型ポリアミド樹脂は、一次成形品用の各種合成樹脂に対する接着性に優れているので、一次成形品の表面を粗面化せずとも、二次金型にセットして該有機酸可溶型ポリアミド樹脂を成形するだけで、一次成形品の表面にレジスト樹脂被覆層として接着させることができる。その後、二次成形品の一次成形品表面露出部を粗面化し、めっきを行えば、一次成形品とめっき層の密着強度が得られる。レジスト樹脂被覆層を除去すれば、非回路部は、粗面化処理されていないので、平滑性の非回路部を有する外観の優れたＭＩＤを製造することができるという効果も得られる。
【００７１】
上記ＭＩＤの製造方法について、図１を参照しながらより具体的に説明する。図１において、合成樹脂を射出成形して一次成形品１１を得る（工程１）。所望により、この一次成形品の表面を粗面化処理する（工程２）。次に、一次成形品の回路を形成すべき部分を除く全表面に、前記の有機酸可溶型ポリアミド樹脂を射出成形して、有機酸可溶型ポリアミド樹脂被覆層１２を有する二次成形品を成形する（工程３）。なお、図１では、明確化のために、有機酸可溶型ポリアミド樹脂被覆層１２を一次成形品１１の垂直部分と平坦部分のみに形成しているように図示しているが、実際には、回路部分を除く全面を被覆している。
【００７２】
次に、回路部分にめっきを施して、めっき層１３を形成する（工程４）が、その前に、必要に応じて、粗面化処理、触媒賦与処理などを行うことができる。最後に、有機酸水溶液を用いて、有機酸可溶型ポリアミド樹脂被覆層１２を溶解除去する（工程５）。
【００７３】
本発明の有機酸可溶型ポリアミド樹脂をレジスト樹脂としてＭＩＤを製造する他の方法は、以下の各工程を含む製造方法である。
（i）回路部品の基板を構成する一次成形品を合成樹脂の射出成形により形成する工程Ｉ、
（ii）必要に応じて、１次成形品の表面を粗面化する工程II、
（iii）一次成形品の回路を形成すべき部分を除く全表面に、前記の有機酸可溶型ポリアミド樹脂を射出成形して、有機酸可溶型ポリアミド樹脂被覆層を有する二次成形品を成形する工程III、
（iv）二次成形品の有機酸可溶型ポリアミド樹脂被覆層部分を除く回路を形成すべき部分に、触媒を賦与する工程IV、
（v）有機酸水溶液を用いて有機酸可溶型ポリアミド樹脂被覆層を溶解除去する工程V、及び
（vi）触媒賦与部分にめっきして導体回路層を形成する工程VI。
【００７４】
この製造方法では、回路形成部分に触媒を付与した後、レジスト樹脂被覆層を溶解除去し、しかる後、触媒を賦与した回路形成部分にめっきを施す。この製造方法によっても、所望の回路パターンを精度良く得ることができ、回路ピッチの微細化にも対応が可能となる。
【００７５】
【実施例】
以下に実施例及び比較例を挙げて、本発明についてより具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。物性及び特性の測定法は、次のとおりである。
【００７６】
（１）軟化点：
軟化点は、ＪＩＳ Ｋ６８６３−１９９４に記載されているホットメルト接着剤の軟化点試験方法に準拠して測定した。
（２）酸価：
酸価は、フェノールフタレインを指示薬とし、水酸化カリウム水溶液を滴定液とする中和滴定法により測定した。
【００７７】
（３）アミン価：
アミン価は、ブロムクレゾールグリーンを指示薬とし、塩酸水溶液を滴定液とする中和滴定法により測定した。
（４）溶融粘度：
溶融粘度は、ＪＩＳ Ｋ６８６２−１９８４に記載されているホットメルト接着剤の溶融粘度試験方法のＢ法に準拠して測定した。
【００７８】
（５）有機酸に対する溶解性：
ポリアミド樹脂を用いて、縦×横×厚み＝１０ｍｍ×１０ｍｍ×１ｍｍの試験片を作製した。この試験片を濃度３０重量％の酢酸水溶液１００ｍｌに６０℃で３０分間浸漬した後、取り出し、８０℃で２４時間乾燥させた。乾燥後の試験片の厚みを測定した。浸漬前の試験片の厚みをＫｍｍとし、浸漬・乾燥後の試験片の厚みをＬｍｍとすると、式「溶解速度＝Ｋ−Ｌ（ｍｍ／３０分）」により溶解速度が算出される。この溶解速度を有機酸に対する溶解性の指標とした。
【００７９】
＜めっき工程＞
めっき工程は、以下の手順により行った。すなわち、下記(1)〜(5)に示した処方にて無電解銅めっきを行い、厚み２μｍの銅めっき層を形成し、引き続いて、(6)の手順で電気銅めっきを行い、めっき層の合計厚みを１５μｍとした。
【００８０】
(1)脱脂処理：
一次成形品を超音波洗浄機で５分間洗浄した後、イオン交換水で洗浄する。
(2)プレディップ：
塩化ナトリウム（１８０ｇ／Ｌ）、塩酸（８０ｍｌ／Ｌ）、及びＯＳ−１５０５〔シプレイ・ファーイースト（株）製、商品名〕（２０ｍｌ／Ｌ）をこれらの比率で混合して処理液を調製し、この処理液を４５℃の温度に設定して、その中に試料を３分間浸漬する。
【００８１】
(3)触媒付与：
塩化ナトリウム（１８０ｇ／Ｌ）、塩酸（１００ｍｌ／Ｌ）、ＯＳ−１５０５〔シプレイ・ファーイースト（株）製、商品名〕（２０ｍｌ／Ｌ）、及びＯＳ−１５５８〔シプレイ・ファーイースト（株）製、商品名〕（２０ｍｌ／Ｌ）をこれらの比率で混合して処理液を調製し、この処理液を３０℃の温度に設定して、その中に試料を８分間浸漬する。浸漬後、試料をイオン交換水で洗浄する。
【００８２】
(4)触媒活性化：
ＯＳ−１５６０〔シプレイ・ファーイースト（株）製、商品名〕（濃度＝２０ｍｌ／Ｌ）からなる処理液を３０℃の温度に設定し、この処理液中に試料を２分間浸漬する。浸漬後、試料をイオン交換水で洗浄する。
【００８３】
(5)無電解銅めっき：
ＯＳ−１５９８Ｍ（４８ｍｌ／Ｌ）、ＯＳ−１５９８Ａ（１０ｍｌ／Ｌ）、ＯＳ−１５９８Ｒ（２ｍｌ／Ｌ）、ＯＳ−１１２０ＳＲ（２．１ｍｌ／Ｌ）、ＣｕｐＺ（２３ｍｌ／Ｌ）、及びＣｕｐＹ（１２ｍｌ／Ｌ）〔それぞれシプレイ・ファーイースト（株）製、商品名〕をこれら比率で混合してめっき液を調製し、次いで、めっき液を４５℃の温度に設定して、その中に試料を１５分浸漬する。浸漬後、試料をイオン交換水で洗浄する。
【００８４】
(6)電気銅めっき：
硫酸銅（２２０ｇ／Ｌ）と硫酸（６０ｇ／Ｌ）をこれらの比率で混合してめっき液を調製し、次いで、めっき液を２５℃の温度に設定して、その中に試料を浸漬し、２Ａ／ｄｍ²の電流密度で２０分間通電することにより、厚み約１５μｍのめっき層を形成する。
【００８５】
［実施例１］
液晶ポリエステル樹脂（ＬＣＰ）〔ベクトラＣ８１０、ポリプラスチック（株）製、商品名〕を、射出成形機（型締力＝１００トン、スクリュー径＝４５ｍｍφ）を用いて、射出圧５０ｋｇ／ｃｍ²、保圧時間１０秒間、金型温度６０℃の条件にて射出成形することにより、図２に示す形状の一次成形品２１を成形した。得られた一次成形品をエタノールで洗浄した後、８０℃に設定した４５％の水酸化ナトリウム水溶液中に５分間浸漬し、次いで、３％の塩酸で中和する方法により粗面化した。粗面化した一次成形品を二次金型内にセットし、レジスト樹脂を射出成形して、一次成形品の回路を形成すべき部分を除く全表面にレジスト樹脂被覆層を形成した（二次成形品の成形）。
【００８６】
レジスト樹脂としては、ダイマー酸（０．６５当量）、セバシン酸（０．３５当量）、エチレンジアミン（０．５３当量）、及びピペラジン（０．５３当量）を重縮合して得られた、軟化点１６０℃、酸価１．０ｍｇＫＯＨ／ｇ、アミン価１０．０ｍｇＫＯＨ／ｇ、溶融粘度３，０００ｍＰａ・ｓ（２１０℃）のポリアミド（Ａ）と、ダイマー酸（１．０当量）及びジエチレントリアミン（１．５当量）を重縮合して得られた、酸価１．０ｍｇＫＯＨ／ｇ、アミン価１００．０ｍｇＫＯＨ／ｇ、溶融粘度１００ｍＰａ・ｓ（２００℃）のポリアミドポリアミン（Ｂ）とを、Ａ：Ｂ＝８０／２０の重量比で配合し、２３０℃で１２時間溶融混合、アミド交換反応させて得られた、軟化点１５０℃、酸価１．０ｍｇＫＯＨ／ｇ、アミン価２５．０ｍｇＫＯＨ／ｇ、溶融粘度３，０００ｍＰａ・ｓ（２００℃）、有機酸に対する溶解速度０．３ｍｍ／３０分の有機酸可溶型ポリアミド樹脂を使用した。
【００８７】
得られた二次成形品に、前記手順で無電解めっき及び電解めっき処理を行った後、６０℃の濃度３０重量％酢酸水溶液中に３０分間浸漬して、レジスト樹脂被覆層を溶解除去して、導体回路２２を有する三次元射出成形回路部品を得た。得られた回路部品は、図２に示すように、回路幅３００μｍ、回路ピッチ６００μｍの回路が形成されており、所望のパターンの導体回路層を高精度で形成することが可能であった。
【００８８】
［実施例２］
ポリブチレンテレフタレート樹脂（ＰＢＴ）〔ＵＢＥ ＰＢＴ ３０００ 宇部興産（株）製、商品名〕１００重量部に炭酸カルシウム２０重量部を添加した樹脂組成物を、射出成形機（型締力１００トン、スクリュー径４５ｍｍφ）を用いて、射出圧５０ｋｇ／ｃｍ²、保圧時間１０秒間、金型温度６０℃の条件にて射出成形することにより、図２に示す形状の一次成形品２１を成形した。この一次成形品をエタノールで洗浄した後、８０℃に設定したの濃度４５重量％水酸化ナトリウム水溶液中に５分間浸漬し、次いで、３％の塩酸で中和する方法で粗面化した。
【００８９】
粗面化した一次成形品を二次金型内にセットし、レジスト樹脂として実施例１で使用したのと同じ有機酸可溶型ポリアミド樹脂を用いて、インサート射出成形により二次成形品を得た。得られた二次成形品に、前記手順で無電解めっき及び電解めっき処理を行った後、６０℃の濃度３０重量％酢酸水溶液中に３０分間浸漬する方法で、レジスト樹脂被覆層を溶解除去し、導体回路２２付き回路部品を得た。この回路部品は、回路幅３００μｍ、回路ピッチ６００μｍの回路を描くことができ、所望のパターンの導体回路層を高精度で形成することが可能であった。
【００９０】
［比較例１］
実施例１で作製したのと同じ一次成形品を使用し、二次成形用のレジスト樹脂として、オキシアルキレン基含有ポリビニルアルコール系樹脂〔エコマティＡＸ２０００、日本合成化学（株）製、商品名〕を使用し、図２に対応する形状を有する二次成形品を得た。
【００９１】
この系では、粗面化工程において、レジスト樹脂の膨潤が見られ、所望の回路幅３００μｍ、回路ピッチ６００μｍのパターンの導体回路層を形成することができなかった。
【００９２】
［比較例２］
実施例１で作製したのと同じ一次成形品を使用し、二次成形用のレジスト樹脂として、実施例１で用いたポリアミド（Ａ）を使用したこと以外は、実施例１と同様にして導体回路の形成を行った。しかし、レジスト除去工程で、レジスト樹脂被覆層を除去することができず、所望の回路幅３００μｍ、回路ピッチ６００μｍのパターンの導体回路層の形成ができなかった。
【００９３】
［比較例３］
実施例１で作製したのと同じ一次成形品を使用し、二次成形用のレジスト樹脂として、実施例１で使用したポリアミドポリアミン（Ｂ）を使用したこと以外は、実施例１と同様にして導体回路の形成を行った。しかし、レジスト樹脂の射出成形工程で、バリ（一次成形品と金型のクリアランスに樹脂が入り込む現象）が発生し、所望の回路幅３００μｍ、回路ピッチ６００μｍのパターンの導体回路層の形成ができなかった。
【００９４】
［比較例４］
実施例１で作製したのと同じ一次成形品を使用し、二次成形用のレジスト樹脂として、実施例１のポリアミド（Ａ）とポリアミドポリアミン（Ｂ）を３０／７０の重量比で混合し、２３０℃で１２時間溶融混合し、アミド交換反応させて得られた、軟化点１２０℃、酸価１．０ｍｇＫＯＨ／ｇ、アミン価７０．０ｍｇＫＯＨ／ｇ、溶融粘度３００ｍＰａ・ｓ（２００℃）、有機酸に対する溶解速度０．２５ｍｍ／３０分の有機酸可溶型ポリアミド樹脂を使用したこと以外は、実施例１と同様にして胴体回路の形成を行った。しかし、レジスト樹脂を射出成形する工程で、バリ（一次成形品と金型のクリアランスに樹脂が入り込み）が発生し、所望の回路幅３００μｍ、回路ピッチ６００μｍのパターンの導体回路層の形成ができなかった。
【００９５】
［比較例５］
実施例１で作製したのと同じ一次成形品を使用し、二次成形用のレジスト樹脂として、実施例１のポリアミド（Ａ）とポリアミドポリアミン（Ｂ）を８０／２０の重量比で配合し、２００℃で２軸混合機（３０ｍｍφ、Ｌ／Ｄ＝３２）にて溶融混合（ブレンド）して得られた、軟化点１５５℃、酸価１．０ｍｇＫＯＨ／ｇ、アミン価２８．０ｍｇＫＯＨ／ｇ、溶融粘度３，０００ｍＰａ・ｓ（２００℃）のポリアミド樹脂を使用したこと以外は、実施例１と同様にして胴体回路の形成を行った。しかし、レジスト除去工程でレジスト樹脂被覆層を除去することができず、所望の回路幅３００μｍ、回路ピッチ６００μｍのパターンの導体回路層の形成ができなかった。
【００９６】
【発明の効果】
本発明によれば、溶融成形性、合成樹脂成形品に対する接着性、めっき処理液に対する耐性、有機酸に対する溶解性に優れた新規な有機酸可溶型ポリアミド樹脂とその製造方法が提供される。また、本発明によれば、このような優れた特性を有する有機酸可溶型ポリアミド樹脂をレジスト樹脂として使用する工程を含む三次元射出成形回路部品の製造方法が提供される。本発明によれば、微細なピッチの導体回路層を有する成形回路部品を製造することができ、成形品上に導体回路層を形成したＭＩＤなどの分野での利用価値は大きいものがある。
【図面の簡単な説明】
【図１】本発明のＭＩＤ製造方法の一例に従って、工程（ａ）から工程（ｅ）を経て、ＭＩＤが製造されることを示す工程図である。
【図２】本発明の製造方法の一例に従って得られるＭＩＤの一例を示す略図であり、斜視図（Ａ）、正面図（Ｂ）、及び側面図（Ｃ）を示す。
【符号の説明】
１１：一次成形品、
１２：レジスト樹脂層、
１３：めっき層（導体回路層）、
２１：一次成形品、
２２：めっき層（導体回路層）。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel organic acid-soluble polyamide resin and a method for producing the same. The organic acid-soluble polyamide resin of the present invention is excellent in melt moldability, adhesion to synthetic resin molded products, resistance to plating solutions, and solubility in organic acids to form a three-dimensional injection molded circuit component. It is suitable as a resist resin. The present invention also relates to a method for producing a three-dimensional injection molded circuit component including a step of using the organic acid-soluble polyamide resin as a resist resin.
[0002]
[Prior art]
As electronic devices become smaller, lighter, and have higher performance, printed circuit boards are being made finer, multilayered, rationalized in devices, and space-saving. From the viewpoint of assembly automation, a wiring rationalization technique aiming at improving assembly is required. In order to meet such demands, a three-dimensional injection molded circuit component (Molded Interconnect Device; hereinafter abbreviated as “MID”) in which wiring (conductor circuit) is three-dimensionally formed on the surface of an injection molded product has been proposed. .
[0003]
MID is a three-dimensional wiring board that integrates synthetic resin injection-molded products and wiring components. It has free three-dimensionality and enables not only rationalization of wiring but also miniaturization and surface mounting of electronic device components. It is what. For example, the integration density can be improved by arranging the MID in a gap in the device. MID is applied to semiconductor packages such as light emitting diodes (LEDs), three-dimensional printed wiring boards, and antenna components for mobile phones.
[0004]
Conventional MID manufacturing methods are roughly classified into a “one-time molding method” and a “two-time molding method”. In the one-time molding method, a molded product is formed by injection molding using a plating grade resin, the entire surface of the molded product is roughened, a catalyst is applied, and then a copper plating film is formed. Next, a resist is applied on the copper plating film, and a circuit is formed by a photolithography technique. Examples of the circuit forming method include a subtractive method using an etching resist and a semi-additive method using a plating resist.
[0005]
In this one-time molding method, in the exposure process to the resist film, since exposure is performed with parallel light using a film mask or a glass mask, it is difficult to form a circuit on the vertical plane. Even if a method of forming the mask so as to match the shape of the molded product is adopted, there is a limit to the shape of the mask that can be formed, and there is a problem that it is limited to a mask shape that can uniformly irradiate exposure light. Therefore, the one-time molding method has a low degree of freedom in forming a conductor circuit. Furthermore, since the circuit is formed by etching in the one-time molding method, it is difficult to increase the thickness of the conductor.
[0006]
The two-time molding method is a method of forming a circuit by a full additive method by molding an integral molded product by two moldings using two types of resins, an easily plating resin and a difficult plating resin. More specifically, an easy-plating resin is injection molded to form a primary molded product, and a catalyst is applied to the surface, or an easy-plating resin containing a catalyst is injection molded in advance to form a primary molded product. To do. Next, a difficult-to-platable resin is injection-molded on the entire surface other than the portion where the circuit of the primary molded product is to be formed, thereby forming a secondary molded product having the hardly-platable resin coating layer. The difficult-to-platable resin coating layer serves as a plating resist during plating. Finally, plating is performed on a portion on the surface of the primary molded product where a circuit is to be formed by a full additive method.
[0007]
According to the two-time molding method, a circuit can be easily formed even on a vertical surface, and therefore, three-dimensional circuit molding that is impossible or difficult with the one-time molding method can be easily performed. In the two-time molding method, since the conductor thickness is also a full additive method, it can be made thicker than the one-time molding method using etching, and a circuit component having a large allowable current can be obtained.
[0008]
However, with the conventional two-time molding method, the second-molded hard-to-platable resin coating layer remains in the product as it is, so that the entire circuit component becomes thicker, and there is a limit to reducing the size and weight. There is. In addition, in the two-time molding method, since a hard-to-platable resin coating layer remains in the product, it is necessary to use a resin material having excellent heat resistance, electrical insulation, mechanical strength, chemical resistance, etc. as the hard-plating resin. This increases the manufacturing cost. Furthermore, since the primary molded product is inserted into the mold and the hard-to-platable resin is injection-molded, if a high-performance resin material is used as the hard-to-platable resin, it becomes necessary to perform injection molding at a high pressure. Therefore, it is necessary to increase the height of the portion or increase the width of the circuit portion.
[0009]
Japanese Patent Application Laid-Open No. 11-145583 proposes a method of elution in the middle of a process so that a secondary molded part does not remain in the product in the two-time molding method. Specifically, the publication discloses (1) a step of injecting a plating-grade liquid crystal polymer into a cavity having a shape that matches the outer shape of a circuit component to form a primary molded product, and (2) the surface of the primary molded product. Step of roughening (3) Inserting the surface-roughened primary molded product into a cavity having a void on the entire surface excluding the circuit portion to be formed in the primary molded product, containing oxyalkylene groups in the cavity A step of injecting a polyvinyl alcohol-based resin to form a secondary molded product; (4) a step of imparting a catalyst such as palladium or gold to the exposed circuit portion after forming the secondary molded product; and (5) a catalyst. A process comprising heating a secondary molded product after application in hot water to elute the part formed by secondary molding into the hot water, and (6) forming a circuit by plating the catalyst applied part. Circuit parts ( Method of manufacturing ID) are disclosed.
[0010]
However, in the method described in the above publication, the water-soluble oxyalkylene group-containing polyvinyl alcohol-based resin is used to form the secondary molded part (coating layer), so that it is used in the catalyst application step and the catalyst activation step. The coating layer swells or dissolves partially with a treatment liquid containing an inorganic acid such as hydrochloric acid or sulfuric acid. As a result, it is difficult to accurately form a desired conductor circuit pattern. In particular, there is a problem that this tendency becomes more prominent as the circuit pitch becomes finer.
[0011]
Japanese Laid-Open Patent Publication No. 7-283513 proposes a method for manufacturing MID that combines a two-time molding method and a photolithography technique. The publication discloses a method for manufacturing MID in which a conductor circuit is formed on a synthetic resin injection molded article having a steep and uneven portion having large irregularities and a smoothly changing smooth portion, and (1) an injection molded article is used as a catalyst for electroless plating. Formed by primary injection molding of easy-plating material blended with and secondary injection molding of difficult-plating material not blended with electroless plating catalyst, and (2) easy-plating material on the surface of the stiff block (3) After primary and secondary injection molding so that the easily plateable material is exposed on the entire surface of the smooth portion, there is no effect on the entire surface of the rugged portion and the smooth portion. (4) A resist film is formed on the entire surface of the steep blocking portion and the smooth portion, and photolithography is applied to the resist coating to form an electroless plating layer on the entire smooth portion so that the conductor circuit of the steep blocking portion is formed. Flat with pattern Method for producing a MID of forming a conductive circuit pattern parts is disclosed.
[0012]
However, since the method described in the above publication uses a photolithography technique, the degree of freedom in forming a three-dimensional conductor circuit is low, and the secondary injection molded portion remains in the product.
[0013]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel organic acid-soluble polyamide resin excellent in melt moldability, adhesion to a synthetic resin molded article, resistance to a plating treatment solution, and solubility in organic acids, and a method for producing the same. is there.
[0014]
Another object of the present invention is to provide a method for producing a three-dimensional injection molded circuit component including a step of using an organic acid-soluble polyamide resin having such excellent characteristics as a resist resin.
[0015]
As a result of diligent research to achieve the above object, the inventors of the present invention have obtained a polyamide obtained by polycondensation of a dicarboxylic acid component containing dimer acid and a specific diamine component, and a dicarboxylic acid component containing dimer acid. It has been found that an organic acid-soluble polyamide resin having various characteristics as described above can be obtained by subjecting a polyamide polyamine obtained by polycondensation of polyalkylene and polyalkylene polyamine to an amide exchange reaction at a specific ratio.
[0016]
The organic acid-soluble polyamide resin of the present invention exhibits good solubility in an aqueous solution of an organic acid such as formic acid or acetic acid, but hardly swells or dissolves in an aqueous inorganic acid solution. The organic acid-soluble polyamide resin of the present invention can be subjected to melt molding such as injection molding, and exhibits good adhesion to a synthetic resin molded product.
[0017]
When the organic acid-soluble polyamide resin of the present invention is used as a resist resin in the plating process of MID production, the resist resin coating layer does not cause problems such as swelling and dissolution by the plating solution, and the resist resin It can be easily removed by dipping the coating layer in an organic acid aqueous solution. Therefore, a desired circuit pattern can be accurately formed by using the organic acid-soluble polyamide resin of the present invention as a resist resin. The present invention has been completed based on these findings.
[0018]
[Means for Solving the Problems]
According to the present invention, a novel organic acid-soluble polyamide resin obtained by subjecting polyamide (A) and polyamide polyamine (B) to an amide exchange reaction,
(1) Polyamide (A)
a) Dimer acid having a dimer fatty acid content of 65% by weight or a derivative thereof (a-1) capable of forming an amide and 20 equivalent% or more of all carboxyl groups and a dicarboxylic acid compound other than a dimer acid or an amide formation thereof A dicarboxylic acid component comprising possible derivative (a-2) of 80 equivalent% or less of the total carboxyl groups;
b) The following formula (I)
[0019]
[Chemical formula 5]

[0020]
[In the formula, R¹Are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y is a hydrogen atom, RNH₂Or it is ROH (R is a C1-C6 alkylene group). ]
A piperazine compound represented by formula (II):
[0021]
[Chemical 6]

[0022]
[In the formula, R¹Are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;²Is a divalent aliphatic hydrocarbon group, Y is a hydrogen atom, RNH₂Or it is ROH (R is a C1-C6 alkylene group). ]
And at least one nitrogen-containing heterocyclic compound (b-1) selected from the group consisting of dipiperidyl compounds represented by the formula: 20 equivalent% or more of the total amino groups and a diamine compound other than the nitrogen-containing heterocyclic compound (b-2) ) And a diamine component consisting of 80 equivalent% or less of all amino groups,
A polyamide obtained by polycondensation within a ratio of total amine equivalent to total carboxyl equivalent of 0.8: 1 to 1.3: 1,
(2) Polyamide polyamine (B)
c) Dimer acid having a dimer fatty acid content of 65% by weight or a derivative thereof capable of forming an amide (c-1) and 20 equivalent% or more of all carboxyl groups and a dicarboxylic acid compound other than the dimer acid or an amide formation thereof A dicarboxylic acid component comprising a possible derivative (c-2) of 80 equivalent% or less of the total carboxyl groups;
d) a polyalkylene polyamine;
A polyamide polyamine obtained by polycondensation within a ratio of total amine equivalent to total carboxyl equivalent of 1.3: 1 to 3.0: 1, and
(4) Following physical properties after amide exchange reaction
i) Softening point of 80-190 ° C.
ii) an acid value of 0-5 mg KOH / g,
iii) an amine value of 10 to 100 mg KOH / g,
iv) a melt viscosity measured at 200 ° C. of 350-80,000 mPa · s, and
v) Dissolution rate measured by immersing in 100 ml of 30% by weight acetic acid aqueous solution at 60 ° C. for 30 minutes is not less than 0.2 mm / 30 minutes.
Have
An organic acid-soluble polyamide resin is provided.
[0023]
According to the present invention, there is also provided a novel method for producing an organic acid-soluble polyamide resin in which a polyamide (A) and a polyamide polyamine (B) are subjected to an amide exchange reaction,
(1) Polyamide (A)
a) Dimer acid having a dimer fatty acid content of 65% by weight or a derivative thereof (a-1) capable of forming an amide and 20 equivalent% or more of all carboxyl groups and a dicarboxylic acid compound other than a dimer acid or an amide formation thereof A dicarboxylic acid component comprising possible derivative (a-2) of 80 equivalent% or less of the total carboxyl groups;
b) The following formula (I)
[0024]
[Chemical 7]

[0025]
[In the formula, R¹Are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y is a hydrogen atom, RNH₂Or it is ROH (R is a C1-C6 alkylene group). ]
A piperazine compound represented by formula (II):
[0026]
[Chemical 8]

[0027]
[In the formula, R¹Are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;²Is a divalent aliphatic hydrocarbon group, Y is a hydrogen atom, RNH₂Or it is ROH (R is a C1-C6 alkylene group). ]
And at least one nitrogen-containing heterocyclic compound (b-1) selected from the group consisting of dipiperidyl compounds represented by the formula: 20 equivalent% or more of the total amino groups and a diamine compound other than the nitrogen-containing heterocyclic compound (b-2) ) And a diamine component consisting of 80 equivalent% or less of all amino groups,
A polyamide obtained by polycondensation within a ratio of total amine equivalent to total carboxyl equivalent of 0.8: 1 to 1.3: 1,
(2) Polyamide polyamine (B)
c) Dimer acid having a dimer fatty acid content of 65% by weight or a derivative thereof capable of forming an amide (c-1) and 20 equivalent% or more of all carboxyl groups and a dicarboxylic acid compound other than the dimer acid or an amide formation thereof A dicarboxylic acid component comprising a possible derivative (c-2) of 80 equivalent% or less of the total carboxyl groups;
d) a polyalkylene polyamine;
A polyamide polyamine obtained by polycondensation in a ratio of total amine equivalents to total carboxyl equivalents in the range of 1.3: 1 to 3.0: 1; and
(3) The polyamide (A) and the polyamide polyamine (B) are melt-mixed at a temperature in the range of 150 to 300 at a weight ratio (A: B) of 95: 5 to 40:60 for 1 hour or more to perform an amide exchange reaction. By letting
(4) Following physical properties after amide exchange reaction
i) Softening point of 80-190 ° C.
ii) an acid value of 0-5 mg KOH / g,
iii) an amine value of 10 to 100 mg KOH / g,
iv) a melt viscosity measured at 200 ° C. of 350-80,000 mPa · s, and
v) Dissolution rate measured by immersing in 100 ml of 30% by weight acetic acid aqueous solution at 60 ° C. for 30 minutes is not less than 0.2 mm / 30 minutes.
A polyamide resin having
A method for producing an organic acid-soluble polyamide resin is provided.
[0028]
Furthermore, according to the present invention, (1) Step 1 of forming a primary molded product constituting a circuit component substrate by injection molding of a synthetic resin;
(2) Step 2 for roughening the surface of the primary molded product if necessary,
(3) A secondary molded article having an organic acid-soluble polyamide resin coating layer is formed by injection molding the organic acid-soluble polyamide resin on the entire surface except the portion where the circuit of the primary molded article is to be formed. Molding step 3,
(4) Step 4 of forming a conductor circuit layer by plating on a portion where a circuit other than the organic acid-soluble polyamide resin coating layer portion of the secondary molded product is to be formed; and
(5) Step 5 of dissolving and removing the organic acid-soluble polyamide resin coating layer using an organic acid aqueous solution
There is provided a method for manufacturing a three-dimensional injection molded circuit component including a series of steps consisting of:
[0029]
Furthermore, according to the present invention, (i) a step I of forming a primary molded product constituting a circuit component substrate by injection molding of a synthetic resin,
(Ii) Step II for roughening the surface of the primary molded product as necessary,
(Iii) A secondary molded article having an organic acid-soluble polyamide resin coating layer formed by injection molding the organic acid-soluble polyamide resin on the entire surface except the portion where the circuit of the primary molded article is to be formed. Molding process III,
(Iv) Step IV in which a catalyst is applied to a portion where a circuit other than the organic acid-soluble polyamide resin coating layer portion of the secondary molded product is to be formed,
(V) Step V of dissolving and removing the organic acid-soluble polyamide resin coating layer using an organic acid aqueous solution, and
(Vi) Step VI to form the conductor circuit layer by plating the catalyst-imparted portion
There is provided a method for manufacturing a three-dimensional injection molded circuit component including a series of steps.
[0030]
DETAILED DESCRIPTION OF THE INVENTION
The polyamide (A) used in the present invention comprises a dimer acid having a dimer fatty acid content of 65% by weight or more, or a derivative (a-1) capable of forming an amide thereof of 20 equivalent% or more of all carboxyl groups, and a dimer acid. A dicarboxylic acid compound comprising a dicarboxylic acid compound or derivative thereof (a-2) capable of forming an amide of 80 equivalent% or less of the total carboxyl groups, and the following formula (I):
[0031]
[Chemical 9]

[0032]
[In the formula, R¹Are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y is a hydrogen atom, RNH₂Or it is ROH (R is a C1-C6 alkylene group). ]
A piperazine compound represented by formula (II):
[0033]
Embedded image

[0034]
[In the formula, R¹Are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;²Is a divalent aliphatic hydrocarbon group, Y is a hydrogen atom, RNH₂Or it is ROH (R is a C1-C6 alkylene group). ]
And at least one nitrogen-containing heterocyclic compound (b-1) selected from the group consisting of dipiperidyl compounds represented by the formula: 20 equivalent% or more of the total amino groups and a diamine compound other than the nitrogen-containing heterocyclic compound (b-2) And a diamine component consisting of 80 equivalent% or less of all amino groups and a polycondensation obtained by polycondensation of the ratio of all amine equivalents to all carboxyl equivalents within the range of 0.8: 1 to 1.3: 1 It is. The polyamide (A) of the present invention can be obtained, for example, by a production method described in Japanese Patent Publication No. 45-6825 and Japanese Patent Publication No. 48-14790.
[0035]
Dimer acid used in the present invention is oleic acid (C₁₈H₃₄O₂), Linoleic acid (C₁₈H₃₂O₂), Linolenic acid (C₁₈H₃₀O₂) And the like, and a dimerized polymerized fatty acid by condensation with a clay catalyst. Dimer acid can also be obtained by polymerizing a saturated fatty acid using a peroxide catalyst. The main component of dimer acid is a dimer, and additionally contains monomers, trimers and the like. A typical dimer acid is a monomer (C₁₈), Dimer (C₃₆) And trimers (C₅₄).
[0036]
A method for producing dimer acid is described in US Pat. No. 3,157,681. Commercial dimer acids produced from fatty acids based on oleic acid and linoleic acid such as tall oil fatty acids are generally C₁₈Monomer acid (monomer) 5-15% by weight, C₃₆Dimer acid (dimer) 60-80% by weight, and C₅₄It has a composition of 10 to 35% by weight of the above higher order polymer acid (trimer).
[0037]
The ratio of the monomer, dimer and trimer in the unfractionated dimer acid depends on the raw material and the polymerization conditions. Monomeric fatty acid means an unpolymerized monomeric acid, dimeric fatty acid means a dimeric fatty acid, and a trimeric fatty acid is mainly composed of a trimeric acid and is higher order. Means a polymer that also contains Dimer acid is a general term for polymerized acids obtained from fatty acids, and is a mixture of monomers, dimers and trimers. The fatty acid used as a raw material for the dimer acid is a saturated, ethylenically unsaturated, acetylenically unsaturated, natural or synthetic fatty acid carboxylic acid having 8 to 24 carbon atoms.
[0038]
Saturated fatty acids are generally polymerized in a slightly different manner than that described in US Pat. No. 3,157,681. That is, saturated fatty acids are polymerized using a peroxide catalyst such as di-t-butyl peroxide at medium temperature. Generally, these raw materials are not industrially important due to the low polymer yield. Saturated fatty acids include linear and side chain acids such as caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, isopalmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. Can be mentioned. The ethylenically and acetylenically unsaturated fatty acids to be polymerized and their polymerization methods are described in US Pat. No. 3,157,681.
[0039]
The content of monomers, dimers, and trimer fatty acids present in the dimer acid is quantified by gas chromatography as the corresponding methyl ester. Other quantitative methods include micromolecular distillation analysis and liquid chromatography.
[0040]
In the present invention, dimer acid having a dimer fatty acid content of 65% by weight or more or a derivative capable of forming an amide (a-1) is used. The content of the dimer fatty acid is preferably 80% by weight or more, particularly preferably 90 to 95% by weight. In order to increase the content of the dimer fatty acid, a method such as fractional distillation of the dimer acid or removal of the monomer by a solvent extraction method can be employed. If the content of the dimer fatty acid is too low, a polyamide having excellent melt moldability cannot be obtained.
[0041]
The dimer acid can be used in the acid form, but can also be a derivative capable of forming an amide. An amide-forming derivative means a derivative that can react with a diamine component to form an amide bond. Such derivatives include esters, halides, and acid anhydrides. Esters can be obtained by reacting dimer acids with alcohols. The ester residue is preferably an alkyl group having 1 to 8 carbon atoms or an aryl group. Among these, alkyl groups having 1 to 4 carbon atoms such as a methyl group and an ethyl group are particularly preferable. As the halogen, there are a chlorine atom, a bromine atom and a fluorine atom, and a chlorine atom is preferable.
[0042]
As the dicarboxylic acid component, a dicarboxylic acid compound other than dimer acid or a derivative (a-2) capable of forming an amide thereof can be used. Examples of such dicarboxylic acid compounds and derivatives thereof include
R^ThreeOOC-COOR^Three
Or the following formula
R^ThreeOOC-R^Four-COOR^Three
The compound represented by these can be mentioned. In these equations, R^ThreeIs an alkyl or aryl group having 1 to 8 carbon atoms, R^FourIs an aliphatic, alicyclic or aromatic group of a divalent hydrocarbon having 1 to 20 carbon atoms. In addition, anhydrides and halides (such as chlorides) of these acids can also be used. The ester is preferably an alkyl ester having 1 to 4 carbon atoms.
[0043]
Examples of such dicarboxylic acid compounds include oxalic acid, malonic acid, adipic acid, succinic acid, suberic acid, sebacic acid, azelaic acid, pimelic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, 1, Examples include 4- or 1,3-cyclohexanedicarboxylic acid.
[0044]
The dicarboxylic acid component is a dimer acid having a dimer fatty acid content of 65% by weight or more, or a derivative capable of forming an amide (a-1) of 20 equivalent% or more, preferably 50 equivalent% or more, more preferably of all carboxyl groups. Is 50 to 90 equivalent%, most preferably 55 to 85 equivalent%, and dicarboxylic acid compound other than dimer acid or its amide-formable derivative (a-2) is 80 equivalent% or less of the total carboxyl groups, preferably 50 equivalents. % Or less, more preferably 10 to 50 equivalent%, most preferably 15 to 45 equivalent%. Here, the total carboxyl group means not only a carboxylic acid but also a functional group derived from its ester, halide, acid anhydride and the like. For the purpose of adjusting the melt viscosity, a monocarboxylic acid compound or a derivative capable of forming an amide thereof can be used in combination as a minor component.
[0045]
The diamine component forming the polyamide (A) is at least one nitrogen-containing heterocyclic compound selected from the group consisting of a piperazine compound represented by the above formula (I) and a dipiperidyl compound represented by the above formula (II) ( b-1) and a diamine compound (b-2) other than the nitrogen-containing heterocyclic compound are used.
[0046]
By using the nitrogen-containing heterocyclic compound (b-1), the adhesion of the polyamide (A) is improved, and furthermore, an organic acid-soluble polyamide exhibiting good adhesion to synthetic resin molded products and the like A resin can be obtained.
[0047]
Specific examples of the nitrogen-containing heterocyclic compound (b-1) include piperazine, 2,5-dimethylpiperazine, 2,5-diethylpiperazine, 2-methylpiperazine, 2-ethylpiperazine, N-aminoethyl-piperazine, N -Aminopropyl-piperazine, 1,3-di (4-piperidyl) propane, 1,2-di (4-piperidyl) ethane, 1,4-di (4-piperidyl) butane, 1- (N-pentahydroxyethyl) -4-piperidyl) -3- (4-piperidyl) propane and the like.
[0048]
The diamine compound (b-2) other than the nitrogen-containing heterocyclic compound has the following formula:
H₂NR^FiveNH₂
It is represented by Where R^FiveIs an aliphatic, alicyclic or aromatic divalent hydrocarbon group having 2 to 36 carbon atoms, or having a polyoxyalkylene group. Specific examples of such diamine compounds include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, octane. Decamethylenediamine, metaxylylenediamine, paraxylenediamine, cyclohexylenediamine, bis (aminoethyl) benzene, cyclohexylbis (methylamine), diamino-dicyclohexylmethane, methylenedianiline, polyoxypropylenediamine, dimerdiamine Can be mentioned. The diamine compound is R^FiveIs preferably an alkylene group having 2 to 6 carbon atoms.
[0049]
The diamine component is a nitrogen-containing heterocyclic compound (b-1) of 20 equivalent% or more, preferably 20 to 90 equivalent%, more preferably 25 to 75 equivalent% of the total amino group, and other than the nitrogen-containing heterocyclic compound. The diamine compound (b-2) is composed of 80 equivalent% or less, preferably 10 to 80 equivalent%, more preferably 25 to 75 equivalent% of the total amino groups. If the equivalent percentage of the nitrogen-containing heterocyclic compound is too small, the adhesion cannot be sufficiently improved.
[0050]
In the polyamide (A) used in the present invention, the ratio of the total amine equivalent to the total carboxyl equivalent of the dicarboxylic acid component and the diamine component is 0.8: 1 to 1.3: 1, preferably 0.9: It is a polyamide obtained by polycondensation within the range of 1 to 1.2: 1. By polycondensing both components at the above ratio (molar equivalent ratio), a stable polyamide (A) can be obtained with an acid value and an amine value of 35 mgKOH / g or less, preferably 30 mgKOH / g or less.
[0051]
A polyamide (A) can be obtained by heating and polycondensing a dicarboxylic acid component and a diamine component. Examples of the heating conditions include a method of heating at 100 to 300 ° C. for about 3 to 10 hours. Heating may be performed under reduced pressure.
[0052]
Polyamide (A) has a softening point of 100 to 200 ° C., an acid value of 0 to 10 mg KOH / g, an amine value of 5 to 30 mg KOH / g, and a melt viscosity of 500 to 100,000 mPa · s measured at 210 ° C. It is desirable to be. When the softening point and melt viscosity of the polyamide (A) are too low, the softening point and melt viscosity of the organic acid-soluble polyamide resin obtained using the polyamide (A) are lowered, and the melt moldability and other characteristics are deteriorated. The softening point of the polyamide (A) is preferably 125 to 190 ° C, more preferably 140 to 180 ° C. The melt viscosity measured at 210 ° C. of the polyamide (A) is preferably 1,000 to 10,000 mPa · s, more preferably 1,500 to 8,000 mPa · s.
[0053]
The polyamide polyamine (B) used in the present invention comprises a dimer acid having a dimer fatty acid content of 65% by weight or more or a derivative capable of forming an amide (c-1) of 20 equivalent% or more of all carboxyl groups, Ratio of dicarboxylic acid compound other than acid or amide-formable derivative thereof (c-2) comprising 80 equivalent% or less of the total carboxyl group, and polyalkylene polyamine to total carboxyl equivalent of total amine equivalent Is a polyamide polyamine obtained by polycondensation within the range of 1.3: 1 to 3.0: 1.
[0054]
Dimer acid or its amide-forming derivative (c-1) and dicarboxylic acid compound other than dimer acid or its amide-forming derivative (c-2) were used to synthesize polyamide (A). The same can be used. The dimer acid or its amide-formable derivative (c-1) is preferably used in an amount of 50 equivalent% or more, more preferably 60 to 100 equivalent% of the total carboxyl groups. The dicarboxylic acid compound other than dimer acid or its amide-formable derivative (c-2) is preferably used in a proportion of 50 equivalent% or less, more preferably 0 to 40 equivalent% of the total carboxyl group. For the purpose of adjusting the melt viscosity, a monocarboxylic acid compound or a derivative capable of forming an amide thereof can be used in combination as a minor component.
[0055]
Examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.
[0056]
The polyamide polyamine (B) is synthesized by polycondensing a dicarboxylic acid component and a polyalkylene polyamine in a ratio of the total amine equivalent to the total carboxyl equivalent within a range of 1.3: 1 to 3.0: 1. Polyamide polyamine having an amine functional group. The polyamide polyamine (B) can be produced, for example, by a synthesis method described in Japanese Patent Publication No. 37-18898.
[0057]
The polyamide polyamine (B) preferably has physical properties of an acid value of 0 to 5 mgKOH / g, an amine value of 50 to 350 mgKOH / g, and a melt viscosity of 50 to 3,000 mPa · s measured at 200 ° C.
[0058]
In order to produce an organic acid soluble polyamide resin, the weight ratio (A: B) of polyamide (A) and polyamide polyamine (B) is 95: 5 to 40:60, preferably 90:10 to 50:50, More preferably, melt mixing is performed at 85:15 to 60:40. When the mixing ratio of the polyamide (A) is too low, it becomes difficult to obtain an organic acid-soluble polyamide resin excellent in melt moldability and other characteristics. If the ratio of the polyamide (A) is too high, the solubility of the resulting polyamide resin in the organic acid is lowered, and if it is too low, the softening point of the produced polyamide resin is lowered, and a long time is required for solidification during injection molding. Or burrs are likely to occur.
[0059]
The polyamide (A) and the polyamide polyamine (B) are usually melt-mixed at a high temperature of 150 to 300 ° C., preferably 200 to 250 ° C., usually for 1 hour or longer, preferably 5 hours or longer, more preferably 10 hours or longer. This causes an amide exchange reaction. The occurrence of the amide exchange reaction is apparent by obtaining an organic acid-soluble polyamide resin having uniform physical properties as a result of melt mixing. During melt mixing, in addition to the amide exchange reaction, a further polycondensation reaction may proceed.
[0060]
The organic acid soluble polyamide resin of the present invention has the following physical properties after the amide exchange reaction.
i) Softening point of 80-190 ° C, preferably 120-180 ° C, more preferably 135-170 ° C,
ii) an acid value of 0-5 mg KOH / g,
iii) an amine value of 10 to 100 mg KOH / g,
iv) a melt viscosity measured at 200 ° C. of 350 to 80,000 mPa · s, preferably 500 to 10,000 mPa · s, more preferably 1,000 to 8,000 mPa · s, and
v) A dissolution rate measured by immersing in 100 ml of 30% by weight acetic acid aqueous solution at 60 ° C. for 30 minutes is 0.2 mm / 30 minutes or more, preferably 0.3 mm / 30 minutes or more.
It is what has.
[0061]
When the softening point and melt viscosity of the organic acid-soluble polyamide resin are too low, the injection moldability is lowered and other physical properties are also deteriorated. Organic acid soluble polyamide resin must be soluble in organic acids such as formic acid and acetic acid. If the solubility in organic acid is too low, it will dissolve in aqueous organic acid solution when used as a resist resin during MID production. It becomes difficult to remove. Solubility in organic acids can be evaluated by a dissolution rate measured by immersing a test piece (10 mm × 10 mm × 1 mm) prepared using a polyamide resin in 100 ml of 30% by weight acetic acid aqueous solution at 60 ° C. for 30 minutes. it can. This method of measuring the dissolution rate is a practical solubility index when the organic acid-soluble polyamide resin is used as a resist resin. Details of the measurement method will be described in the examples described later.
[0062]
Polyamide (A) alone can be melt-molded by an injection molding method, and can provide excellent adhesion to other synthetic resin molded products, but is insufficiently soluble in an organic acid aqueous solution. On the other hand, the polyamide polyamine (B) alone exhibits high solubility in an organic acid aqueous solution, but it does not have a softening point, and thus a melt molding method such as an injection molding method cannot be applied. Further, simply mixing the polyamide (A) and the polyamide polyamine (B) results in insufficient solubility in the organic acid aqueous solution.
[0063]
The organic acid-soluble polyamide resin of the present invention is suitable as a resist resin during MID production because it is excellent in melt moldability, adhesion to synthetic resin molded products, resistance to plating solutions, and solubility in organic acids. It is. Moreover, since the organic acid-soluble polyamide resin of the present invention can be easily dissolved and removed by an organic acid aqueous solution after being used as a resist resin, it is suitable for the production of MID in which the resist resin coating layer does not remain.
[0064]
A preferred specific example of the MID production method using the organic acid-soluble polyamide resin of the present invention as a resist resin has the following series of steps.
(1) Step 1 of forming a primary molded product constituting a circuit component substrate by synthetic resin injection molding,
(2) Step 2 for roughening the surface of the primary molded product if necessary,
(3) A secondary molded article having an organic acid-soluble polyamide resin coating layer is formed by injection molding the organic acid-soluble polyamide resin on the entire surface except the portion where the circuit of the primary molded article is to be formed. Molding step 3,
(4) Step 4 of forming a conductor circuit layer by plating on a portion where a circuit other than the organic acid-soluble polyamide resin coating layer portion of the secondary molded product is to be formed; and
(5) Step 5 of dissolving and removing the organic acid-soluble polyamide resin coating layer using an organic acid aqueous solution.
[0065]
Synthetic resins used for primary molded products include super engineering plastics such as liquid crystal polymer (LCP) and polyphenylene sulfide (PPS) resins; thermoplastic polyester resins such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET); polyamide 6 And polyamide resins such as polyamide 66, polyamide 46, polyamide 6T, and polyamide 9T. These synthetic resins are preferably plating grade.
[0066]
These synthetic resins are injection-molded to form a primary molded product, and the surface is roughened as necessary. Examples of the surface roughening method include a method in which an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide is heated to 50 to 90 ° C., and the primary molded product is immersed in the solution for about 1 to 60 minutes. Other methods can also be applied. If desired, a catalyst for imparting plating can be added to the synthetic resin.
[0067]
To form a secondary molded article having an organic acid-soluble polyamide resin coating layer by injection molding the organic acid-soluble polyamide resin on the entire surface except the portion where the circuit of the primary molded article is to be formed. The primary molded product is set in a secondary mold, and an organic acid-soluble polyamide resin is coated on a portion that is not a circuit by injection insert molding.
[0068]
The conductor circuit layer is formed by plating on the portion of the secondary molded product where the circuit other than the organic acid-soluble polyamide resin coating layer portion is to be formed. In this case, according to the conventional method, catalyst application, catalyst activation, etc. Perform pre-processing. Plating is performed by a method such as electroless plating followed by electrolytic plating, thereby forming a conductor circuit layer.
[0069]
Thereafter, the organic acid-soluble polyamide resin coating layer on the secondary molded product is dissolved and removed using an organic acid aqueous solution. Specifically, the secondary molded article plated with an aqueous solution having a concentration of 5 to 50% by weight, preferably 20 to 40% by weight of an organic acid (for example, formic acid or acetic acid) set at a temperature of 40 to 60 ° C. The resist resin coating layer can be easily removed by a method of dipping for 60 minutes, preferably 5 to 30 minutes. Since the organic acid-soluble polyamide resin used in the present invention is stable with respect to various processing solutions containing inorganic acids used in the plating process, a desired circuit pattern can be obtained with high accuracy and a circuit pitch. It is also possible to cope with the miniaturization.
[0070]
In addition, the organic acid-soluble polyamide resin of the present invention has excellent adhesion to various synthetic resins for primary molded products, so it can be set in a secondary mold without roughening the surface of the primary molded product. By simply molding the organic acid-soluble polyamide resin, it can be adhered to the surface of the primary molded product as a resist resin coating layer. Thereafter, when the exposed surface of the primary molded product is roughened and plated, the adhesion strength between the primary molded product and the plating layer can be obtained. If the resist resin coating layer is removed, since the non-circuit portion is not roughened, an effect of producing a MID having a smooth non-circuit portion and having an excellent appearance can be obtained.
[0071]
The manufacturing method of the MID will be described more specifically with reference to FIG. In FIG. 1, a synthetic resin is injection-molded to obtain a primary molded product 11 (step 1). If desired, the surface of the primary molded product is roughened (step 2). Next, a secondary molded article having the organic acid-soluble polyamide resin coating layer 12 formed by injection molding the organic acid-soluble polyamide resin on the entire surface except the portion where the circuit of the primary molded article is to be formed. Is formed (step 3). In FIG. 1, for the sake of clarity, the organic acid-soluble polyamide resin coating layer 12 is illustrated as being formed only on the vertical portion and the flat portion of the primary molded product 11. The whole surface except the circuit part is covered.
[0072]
Next, the circuit portion is plated to form the plating layer 13 (step 4), but before that, a roughening treatment, a catalyst applying treatment, or the like can be performed as necessary. Finally, the organic acid soluble polyamide resin coating layer 12 is dissolved and removed using an organic acid aqueous solution (step 5).
[0073]
Another method for producing MID using the organic acid-soluble polyamide resin of the present invention as a resist resin is a production method including the following steps.
(I) Step I of forming a primary molded product constituting a circuit component substrate by injection molding of synthetic resin,
(Ii) Step II for roughening the surface of the primary molded product as necessary,
(Iii) A secondary molded article having an organic acid-soluble polyamide resin coating layer formed by injection molding the organic acid-soluble polyamide resin on the entire surface except the portion where the circuit of the primary molded article is to be formed. Molding process III,
(Iv) Step IV in which a catalyst is applied to a portion where a circuit other than the organic acid-soluble polyamide resin coating layer portion of the secondary molded product is to be formed,
(V) Step V of dissolving and removing the organic acid-soluble polyamide resin coating layer using an organic acid aqueous solution, and
(Vi) Step VI of forming a conductor circuit layer by plating the catalyst-giving portion.
[0074]
In this manufacturing method, after a catalyst is applied to the circuit formation portion, the resist resin coating layer is dissolved and removed, and then the circuit formation portion to which the catalyst is applied is plated. Also by this manufacturing method, a desired circuit pattern can be obtained with high accuracy, and it is possible to cope with miniaturization of the circuit pitch.
[0075]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited only to these examples. The measuring methods of physical properties and characteristics are as follows.
[0076]
(1) Softening point:
The softening point was measured according to a softening point test method for a hot melt adhesive described in JIS K6863-1994.
(2) Acid value:
The acid value was measured by a neutralization titration method using phenolphthalein as an indicator and a potassium hydroxide aqueous solution as a titrant.
[0077]
(3) Amine number:
The amine value was measured by a neutralization titration method using bromcresol green as an indicator and a hydrochloric acid aqueous solution as a titrant.
(4) Melt viscosity:
The melt viscosity was measured according to the method B of the melt viscosity test method for hot melt adhesives described in JIS K6862-1984.
[0078]
(5) Solubility in organic acids:
A test piece of length × width × thickness = 10 mm × 10 mm × 1 mm was prepared using a polyamide resin. The test piece was immersed in 100 ml of an acetic acid aqueous solution having a concentration of 30% by weight at 60 ° C. for 30 minutes, then taken out and dried at 80 ° C. for 24 hours. The thickness of the test piece after drying was measured. When the thickness of the test piece before immersion is K mm and the thickness of the test piece after immersion / drying is L mm, the dissolution rate is calculated by the formula “dissolution rate = KL (mm / 30 minutes)”. This dissolution rate was used as an index of solubility in organic acids.
[0079]
<Plating process>
The plating process was performed according to the following procedure. That is, electroless copper plating is performed according to the formulations shown in the following (1) to (5) to form a copper plating layer having a thickness of 2 μm, followed by electrolytic copper plating according to the procedure of (6). The total thickness of was set to 15 μm.
[0080]
(1) Degreasing treatment:
The primary molded product is washed with an ultrasonic cleaner for 5 minutes, and then washed with ion-exchanged water.
(2) Pre-dip:
Sodium chloride (180 g / L), hydrochloric acid (80 ml / L), and OS-1505 [manufactured by Shipley Far East Co., Ltd., trade name] (20 ml / L) were mixed at these ratios to prepare a treatment solution. The treatment liquid is set at a temperature of 45 ° C., and the sample is immersed in it for 3 minutes.
[0081]
(3) Adding catalyst:
Sodium chloride (180 g / L), hydrochloric acid (100 ml / L), OS-1505 [manufactured by Shipley Far East Co., Ltd., trade name] (20 ml / L), and OS-1558 [manufactured by Shipley Far East Co., Ltd.] , Trade name] (20 ml / L) is mixed at these ratios to prepare a treatment liquid, the treatment liquid is set at a temperature of 30 ° C., and the sample is immersed in the treatment liquid for 8 minutes. After immersion, the sample is washed with ion exchange water.
[0082]
(4) Catalyst activation:
A treatment liquid composed of OS-1560 [trade name, manufactured by Shipley Far East Co., Ltd.] (concentration = 20 ml / L) is set at a temperature of 30 ° C., and the sample is immersed in this treatment liquid for 2 minutes. After immersion, the sample is washed with ion exchange water.
[0083]
(5) Electroless copper plating:
OS-1598M (48 ml / L), OS-1598A (10 ml / L), OS-1598R (2 ml / L), OS-1120SR (2.1 ml / L), CupZ (23 ml / L), and CupY (12 ml / L) L) [Each product manufactured by Shipley Far East Co., Ltd., trade name] was mixed at these ratios to prepare a plating solution, and then the plating solution was set at a temperature of 45 ° C., and the sample was placed therein for 15 minutes. Immerse. After immersion, the sample is washed with ion exchange water.
[0084]
(6) Copper electroplating:
Copper sulfate (220 g / L) and sulfuric acid (60 g / L) are mixed at these ratios to prepare a plating solution. Then, the plating solution is set at a temperature of 25 ° C., and the sample is immersed therein. 2A / dm²By energizing with a current density of 20 minutes, a plating layer having a thickness of about 15 μm is formed.
[0085]
[Example 1]
Using an injection molding machine (clamping force = 100 tons, screw diameter = 45 mmφ), an injection pressure of 50 kg / cm is used for liquid crystal polyester resin (LCP) [Vectra C810, manufactured by Polyplastics Co., Ltd., trade name].²The primary molded product 21 having the shape shown in FIG. 2 was molded by injection molding under the conditions of a holding temperature of 10 seconds and a mold temperature of 60 ° C. The obtained primary molded article was washed with ethanol, then immersed in a 45% aqueous sodium hydroxide solution set at 80 ° C. for 5 minutes, and then roughened by neutralizing with 3% hydrochloric acid. The roughened primary molded product is set in a secondary mold, and a resist resin is injection-molded to form a resist resin coating layer on the entire surface except the portion where the circuit of the primary molded product is to be formed (secondary Molding of molded products).
[0086]
The resist resin was obtained by polycondensation of dimer acid (0.65 equivalent), sebacic acid (0.35 equivalent), ethylenediamine (0.53 equivalent), and piperazine (0.53 equivalent). Polyamide (A) having 160 ° C., acid value of 1.0 mg KOH / g, amine value of 10.0 mg KOH / g, melt viscosity of 3,000 mPa · s (210 ° C.), dimer acid (1.0 equivalent) and diethylenetriamine (1. 5 equivalents), polyamidopolyamine (B) having an acid value of 1.0 mgKOH / g, an amine value of 100.0 mgKOH / g, and a melt viscosity of 100 mPa · s (200 ° C.), A: B = Blended at a weight ratio of 80/20, melt-mixed at 230 ° C. for 12 hours, and obtained by amide exchange reaction, softening point 150 ° C., acid value 1.0 mgKOH / g, amine value 25.0 g KOH / g, the melt viscosity of 3,000mPa · s (200 ℃), it was used the dissolution rate 0.3 mm / 30 min of the organic acid-soluble polyamide resin in an organic acid.
[0087]
The obtained secondary molded article was subjected to electroless plating and electrolytic plating treatment according to the procedure described above, and then immersed in a 30 wt% acetic acid aqueous solution at 60 ° C. for 30 minutes to dissolve and remove the resist resin coating layer. A three-dimensional injection molded circuit component having a conductor circuit 22 was obtained. As shown in FIG. 2, the obtained circuit component has a circuit with a circuit width of 300 μm and a circuit pitch of 600 μm, and a conductor circuit layer having a desired pattern can be formed with high accuracy.
[0088]
[Example 2]
Polybutylene terephthalate resin (PBT) [UBE PBT 3000, manufactured by Ube Industries, Ltd., trade name] A resin composition obtained by adding 20 parts by weight of calcium carbonate to 100 parts by weight of an injection molding machine (clamping force 100 tons, screw diameter) 45mmφ), injection pressure 50kg / cm²The primary molded product 21 having the shape shown in FIG. 2 was molded by injection molding under the conditions of a holding temperature of 10 seconds and a mold temperature of 60 ° C. The primary molded article was washed with ethanol, then immersed in a 45 wt% aqueous sodium hydroxide solution set at 80 ° C. for 5 minutes, and then roughened by neutralizing with 3% hydrochloric acid.
[0089]
The roughened primary molded product is set in a secondary mold, and the same organic acid-soluble polyamide resin as used in Example 1 is used as the resist resin to obtain a secondary molded product by insert injection molding. It was. After the electroless plating and the electroplating treatment were performed on the obtained secondary molded article according to the above procedure, the resist resin coating layer was dissolved and removed by a method of immersing in a 30 wt% acetic acid aqueous solution at 60 ° C. for 30 minutes. A circuit component with a conductor circuit 22 was obtained. With this circuit component, a circuit having a circuit width of 300 μm and a circuit pitch of 600 μm can be drawn, and a conductor circuit layer having a desired pattern can be formed with high accuracy.
[0090]
[Comparative Example 1]
The same primary molded product as that prepared in Example 1 was used, and an oxyalkylene group-containing polyvinyl alcohol resin [Ecomaty AX2000, manufactured by Nippon Synthetic Chemical Co., Ltd., trade name] was used as a resist resin for secondary molding. Thus, a secondary molded product having a shape corresponding to FIG. 2 was obtained.
[0091]
In this system, swelling of the resist resin was observed in the roughening step, and a conductor circuit layer having a desired circuit width of 300 μm and a circuit pitch of 600 μm could not be formed.
[0092]
[Comparative Example 2]
The conductor is the same as in Example 1 except that the same primary molded product as that produced in Example 1 is used and the polyamide (A) used in Example 1 is used as a resist resin for secondary molding. A circuit was formed. However, the resist resin coating layer cannot be removed in the resist removal step, and a conductor circuit layer having a desired circuit width of 300 μm and a circuit pitch of 600 μm cannot be formed.
[0093]
[Comparative Example 3]
The same primary molded product as that produced in Example 1 was used, and the polyamide polyamine (B) used in Example 1 was used as a resist resin for secondary molding in the same manner as in Example 1. Conductor circuits were formed. However, in the resist resin injection molding process, burrs (a phenomenon in which the resin enters the clearance between the primary molded product and the mold) occur, and it is impossible to form a conductor circuit layer having a desired circuit width of 300 μm and a circuit pitch of 600 μm. It was.
[0094]
[Comparative Example 4]
Using the same primary molded product produced in Example 1 and mixing the polyamide (A) and polyamide polyamine (B) of Example 1 in a weight ratio of 30/70 as a resist resin for secondary molding, Melted and mixed at 230 ° C. for 12 hours, and subjected to an amide exchange reaction, softening point 120 ° C., acid value 1.0 mgKOH / g, amine value 70.0 mgKOH / g, melt viscosity 300 mPa · s (200 ° C.), organic A body circuit was formed in the same manner as in Example 1 except that an organic acid-soluble polyamide resin having a dissolution rate with respect to an acid of 0.25 mm / 30 minutes was used. However, a burr (resin enters the clearance between the primary molded product and the mold) occurs in the resist resin injection molding process, and a conductor circuit layer having a desired circuit width of 300 μm and a circuit pitch of 600 μm cannot be formed. It was.
[0095]
[Comparative Example 5]
Using the same primary molded product produced in Example 1 and blending the polyamide (A) and polyamide polyamine (B) of Example 1 in a weight ratio of 80/20 as a resist resin for secondary molding, Obtained by melt mixing (blending) at 200 ° C. with a twin screw mixer (30 mmφ, L / D = 32), softening point 155 ° C., acid value 1.0 mgKOH / g, amine value 28.0 mgKOH / g, A fuselage circuit was formed in the same manner as in Example 1 except that a polyamide resin having a melt viscosity of 3,000 mPa · s (200 ° C.) was used. However, the resist resin coating layer could not be removed in the resist removal step, and a conductor circuit layer having a desired circuit width of 300 μm and a circuit pitch of 600 μm could not be formed.
[0096]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the novel organic acid soluble type polyamide resin excellent in melt moldability, the adhesiveness with respect to a synthetic resin molded product, the tolerance with respect to a plating process liquid, and the solubility with respect to an organic acid and its manufacturing method are provided. Moreover, according to this invention, the manufacturing method of the three-dimensional injection molding circuit component including the process of using the organic acid soluble type polyamide resin which has such an outstanding characteristic as a resist resin is provided. ADVANTAGE OF THE INVENTION According to this invention, the molded circuit component which has a conductive circuit layer of a fine pitch can be manufactured, and there exists a big utility value in field | areas, such as MID which formed the conductive circuit layer on the molded article.
[Brief description of the drawings]
FIG. 1 is a process diagram showing that MID is manufactured through steps (a) to (e) according to an example of the MID manufacturing method of the present invention.
FIG. 2 is a schematic diagram showing an example of MID obtained according to an example of the manufacturing method of the present invention, and shows a perspective view (A), a front view (B), and a side view (C).
[Explanation of symbols]
11: Primary molded product,
12: Resist resin layer,
13: Plating layer (conductor circuit layer),
21: Primary molded product,
22: Plating layer (conductor circuit layer).

Claims (9)

A novel organic acid-soluble polyamide resin obtained by subjecting polyamide (A) and polyamide polyamine (B) to an amide exchange reaction,
(1) Polyamide (A)
a) Dimer acid having a dimer fatty acid content of 65% by weight or a derivative thereof (a-1) capable of forming an amide and 20 equivalent% or more of all carboxyl groups and a dicarboxylic acid compound other than a dimer acid or an amide formation thereof A dicarboxylic acid component comprising possible derivative (a-2) of 80 equivalent% or less of the total carboxyl groups;
b) The following formula (I)

[Wherein, R ¹ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y is a hydrogen atom, RNH ₂ or ROH (R is an alkylene group having 1 to 6 carbon atoms). It is. ]
A piperazine compound represented by formula (II):

[Wherein, R ¹ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² is a divalent aliphatic hydrocarbon group, and Y is a hydrogen atom, RNH ₂ or ROH (R is an alkylene group having 1 to 6 carbon atoms). ]
And at least one nitrogen-containing heterocyclic compound (b-1) selected from the group consisting of dipiperidyl compounds represented by the formula: 20 equivalent% or more of the total amino groups and a diamine compound other than the nitrogen-containing heterocyclic compound (b-2) ) And a diamine component consisting of 80 equivalent% or less of all amino groups,
A polyamide obtained by polycondensation within a ratio of total amine equivalent to total carboxyl equivalent of 0.8: 1 to 1.3: 1,
(2) Polyamide polyamine (B)
c) Dimer acid having a dimer fatty acid content of 65% by weight or a derivative thereof capable of forming an amide (c-1) and 20 equivalent% or more of all carboxyl groups and a dicarboxylic acid compound other than the dimer acid or an amide formation thereof A dicarboxylic acid component comprising a possible derivative (c-2) of 80 equivalent% or less of the total carboxyl groups;
d) a polyalkylene polyamine;
A polyamide polyamine obtained by polycondensation within a ratio of the total amine equivalent to the total carboxyl equivalent of 1.3: 1 to 3.0: 1,
(3) The weight ratio (A: B) of the polyamide (A) and the polyamide polyamine (B) is 95: 5 to 40:60, and
(4) The following physical properties after the amide exchange reaction i) Softening point of 80-190 ° C,
ii) an acid value of 0-5 mg KOH / g,
iii) an amine value of 10 to 100 mg KOH / g,
iv) a melt viscosity measured at 200 ° C. of 350-80,000 mPa · s, and
v) An organic acid-soluble polyamide resin having a dissolution rate of 0.2 mm / 30 minutes or more measured by immersing in 100 ml of an acetic acid aqueous solution having a concentration of 30% by weight at 60 ° C. for 30 minutes. The polyamide (A) has a softening point of 100 to 200 ° C., an acid value of 0 to 10 mg KOH / g, an amine value of 5 to 30 mg KOH / g, and a melt viscosity of 500 to 100,000 mPa · s measured at 210 ° C. The organic acid-soluble polyamide resin according to claim 1. The polyamide polyamine (B) has a physical property of an acid value of 0 to 5 mgKOH / g, an amine value of 50 to 350 mgKOH / g, and a melt viscosity of 50 to 3,000 mPa · s measured at 200 ° C. Organic acid soluble polyamide resin. The organic acid-soluble type according to claim 1, wherein the polyamide (A) and the polyamide polyamine (B) are subjected to an amide exchange reaction by melting and mixing at a temperature in the range of 150 to 300 ° C for 1 hour or more. Polyamide resin. A method for producing a novel organic acid-soluble polyamide resin in which a polyamide (A) and a polyamide polyamine (B) are subjected to an amide exchange reaction,
(1) Polyamide (A)
a) Dimer acid having a dimer fatty acid content of 65% by weight or a derivative thereof (a-1) capable of forming an amide and 20 equivalent% or more of all carboxyl groups and a dicarboxylic acid compound other than a dimer acid or an amide formation thereof A dicarboxylic acid component comprising possible derivative (a-2) of 80 equivalent% or less of the total carboxyl groups;
b) The following formula (I)

[Wherein, R ¹ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y is a hydrogen atom, RNH ₂ or ROH (R is an alkylene group having 1 to 6 carbon atoms). It is. ]
A piperazine compound represented by formula (II):

[Wherein, R ¹ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² is a divalent aliphatic hydrocarbon group, and Y is a hydrogen atom, RNH ₂ or ROH (R is an alkylene group having 1 to 6 carbon atoms). ]
And at least one nitrogen-containing heterocyclic compound (b-1) selected from the group consisting of dipiperidyl compounds represented by the formula: 20 equivalent% or more of the total amino groups and a diamine compound other than the nitrogen-containing heterocyclic compound (b-2) ) And a diamine component consisting of 80 equivalent% or less of all amino groups,
A polyamide obtained by polycondensation within a ratio of total amine equivalent to total carboxyl equivalent of 0.8: 1 to 1.3: 1,
(2) Polyamide polyamine (B)
c) Dimer acid having a dimer fatty acid content of 65% by weight or a derivative thereof capable of forming an amide (c-1) and 20 equivalent% or more of all carboxyl groups and a dicarboxylic acid compound other than the dimer acid or an amide formation thereof A dicarboxylic acid component comprising a possible derivative (c-2) of 80 equivalent% or less of the total carboxyl groups;
d) a polyalkylene polyamine;
A polyamide polyamine obtained by polycondensation in a ratio of total amine equivalents to total carboxyl equivalents in the range of 1.3: 1 to 3.0: 1; and
(3) The polyamide (A) and the polyamide polyamine (B) are melt-mixed at a temperature in the range of 150 to 300 at a weight ratio (A: B) of 95: 5 to 40:60 for 1 hour or more to perform an amide exchange reaction. By letting
(4) The following physical properties after the amide exchange reaction i) Softening point of 80-190 ° C,
ii) an acid value of 0-5 mg KOH / g,
iii) an amine value of 10 to 100 mg KOH / g,
iv) a melt viscosity measured at 200 ° C. of 350-80,000 mPa · s, and
v) Organic acid-soluble polyamide resin characterized by producing a polyamide resin having a dissolution rate of 0.2 mm / 30 minutes or more measured by immersing in 100 ml of acetic acid aqueous solution having a concentration of 30% by weight at 60 ° C. for 30 minutes. Manufacturing method. (1) Step 1 of forming a primary molded product constituting a circuit component substrate by synthetic resin injection molding,
(2) Step 2 for roughening the surface of the primary molded product if necessary,
(3) The organic acid-soluble type polyamide resin according to any one of claims 1 to 4 is injection-molded on the entire surface excluding the portion where the circuit of the primary molded product is to be formed, Step 3 for forming a secondary molded article having a polyamide resin coating layer,
(4) Step 4 in which a conductor circuit layer is formed by plating on a portion where a circuit other than the organic acid-soluble polyamide resin coating layer portion of the secondary molded product is to be formed, and (5) organic using an organic acid aqueous solution. Step 5 for dissolving and removing the acid-soluble polyamide resin coating layer
A method for manufacturing a three-dimensional injection molded circuit component comprising a series of steps consisting of: The process according to claim 6, wherein in step 5, an aqueous solution of formic acid or acetic acid having a concentration of 5 to 50% by weight is used as the organic acid aqueous solution. (I) Step I of forming a primary molded product constituting a circuit component substrate by injection molding of synthetic resin,
(Ii) Step II for roughening the surface of the primary molded product as necessary,
(Iii) The organic acid-soluble type polyamide resin according to any one of claims 1 to 4 is injection-molded on the entire surface excluding the portion where the circuit of the primary molded product is to be formed, Step III for forming a secondary molded article having a polyamide resin coating layer,
(Iv) Step IV in which a catalyst is applied to a portion where a circuit other than the organic acid-soluble polyamide resin coating layer portion of the secondary molded product is to be formed,
(V) Step V for dissolving and removing the organic acid-soluble polyamide resin coating layer using an organic acid aqueous solution, and (vi) Step VI for forming a conductor circuit layer by plating the catalyst-giving portion.
A method for manufacturing a three-dimensional injection molded circuit component comprising a series of steps consisting of: The process according to claim 8, wherein in step V, an aqueous solution of formic acid or acetic acid having a concentration of 5 to 50% by weight is used as the aqueous organic acid solution.

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