JP3902992B2 - Conductive polyurea resin composition, conductive polyurea resin curing agent, composition set for forming conductive polyurea resin, and method for producing conductive polyurea resin composition - Google Patents

Description

【００１１】
（式中、Ｒ₁、Ｒ₂は、それぞれ１〜１０の炭素原子を有するアルキル基であり、同一であっても異なっていてもよい。Ｒ₃〜Ｒ₆は、それぞれ水素原子または１〜５の炭素原子を有するアルキル基であり、同一であっても異なっていてもよい。）
【００１２】
本発明の導電性ポリウレア樹脂組成物は、「前記導電性充填剤（Ｃ）が、金属微粒子、導電性カーボン粉末、導電性金属酸化物、導電性ポリマーから選ばれること」、「前記アミン化合物（Ｂ）において、Ｒ₁，Ｒ₂がブチル基、Ｒ₃，Ｒ₄が水素原子又はメチル基、及びＲ₅，Ｒ₆が水素原子であること」、「前記ポリイソシアネート（Ａ）が、脂肪族および／または脂環族であること」、「ＮＣＯ／ＮＨの当量比が０．８〜１．４であること」を好ましい態様として含むものである。
【００１３】
また、本発明の導電性ポリウレア樹脂用硬化剤は、少なくとも、上記一般式（１）で示されるアミン化合物（Ｂ）、および導電性充填剤（Ｃ）を含有することを特徴とする。
【００１４】
本発明の導電性ポリウレア樹脂用硬化剤は、「前記導電性充填剤（Ｃ）が、金属微粒子、導電性カーボン粉末、導電性金属酸化物、導電性ポリマーから選ばれること」、「前記アミン化合物（Ｂ）において、Ｒ₁，Ｒ₂がブチル基、Ｒ₃，Ｒ₄が水素原子又はメチル基、及びＲ₅，Ｒ₆が水素原子であること」を好ましい態様として含むものである。
【００１５】
また、本発明の導電性ポリウレア樹脂形成用の組成物セットは、ポリイソシアネート成分と、ポリアミン成分とを独立して有している導電性ポリウレア樹脂形成用の組成物セットであって、前記ポリアミン成分が、少なくとも、上記一般式（１）で示されるアミン化合物（Ｂ）を含有し、ポリイソシアネート成分とポリアミン成分のいずれか一方に導電性充填剤（Ｃ）を含有することを特徴とする。
【００１６】
本発明の導電性ポリウレア樹脂形成用の組成物セットは、「前記導電性充填剤（Ｃ）が、金属微粒子、導電性カーボン粉末、導電性金属酸化物、導電性ポリマーから選ばれること」、「前記アミン化合物（Ｂ）において、Ｒ₁，Ｒ₂がブチル基、Ｒ₃，Ｒ₄が水素原子又はメチル基、及びＲ₅，Ｒ₆が水素原子であること」、「前記ポリイソシアネート成分中のポリイソシアネート（Ａ）が、脂肪族および／または脂環族であること」を好ましい態様として含むものである。
【００１７】
また、本発明の導電性ポリウレア樹脂組成物の製造方法は、６０℃以下の保温状態で７００ｃｐｓ以下の粘度であるポリイソシアネート（Ａ）と、５０℃以下の保温状態で１００ｃｐｓ以下の粘度である上記一般式（１）で示されるアミン化合物（Ｂ）に、導電性充填剤（Ｃ）を分散させたポリアミン成分とを、ＮＣＯ／ＮＨ官能基比が０．８当量以上１．４当量以下となるように混合し常温硬化させることを特徴とする。
【００１８】
また、本発明の導電性ポリウレア樹脂組成物の製造方法は、６０℃以下の保温状態で７００ｃｐｓ以下の粘度であるポリイソシアネート（Ａ）に、導電性充填剤（Ｃ）を分散させたポリイソシアネート成分と、５０℃以下の保温状態で１００ｃｐｓ以下の粘度である上記一般式（１）で示されるアミン化合物（Ｂ）とを、ＮＣＯ／ＮＨ官能基比が０．８当量以上１．４当量以下となるように混合し常温硬化させることを特徴とする。
【００１９】
【発明の実施の形態】
以下、本発明について詳細に説明する。
【００２０】
＜ポリイソシアネート（Ａ）＞
本発明におけるポリイソシアネート（Ａ）とは、末端に少なくとも２つ以上の活性イソシアネート基を有する二量体以上の化合物を指す。使用目的に応じて反応速度や樹脂の硬度を制御するために、異なる構造を持つポリイソシアネートの混合物を使用しても良い。
【００２１】
ただし、多官能性の単量体イソシアネート化合物の使用は、生体への有害性や成型物の安定性の面から好ましくない。また、アミン化合物（Ｂ）との相溶性および硬化樹脂の光安定性を勘案するとポリイソシアネート（Ａ）は脂肪族および／または脂環族であることが好ましい。
【００２２】
本発明に用いられるポリイソシアネートの例としては、ヘキサメチレンジイソシアネート（ＨＤＩ）のウレトジオン体、ビウレット体、イソシアヌレート体、アロファネート体、トリメチルプロパン付加体などが挙げられるが、上記の条件を満たすものであれば他のポリイソシアネートおよびその混合物を用いても良い。例えば、ポリアミンやポリオールで鎖延長を施したポリイソシアネートプレポリマーを成分として用いても良い。
【００２３】
＜アミン化合物（Ｂ）＞
本発明に用いられるアミン化合物（Ｂ）は、下記一般式（１）で示さるビス（Ｎ−アルキルアミノシクロヘキシル）メタン類であり、特許第２７５９０５３号公報に開示されている。
【００２４】
【化７】

【００２５】
（式中、Ｒ₁、Ｒ₂は、それぞれ１〜１０の炭素原子を有するアルキル基であり、同一であっても異なっていてもよい。Ｒ₃〜Ｒ₆は、それぞれ水素原子または１〜５の炭素原子を有するアルキル基であり、同一であっても異なっていてもよい。）
【００２６】
式中のＲ₁及びＲ₂は、１〜１０の炭素原子を有するアルキル基であり、直鎖または分岐してもよい。Ｒ₁及びＲ₂は異なっていてもよいが、ほとんどの場合、調整上同一である。代表的なアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、第二ブチル、第三ブチル、および種々のペンチル異性体、ヘキシル、ヘプチル、オクチル、およびデシル基である。好ましいＲ₁とＲ₂は少なくとも３つの炭素原子を含んでおり、特にブチル基が好ましくそして後者のうちでは第二ブチル基が特に好ましい。
【００２７】
Ｒ₃〜Ｒ₆は、それぞれ水素原子及び１〜５個の炭素原子を有するアルキル基で構成される群から選択されるが、ほとんどの場合Ｒ₃とＲ₄とは同じである。代表的なアルキル基は、Ｒ₁、Ｒ₂として上述したもののうち１〜５個の炭素原子を有するものと同じである。Ｒ₅及びＲ₆が共に水素である場合が最も好ましい。
【００２８】
また、アルキルアミノ基はＣＲ₅Ｒ₆基に対して環のいずれの位置にあってもよく、Ｒ₃とＲ₄がアルキルアミノ基に対してどの位置を占めてもよいような構造である。アルキルアミノ基及びＲ₃とＲ₄の相対的な位置に関しては制約はないが、アルキルアミノ基がＣＲ₅Ｒ₆の結合位に対して４，４’−位置にある種類が最も一般的であり、Ｒ₃とＲ₄がアルキル基である場合、それらが３−及び３’−の位置を占めるのが最も一般的である。
【００２９】
ポリイソシアネートとの相溶性を考慮すると、Ｒ₁，Ｒ₂がブチル基、Ｒ₃，Ｒ₄が水素原子又はメチル基、及びＲ₅，Ｒ₆が水素原子であることが好ましい。
【００３０】
上記に相当するアミン化合物（Ｂ）は、ＵＯＰ社よりＣｌｅａｒｌｉｎｋ１０００、Ｃｌｅａｒｌｉｎｋ３０００の名称で市販されており、本発明においても広く用いることができる。
【００３１】
これらのアミン化合物（Ｂ）は単独で使用してもよいが、反応速度や樹脂の硬度を制御するために、脂肪族および／または脂環族のアミン類を併用して使用しても良い。
【００３２】
また、本発明の組成物は常温において硬化速度は十分に早いが、さらに硬化性を向上させるために、硬化促進剤を配合して使用しても構わない。
【００３３】
＜導電性充填剤（Ｃ）＞
導電性充填剤（Ｃ）は、金属微粒子、導電性カーボン粉末、導電性金属酸化物、導電性ポリマーから選ばれる。
【００３４】
金属微粒子は導電性が良好で酸化の影響を受けにくいものを用いる。例としては、金、銀、銅、ニッケル、パラジウム錫およびそれらからなる混合物の微粒子が好ましく使用される。これらの金属微粒子は平均粒径が０．１〜３５μｍの範囲であるものが好ましい。平均粒径は３５μｍを越えると微粒子間の接点が不足して導電性が低下する可能性があり、０．１μｍ未満では、接触抵抗が増加して導電性が低下する可能性がある。金属微粒子の形状は、球状もしくはフレーク状が好ましい。
【００３５】
導電性カーボン粉末は、導電性カーボンブラック、導電性カーボングラファイト、導電性カーボンナノチューブ、フラーレンなどが好ましく使用される。導電性カーボンブラックの例としては、ＥＣ（Ｅｘｔｒａ Ｃｏｎｄｕｃｔｉｖｅ）、ＥＣＦ（Ｅｘｔｒａ Ｃｏｎｄｕｃｔｉｖｅ Ｆｕｒｎａｃｅ）、ＳＣＦ（Ｓｕｐｅｒ ｃｏｎｄｕｃｔｉｖｅ Ｆｕｒｎａｃｅ）、ＣＦ（Ｃｏｎｄｕｃｔｉｖｅ Ｆｕｒｎａｃｅ）、アセチレンブラック等（ケッチェンブラックＥＣ（ＥＣ６００ＪＤ）を含む。）、ＳＡＦ（Ｓｕｐｅｒ Ａｂｒａｓｉｏｎ Ｆｕｒｎａｃｅ）、ＩＳＡＦ（Ｉｎｔｅｒｍｅｄｉａｔｅ ＳＡＦ）、ＨＡＦ（ＨｉｇｈＡｂｒａｓｉｏｎ Ｆｕｒｎａｃｅ）、ＦＥＦ（Ｆａｓｔ Ｅｘｔｒｕｄｉｎｇ Ｆｕｒｎａｃｅ）、ＧＰＦ（Ｇｅｎｅｒａｌ Ｐｕｒｐｏｓｅ Ｆｕｒｎａｃｅ）、ＳＡＦ（Ｓｅｍｉ Ｒｅｉｎｆｏｒｃｉｎｇ Ｆｕｒｎａｃｅ）、ＦＴ（Ｆｉｎｅ Ｆｕｒｎａｃｅ）、ＭＴ（Ｍｅｄｉｕｍ Ｔｈｅｒｍａｌ）などが挙げられる。
【００３６】
導電性金属酸化物は酸化チタン、酸化亜鉛、酸化錫、酸化インジウムおよびそれらからなる混合物などが好ましく使用される。
【００３７】
導電性ポリマーはポリピロール、ポリアニリン、ポリチオフェンおよびそれらからなる混合物などが好ましく使用される。
【００３８】
金属微粒子と導電性ポリマーを併用すると、反応温度では融解しない金属間の接合に一部不完全なところがあったとしても導電性ポリマーによる補充により、金属間の電気的接続がより確実となり、低抵抗となる。
【００３９】
導電性充填剤（Ｃ）は、充分に乾燥させて硬化反応を阻害する水分を切ってから、ポリイソシアネート（Ａ）もしくはアミン化合物（Ｂ）に分散させる。
【００４０】
導電性充填剤（Ｃ）の分散量は、その種類や目的とする導電度にあわせて適宜選択される。ただし、導電性充填剤（Ｃ）が少なすぎると、得られる樹脂組成物の電気抵抗値が十分に低くならない可能性があり、逆に過剰に加えると樹脂の硬化反応を阻害する可能性があるので、樹脂組成物１００重量部に対して８〜１０００重量部、好ましくは１０〜６００重量部の割合で選ばれる。
【００４１】
＜樹脂組成物＞
ポリイソシアネート（Ａ）とアミン化合物（Ｂ）を混合する際の粘度は、反応の均一性および塗布品質に大きな影響を与える。よって、導電充填剤（Ｃ）をポリイソシアネート（Ａ）、アミン化合物（Ｂ）のいずれに分散させる場合においても、ポリイソシアネート（Ａ）の粘度が６０℃以下の保温状態で７００ｃｐｓ以下となり、アミン化合物（Ｂ）の粘度が５０℃以下の保温状態で１００ｃｐｓ以下となるように原料を選択することが好ましい。揮発性のない無溶剤系希釈剤により粘度調整を行っても良い。
【００４２】
また、ポリイソシアネート（Ａ）とアミン化合物（Ｂ）の混合比は、アミン化合物（Ｂ）中のアミノ基に対してポリイソシアネート（Ａ）中のイソシアネート基が０．８当量以上１．４当量以下となるよう選択することが好ましい。この当量比が０．８を下回ると硬化が不十分になる可能性があり、１．４を上回ると得られる硬化物が脆くなるおそれがある。
【００４３】
本発明の樹脂組成物に含まれる揮発性有機化合物（以下、溶剤）は０．１重量％以下にすることが好ましい。そうすることで、使用時の人体への悪影響を無くすことができるほか、塗布時に不必要な部分への回り込みがない、基材への浸透による電流リークを防ぐことができるといった利点を得ることができる。
【００４４】
本発明の樹脂組成物の販売、流通形態としては、たとえばポリイソシアネート成分と、ポリアミン成分とが各々独立の容器に入れられた、組成物セットの形態等が考えられる。
【００４５】
【実施例】
以下に、実施例、比較例により本発明をさらに具体的に説明するが、本発明はこれらの記載に限定されるものではない。尚、実施例で用いた化合物は以下の通りである。
【００４６】
ポリイソシアネート（Ａ）
ＨＤ−１００：Ｂａｙｅｒ社製、１，６−ヘキサメチレンジイソシアネート（ＨＤＩ）のウレトジオン体およびイソシアヌレート体が含まれる。
Ｄｅｓｍｏｄｕｒ ＸＰ−７１００：Ｂａｙｅｒ社製、１，６−ヘキサメチレンジイソシアネート（ＨＤＩ）のアロファネート体およびイソシアヌレート体が含まれる。
【００４７】
アミン化合物（Ｂ）
クリアリンク１０００：ＵＯＰ社製ビス（Ｎ−イソブチルアミノシクロヘキシル）メタン。
クリアリンク３０００：ＵＯＰ社製ビス（Ｎ−イソブチルアミノメチルシクロヘキシル）メタン。
【００４８】
［実施例１］
クリアリンク１０００（アミン化合物（Ｂ））１００重量部に、あらかじめ導電性充填剤（Ｃ）として市販の銀粉（３２５ｍｅｓｈ）４０重量部を攪拌分散させたポリアミン成分に、室温常湿の環境下でＮＣＯ基／ＮＨ基が１．０５当量となるように、ＨＤ−１００（ポリイソシアネート成分）を添加し、ミキサーで数秒混合後、速やかに絶縁基板上にコートして厚さ３００μｍの膜状硬化物を形成した。
【００４９】
ポリアミン成分とポリイソシアネート成分の混合時を基準とした場合の指触乾燥時間は９０秒であった。
【００５０】
四端子抵抗計（三菱化学社製）による測定の結果、体積抵抗値は２×１０^-3Ω・ｃｍと導電性を示した。
【００５１】
また、耐光性試験としてキセノンテスター（島津製作所製）中に４００時間放置して、初期との色差ΔＥを測定したところΔＥの値は０．５であった。ΔＥは、その値が小さいほど変化の少ないことを示す。
【００５２】
［実施例２〜４］
表１に示すポリイソシアネート成分とポリアミン成分を用いた以外は、実施例１と同様にして膜状硬化物を形成し、評価した。結果を表１に示す。実施例２においては、導電性充填剤としてカーボン粉末を用いたため膜状硬化物が光沢の無い黒色となり、有意の色差ΔＥを測定より求めることはできなかった。しかし、目視による観察では耐光性試験前後に硬化物の外観の変化は見られなかった。
【００５３】
【表１】

【００５４】
［比較例１］
本発明との比較のため、市販の常温乾燥型銀ペースト（スリーボンド社製３３５０Ｃ）を用いて導電膜を形成した。
【００５５】
比抵抗は７×１０^-4Ω・ｃｍと実施例１の膜状硬化物よりやや低かったが、溶剤の乾燥に２４時間以上要する上、不必要な個所への回り込みによる電流リークや収縮がひどく精密な形状制御ができなかった。
【００５６】
［比較例２］
本発明との比較のため、市販の無溶剤系短時間硬化導電性接着剤（九州松下電器社製ＤＢＣ２３０Ｓ）を用いて導電膜を形成した。
【００５７】
硬化時間は３０秒で、比抵抗は９×１０^-4Ω・ｃｍと実施例１の膜状硬化物と同等であったが、硬化に１８０℃の加熱が必要なためプラスチック基板上に塗布した場合は基板が変形してしまった。また、色差ΔＥの値は３．８であり、肉眼の観察でも色の変化が確認された。
【００５８】
【発明の効果】
以上説明のように、本発明によれば、硬化反応が常温で速やかに進行するため、これまでの導電性接着剤で必要とされた加熱プロセスや光照射プロセスは必要としない。よってこの樹脂は広範な基材の被覆、接着が可能であり、耐候性も優れているので多様な用途への応用が期待される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a conductive polyurea resin composition, a curing agent for conductive polyurea resin, a composition set for forming a conductive polyurea resin, and a method for producing a conductive polyurea resin composition.
[0002]
[Prior art]
In recent years, with the progress of the electronics industry, especially the semiconductor industry, soldering from the viewpoint of workability and cost reduction for the purpose of bonding semiconductor elements and substrates (die bonding) and forming fine circuits and electrodes of printed wiring boards. As an alternative to this, a conductive resin paste is mainly used.
[0003]
Its constituents are made by dispersing conductive fillers such as metal powder and conductive carbon in synthetic resins and diluents, and many are known to contain various additives and solvents depending on their intended use. ing.
[0004]
Currently, the conductive resin paste composition is required to be cured in a short time by a simple process in order to realize further high throughput and high productivity. In addition, with the miniaturization of products, moldability to minute locations is also required.
[0005]
[Problems to be solved by the invention]
However, conventional conductive adhesives and pastes have a drawback that the function of the device is impaired because the solvent wraps around to unnecessary portions during application or permeates the base material to cause current leakage. Moreover, after application | coating, many things require a heating process for thermosetting or solvent drying, and there also existed a fault that a base material was damaged by heat. Further, for example, JP-A-10-116517 and JP-A-2002-109959 describe solventless type conductive pastes. However, the solventless type conductive pastes proposed in these publications still require baking at a high temperature, for example, 120 ° C. or 150 ° C. for curing, and the selection of the material of the substrate is also necessary. There will be strict restrictions.
[0006]
Furthermore, in order to compensate for these drawbacks, solvent-free conductive resin compositions that cure at room temperature have been developed and marketed, but many of these require processes such as light irradiation and pressurization to cure. Therefore, the material and shape of the base material that can be used are limited.
[0007]
Therefore, the present invention solves such problems, and its purpose is excellent in conductivity, moldability, and stability, and it has high weather resistance at room temperature from a solvent-free raw material group without using a special curing acceleration process. It is in providing the conductive polyurea resin composition which can obtain hardened | cured material, the hardening | curing agent for conductive polyurea resins, the composition set for conductive polyurea resin formation, and the manufacturing method of a conductive polyurea resin composition.
[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventor has intensively studied paying attention to the fluidity of the raw materials, the reaction rate, and the stability after curing, and the polyurea resin composition obtained in the present invention has the optimum results. As a result, the present invention has been found.
[0009]
That is, the conductive polyurea resin composition of the present invention contains at least a polyisocyanate (A), an amine compound (B) represented by the following general formula (1), and a conductive filler (C). And
[0010]
[Chemical 6]

[0011]
Wherein R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms and may be the same or different. R _{3 to} R ₆ are each a hydrogen atom or 1 to 5 And may be the same or different.)
[0012]
The conductive polyurea resin composition according to the present invention includes: “the conductive filler (C) is selected from metal fine particles, conductive carbon powder, conductive metal oxide, conductive polymer”, “the amine compound ( B), R ₁ and R ₂ are butyl groups, R ₃ and R ₄ are hydrogen atoms or methyl groups, and R ₅ and R ₆ are hydrogen atoms, ”“ the polyisocyanate (A) is aliphatic. And / or “being alicyclic” and “equivalent ratio of NCO / NH being 0.8 to 1.4” are included as preferred embodiments.
[0013]
Moreover, the curing agent for conductive polyurea resin of the present invention is characterized by containing at least the amine compound (B) represented by the general formula (1) and the conductive filler (C).
[0014]
The curing agent for conductive polyurea resin according to the present invention is “the conductive filler (C) is selected from metal fine particles, conductive carbon powder, conductive metal oxide, conductive polymer”, “the amine compound” In (B), R ₁ and R ₂ are butyl groups, R ₃ and R ₄ are hydrogen atoms or methyl groups, and R ₅ and R ₆ are hydrogen atoms ”as a preferred embodiment.
[0015]
The composition set for forming a conductive polyurea resin according to the present invention is a composition set for forming a conductive polyurea resin having a polyisocyanate component and a polyamine component independently, and the polyamine component Is characterized by containing at least the amine compound (B) represented by the general formula (1) and containing a conductive filler (C) in one of the polyisocyanate component and the polyamine component.
[0016]
The composition set for forming a conductive polyurea resin according to the present invention is “the conductive filler (C) is selected from metal fine particles, conductive carbon powder, conductive metal oxide, and conductive polymer”, “ In the amine compound (B), R ₁ and R ₂ are butyl groups, R ₃ and R ₄ are hydrogen atoms or methyl groups, and R ₅ and R ₆ are hydrogen atoms, ”“ in the polyisocyanate component ” The polyisocyanate (A) includes “aliphatic and / or alicyclic” as a preferred embodiment.
[0017]
Moreover, the manufacturing method of the electroconductive polyurea resin composition of this invention is the above-mentioned polyisocyanate (A) which is a viscosity of 700 cps or less in a heat retention state of 60 ° C. or less, and a viscosity of 100 cps or less in a heat insulation state of 50 ° C. or less. The polyamine component in which the conductive filler (C) is dispersed in the amine compound (B) represented by the general formula (1) has an NCO / NH functional group ratio of 0.8 equivalents to 1.4 equivalents. The mixture is mixed and cured at room temperature.
[0018]
Moreover, the manufacturing method of the electroconductive polyurea resin composition of this invention is the polyisocyanate component which disperse | distributed the electroconductive filler (C) in the polyisocyanate (A) which is 700 cps or less in the heat retention state of 60 degrees C or less. And an amine compound (B) represented by the above general formula (1) having a viscosity of 100 cps or less at a temperature of 50 ° C. or less, an NCO / NH functional group ratio of 0.8 equivalents or more and 1.4 equivalents or less. It mixes so that it may become, and it makes it normal temperature harden | cure.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0020]
<Polyisocyanate (A)>
The polyisocyanate (A) in the present invention refers to a dimer or higher compound having at least two or more active isocyanate groups at the terminal. A mixture of polyisocyanates having different structures may be used in order to control the reaction rate and the hardness of the resin depending on the purpose of use.
[0021]
However, the use of a polyfunctional monomeric isocyanate compound is not preferable from the viewpoint of harm to the living body and stability of the molded product. In view of the compatibility with the amine compound (B) and the light stability of the cured resin, the polyisocyanate (A) is preferably aliphatic and / or alicyclic.
[0022]
Examples of polyisocyanates used in the present invention include uretdione, biuret, isocyanurate, allophanate, and trimethylpropane adducts of hexamethylene diisocyanate (HDI), as long as the above conditions are satisfied. For example, other polyisocyanates and mixtures thereof may be used. For example, a polyisocyanate prepolymer subjected to chain extension with polyamine or polyol may be used as a component.
[0023]
<Amine compound (B)>
The amine compound (B) used in the present invention is bis (N-alkylaminocyclohexyl) methanes represented by the following general formula (1), and is disclosed in Japanese Patent No. 2759053.
[0024]
[Chemical 7]

[0025]
Wherein R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms and may be the same or different. R _{3 to} R ₆ are each a hydrogen atom or 1 to 5 And may be the same or different.)
[0026]
R ₁ and R ₂ in the formula are alkyl groups having 1 to 10 carbon atoms and may be linear or branched. R ₁ and R ₂ may be different but in most cases are the same for adjustment. Representative alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, and various pentyl isomers, hexyl, heptyl, octyl, and decyl groups. Preferred R ₁ and R ₂ contain at least 3 carbon atoms, in particular the butyl group is preferred and of the latter the secondary butyl group is particularly preferred.
[0027]
R _{3 to} R ₆ are each selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, but in most cases R ₃ and R ₄ are the same. Representative alkyl groups are the same as those having 1 to 5 carbon atoms among those described above as R ₁ and R ₂ . When R ₅ and R ₆ are both hydrogen are most preferred.
[0028]
In addition, the alkylamino group may be in any position of the ring with respect to the CR ₅ R ₆ group, and R ₃ and R ₄ may occupy any position with respect to the alkylamino group. There is no restriction on the alkylamino group and the relative positions of R ₃ and R ₄ , but the most common type is the alkylamino group in the 4,4′-position with respect to the CR ₅ R ₆ binding position. Most commonly, when R ₃ and R ₄ are alkyl groups, they occupy the 3- and 3′-positions.
[0029]
In consideration of compatibility with the polyisocyanate, R ₁ and R ₂ are preferably butyl groups, R ₃ and R ₄ are hydrogen atoms or methyl groups, and R ₅ and R ₆ are preferably hydrogen atoms.
[0030]
The amine compound (B) corresponding to the above is commercially available from UOP under the names Clearlink 1000 and Clearlink 3000, and can be widely used in the present invention.
[0031]
These amine compounds (B) may be used alone or in combination with aliphatic and / or alicyclic amines in order to control the reaction rate and the hardness of the resin.
[0032]
The composition of the present invention has a sufficiently high curing rate at room temperature, but may further be used with a curing accelerator in order to further improve the curability.
[0033]
<Conductive filler (C)>
The conductive filler (C) is selected from metal fine particles, conductive carbon powder, conductive metal oxide, and conductive polymer.
[0034]
As the metal fine particles, those having good conductivity and being hardly affected by oxidation are used. As an example, fine particles of gold, silver, copper, nickel, palladium tin and a mixture thereof are preferably used. These metal fine particles preferably have an average particle size in the range of 0.1 to 35 μm. If the average particle size exceeds 35 μm, the contact between the fine particles may be insufficient and the conductivity may decrease, and if it is less than 0.1 μm, the contact resistance may increase and the conductivity may decrease. The shape of the metal fine particles is preferably spherical or flaky.
[0035]
As the conductive carbon powder, conductive carbon black, conductive carbon graphite, conductive carbon nanotube, fullerene and the like are preferably used. Examples of the conductive carbon black include EC (Extra Conductive), ECF (Extra Conductive Furnace), SCF (Super Conductive Furnace), CF (Conductive Furnace), and EC (J). , SAF (Super Abrasion Furnace), ISAF (Intermediate SAF), HAF (High Abrasion Furnace), FEF (Fast Extrusion Furnace), GPF (General Purpose FurSens, FRS) dium Thermal) and the like.
[0036]
As the conductive metal oxide, titanium oxide, zinc oxide, tin oxide, indium oxide and a mixture thereof are preferably used.
[0037]
As the conductive polymer, polypyrrole, polyaniline, polythiophene and a mixture thereof are preferably used.
[0038]
When metal fine particles and a conductive polymer are used in combination, even if there is a partial imperfection in the bonding between metals that does not melt at the reaction temperature, replenishment with the conductive polymer ensures a more reliable electrical connection between the metals and lower resistance. It becomes.
[0039]
The conductive filler (C) is sufficiently dried to remove moisture that inhibits the curing reaction, and then dispersed in the polyisocyanate (A) or the amine compound (B).
[0040]
The dispersion amount of the conductive filler (C) is appropriately selected according to the type and the target conductivity. However, if the amount of the conductive filler (C) is too small, the electric resistance value of the resulting resin composition may not be sufficiently low, and conversely if added excessively, the resin curing reaction may be inhibited. Therefore, it is selected at a ratio of 8 to 1000 parts by weight, preferably 10 to 600 parts by weight, with respect to 100 parts by weight of the resin composition.
[0041]
<Resin composition>
The viscosity at the time of mixing the polyisocyanate (A) and the amine compound (B) greatly affects the uniformity of the reaction and the coating quality. Therefore, in the case where the conductive filler (C) is dispersed in either the polyisocyanate (A) or the amine compound (B), the viscosity of the polyisocyanate (A) is 700 cps or less in a heat retaining state of 60 ° C. or less, and the amine compound It is preferable to select the raw material so that the viscosity of (B) is 100 cps or less in a heat retaining state of 50 ° C. or less. The viscosity may be adjusted with a non-volatile solventless diluent.
[0042]
The mixing ratio of the polyisocyanate (A) and the amine compound (B) is such that the isocyanate group in the polyisocyanate (A) is 0.8 equivalent or more and 1.4 equivalent or less with respect to the amino group in the amine compound (B). It is preferable to select such that If this equivalent ratio is less than 0.8, curing may be insufficient, and if it exceeds 1.4, the resulting cured product may be brittle.
[0043]
The volatile organic compound (hereinafter, solvent) contained in the resin composition of the present invention is preferably 0.1% by weight or less. By doing so, the adverse effects on the human body during use can be eliminated, there is no wraparound to unnecessary parts during application, and current leakage due to penetration into the substrate can be obtained. it can.
[0044]
As a sales and distribution form of the resin composition of the present invention, for example, a form of a composition set in which a polyisocyanate component and a polyamine component are placed in independent containers can be considered.
[0045]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these descriptions. The compounds used in the examples are as follows.
[0046]
Polyisocyanate (A)
HD-100: The uretdione body and isocyanurate body of 1,6-hexamethylene diisocyanate (HDI) manufactured by Bayer are included.
Desmodur XP-7100: Bayer, allophanate and isocyanurate forms of 1,6-hexamethylene diisocyanate (HDI) are included.
[0047]
Amine compound (B)
Clearlink 1000: Bis (N-isobutylaminocyclohexyl) methane manufactured by UOP.
Clearlink 3000: Bis (N-isobutylaminomethylcyclohexyl) methane manufactured by UOP.
[0048]
[Example 1]
To 100 parts by weight of Clearlink 1000 (amine compound (B)), 40 parts by weight of a commercially available silver powder (325 mesh) as a conductive filler (C) was previously stirred and dispersed in a polyamine component under an environment of room temperature and humidity. HD-100 (polyisocyanate component) is added so that the group / NH group becomes 1.05 equivalent, mixed for several seconds with a mixer, and then quickly coated on an insulating substrate to form a film-like cured product having a thickness of 300 μm. Formed.
[0049]
The touch-drying time based on the mixing of the polyamine component and the polyisocyanate component was 90 seconds.
[0050]
As a result of measurement with a four-terminal resistance meter (manufactured by Mitsubishi Chemical Corporation), the volume resistance value was 2 × 10 ⁻³ Ω · cm, indicating conductivity.
[0051]
Further, as a light resistance test, the sample was left in a xenon tester (manufactured by Shimadzu Corporation) for 400 hours and measured for a color difference ΔE from the initial value, the value of ΔE was 0.5. ΔE indicates that the smaller the value, the less change.
[0052]
[Examples 2 to 4]
A film-like cured product was formed and evaluated in the same manner as in Example 1 except that the polyisocyanate component and the polyamine component shown in Table 1 were used. The results are shown in Table 1. In Example 2, since carbon powder was used as the conductive filler, the film-like cured product became dull black, and a significant color difference ΔE could not be obtained from the measurement. However, visual observation showed no change in the appearance of the cured product before and after the light resistance test.
[0053]
[Table 1]

[0054]
[Comparative Example 1]
For comparison with the present invention, a conductive film was formed using a commercially available room-temperature dry silver paste (3350C manufactured by Three Bond Co., Ltd.).
[0055]
The specific resistance was 7 × 10 ⁻⁴ Ω · cm, which was slightly lower than the film-like cured product of Example 1. However, it took 24 hours or more to dry the solvent, and current leakage and shrinkage due to wraparound to unnecessary parts were severe. Precise shape control was not possible.
[0056]
[Comparative Example 2]
For comparison with the present invention, a conductive film was formed using a commercially available solventless short-time curing conductive adhesive (DBC230S manufactured by Kyushu Matsushita Electric Co., Ltd.).
[0057]
The curing time was 30 seconds and the specific resistance was 9 × 10 ⁻⁴ Ω · cm, which was the same as the film-like cured product of Example 1, but it was applied on a plastic substrate because heating at 180 ° C. was required for curing. In that case, the substrate was deformed. Further, the value of the color difference ΔE was 3.8, and the color change was confirmed even by observation with the naked eye.
[0058]
【The invention's effect】
As described above, according to the present invention, the curing reaction proceeds promptly at room temperature, so that the heating process and the light irradiation process required with the conventional conductive adhesive are not required. Therefore, this resin can be applied to a wide range of base materials and bonded, and has excellent weather resistance, so that it is expected to be applied to various applications.

Claims (14)

A conductive polyurea resin composition comprising at least a polyisocyanate (A), an amine compound (B) represented by the following general formula (1), and a conductive filler (C).

Wherein R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms and may be the same or different. R _{3 to} R ₆ are each a hydrogen atom or 1 to 5 And may be the same or different.) The conductive polyurea resin composition according to claim 1, wherein the conductive filler (C) is selected from metal fine particles, conductive carbon powder, conductive metal oxide, and conductive polymer. _{3. The} amine compound (B), wherein R ₁ and R ₂ are butyl groups, R ₃ and R ₄ are hydrogen atoms or methyl groups, and R ₅ and R ₆ are hydrogen atoms. The conductive polyurea resin composition described in 1. The conductive polyurea resin composition according to claim 1, wherein the polyisocyanate (A) is aliphatic and / or alicyclic. The conductive polyurea resin composition according to claim 1, wherein the NCO / NH equivalent ratio is 0.8 to 1.4. A curing agent for conductive polyurea resin, comprising at least an amine compound (B) represented by the following general formula (1) and a conductive filler (C).

Wherein R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms and may be the same or different. R _{3 to} R ₆ are each a hydrogen atom or 1 to 5 And may be the same or different.) The curing agent for conductive polyurea resin according to claim 6, wherein the conductive filler (C) is selected from metal fine particles, conductive carbon powder, conductive metal oxide, and conductive polymer. 8. The amine compound (B), wherein R ₁ and R ₂ are butyl groups, R ₃ and R ₄ are hydrogen atoms or methyl groups, and R ₅ and R ₆ are hydrogen atoms. Curing agent for conductive polyurea resin as described in 1. A composition set for forming a conductive polyurea resin having a polyisocyanate component and a polyamine component independently, wherein the polyamine component is at least an amine compound represented by the following general formula (1) (B And a conductive filler (C) in either one of the polyisocyanate component and the polyamine component. A composition set for forming a conductive polyurea resin.

Wherein R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms and may be the same or different. R _{3 to} R ₆ are each a hydrogen atom or 1 to 5 And may be the same or different.) The composition for forming a conductive polyurea resin according to claim 9, wherein the conductive filler (C) is selected from metal fine particles, conductive carbon powder, conductive metal oxide, and conductive polymer. set. 11. The amine compound (B), wherein R ₁ and R ₂ are butyl groups, R ₃ and R ₄ are hydrogen atoms or methyl groups, and R ₅ and R ₆ are hydrogen atoms. A composition set for forming a conductive polyurea resin as described in 1. The composition set for forming a conductive polyurea resin according to any one of claims 9 to 11, wherein the polyisocyanate (A) in the polyisocyanate component is aliphatic and / or alicyclic. A polyisocyanate (A) having a viscosity of 700 cps or less at a temperature of 60 ° C. or less and an amine compound (B) represented by the following general formula (1) having a viscosity of 100 cps or less at a temperature of 50 ° C. or less are electrically conductive. Conductive polyurea resin characterized by mixing a polyamine component in which a conductive filler (C) is dispersed with an NCO / NH functional group ratio of 0.8 equivalents to 1.4 equivalents and curing at room temperature A method for producing the composition.

Wherein R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms and may be the same or different. R _{3 to} R ₆ are each a hydrogen atom or 1 to 5 And may be the same or different.) A polyisocyanate component in which a conductive filler (C) is dispersed in a polyisocyanate (A) having a viscosity of 700 cps or less in a heat retention state of 60 ° C. or less, and a viscosity of 100 cps or less in a heat insulation state of 50 ° C. or less. Conductive polyurea characterized in that the amine compound (B) represented by the general formula (1) is mixed and cured at room temperature so that the NCO / NH functional group ratio is 0.8 equivalent or more and 1.4 equivalent or less. A method for producing a resin composition.

Wherein R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms and may be the same or different. R _{3 to} R ₆ are each a hydrogen atom or 1 to 5 And may be the same or different.)