1.Guangdong Key Laboratory of Industrial Surfactant,Institute of Chemical Engineering,Guangdong Academy of Sciences;2.Guangdong Key Laboratory of Industrial Surfactant, Institute of Chemical Engineering,Guangdong Academy of Sciences;3.Institute of Chemical Engineering, Guangdong Academy of Sciences
Guangzhou Science and Technology Plan Project (202102080461，202201010309); Guangzhou Key R&D plan Major Science and Technology Special Project (20220602JBGS02); GDAS Sepecial Project of Guangdong Academy of Sciences (2022GDASZH-2022010109).
以異氰酸丙基三乙氧基硅烷、2-氨基噻唑和咪唑為主要原料，合成了（2-噻唑脲基）丙基三乙氧基硅烷（TUP）和咪唑酰胺基丙基三乙氧基硅烷（IAP）兩種唑硅烷偶聯劑。再分別以TUP和IAP為主成膜劑，采用浸涂法在銅箔表面固化成膜制備了具有高頻印制電路（PCB）應用價值的有機金屬涂層，并與棕化膜和甲基三乙氧基硅烷（KH132）、巰基丙基三乙氧基硅烷（KH580）有機涂層進行對比。利用FTIR、SEM、AFM和接觸角測量儀對涂層的結構、表面形貌、平整性和疏水性進行了表征。通過電化學、鹽霧和鹽水浸泡實驗對涂層的防腐性能進行測定，并分析了壓合后銅面/環氧樹脂層間附著力。結果表明，TUP和IAP唑硅烷偶聯劑均成功接枝到銅基表面，形成了一層相對平整光滑且致密均勻的有機保護膜。TUP含量為3%（以乙醇和水總質量為基準）形成的有機金屬涂層平整性較好，算術平均粗糙度（Ra）和均方根粗糙度（Rq）均低于21 nm，疏水性較優，水接觸角高達142°，耐腐蝕性較強，緩蝕效率可達99.2%，耐鹽霧可達14 d，壓合后銅/樹脂層間剝離強度為5.97 N/cm，滿足印制電路內層板附著力要求。
Two azole silane couple agents TUP and IAP were synthesized from 3-isocyanatopropyltriethoxysilane, 2-aminothiazole and imidazole. Organometallic coatings were obtained by dipping method on copper foil surface using TUP and IAP as main film-forming agents applied in high-frequency PCB, and then compared with brown oxidation film and polymeric coatings containing KH132 and KH580. The structure, surface morphology, flatness and hydrophobicity of the films were characterized by FTIR, SEM, AFM and contact angle measurement, respectively. The corrosion resistance of the layers was evaluated by electrochemical, salt spray and saline immersion tests, and the interfacial adhesion between copper foil and epoxy resin was investigated after laminates process. The results indicated that two azole silane coupling agents were both successfully grafted onto the copper surface, fabricating relatively smooth and compact organic protective films. The organometallic coatings formed by TUP with a concentration of 3% (based on the total mass of ethanol and water) exhibited excellent smoothness with Ra and Rq both below 21 nm，optimal hydrophobicity with water contact angle up to 142°. Furthermore, the corrosion inhibition efficiency could reach 99.2% and salt spray resistance up to 14 d revealing best barrier performance. In addition, the peel strength of copper/resin laminates achieved 5.97 N/cm appropriately, satisfying interfacial adhesion requirement of PCB.