PURPOSE: To produce a highly reliable copper through-hole printed circuit board at a low cost with good productivity at the time of producing the board by the negative forming method by forming an etching resist film with a specified compd.

CONSTITUTION: Copper chemical plating and copper electroplating are applied on the surface of a copper-clad laminate having many holes, then a negative circuit is formed with a resist ink soluble in an aq. alkaline soln., alkali- developed liq. resist or alkali-developed photosensitive film, and the circuit is dipped in an acidic soln. mixed with 0.01-40% one or ≥2 kinds of compds. shown by formulas I, II and III as an effective component to form an etching resist film on the copper surface. The circuit is then dipped in a buffer contg. 50-150ppm copper ion and kept at pH 6.5-5.0. The obtained copper-clad laminte is dried and then brought into contact with an aq. alkaline soln. to remove the negative photosensitive film or resist film and treated with an alkaline liq. etchant to stably produce an excellent printed circuit board.