Copper electrolytic solution containing quaternary amine compound polymer with specific skeleton and organo-sulfur compound as additives, and electrolytic copper foil manufactured using the same

Abstract

There is obtained a low-profile electrolytic copper foil with a small surface roughness on the side of the rough surface (the opposite side from the lustrous surface) in the manufacture of an electrolytic copper foil using a cathode drum, and more particularly an electrolytic copper foil which allows fine patterning, and is superior in terms of elongation and tensile strength at ordinary temperatures and high temperatures. The present invention provides a copper electrolytic solution, containing as additives an organo-sulfur compound and a quaternary amine compound polymer obtained by homopolymerizing a compound in which nitrogen of an acrylic type compound having a dialkylamino group is quaternized, or copolymerizing the compound with another compound having an unsaturated bond, and an electrolytic copper foil manufactured using this electrolytic solution.

1 . A copper electrolytic solution, containing as additives an organo-sulfur compound and a quaternary amine compound polymer obtained by homopolymerizing a compound in which nitrogen of an acrylic type compound having a dialkylamino group is quaternized, or copolymerizing the compound with another compound having an unsaturated bond.  
     
     
         2 . The copper electrolytic solution according to  claim 1 , wherein said compound obtained by quaternizing nitrogen of an acrylic type compound having a dialkylamino group is expressed by the following general formula (1), (2) or (3).  
       
         
           
           
               
               
           
         
       
       (In general formulae (1) through (3), R 1  indicates hydrogen or an alkyl group with 1 to 5 carbon atoms, each of R 2  indicates an alkyl group with 1 to 5 carbon atoms, R 3  indicates an alkyl group with 1 to 5 carbon atoms, a benzyl group or an allyl group, X 1   −  indicates Cl − , Br −  or CH 3 SO 4   − , and n indicates an integer of 1 to 5.)  
     
     
         3 . The copper electrolytic solution according to  claim 1 , wherein said organo-sulfur compound is a compound expressed by the following general formula (4) or (5).  
         X—R 1 —(S) n —R 2 —Y  (4)  R 4 —S—R 3 —SO 3 Z  (5)  
       (In general formulae (4) and (5), R 1 , R 2  and R 3  each indicate an alkylene group with 1 to 8 carbon atoms, R 4  indicates a group selected from the group consisting of hydrogen,  
       
         
           
           
               
               
           
         
       
       X is selected from the group consisting of hydrogen, a sulfonic acid group, a phosphonic acid group, and an alkali metal salt group or ammonium salt group of sulfonic acid or phosphonic acid, Y is selected from the group consisting of a sulfonic acid group, a phosphonic acid group, and an alkali metal salt group of sulfonic acid or phosphonic acid, Z indicates hydrogen or an alkali metal, and n is 2 or 3.)  
     
     
         4 . An electrolytic copper foil which is manufactured using the copper electrolytic solution according to  claim 1 .  
     
     
         5 . A copper-clad laminate which is formed using the copper electrolytic foil according to  claim 4.