Electrically conductive liquids based on metal-diphosphonate complexes

Abstract

The invention relates to electrically conducting liquids based on diphosphonate complexes and to the use thereof in methods for electrolytically modifying the surface of a flat metal workpiece. The invention further relates to the flat metal workpieces produced by said method and to the use of the metal workpieces as a substrate for forming permanent adhesive bonds with a plurality of materials and for accommodating liquid and solid materials.

1 - 21 . (canceled) 
     
     
         22 . Electrically conductive liquid comprising an aqueous solution of a metal complex,
 wherein the metal complex is a complex of
 (i) one or more metals selected from the group consisting of Cu, Zn, Mn, In, Sn, Sb, Bi, Fe, Ni, Co, Ti, Zr, Nb, Y, Ce, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and mixtures thereof, and 
 (ii) one or more diphosphonate ligands of the general formula (I)
   O═P(OH) 2 —X—(OH) 2 P═O  (I)
 
 
   wherein:   X=O, NR 1  or CR 1 R 2 ,   R 1 =H, C 1 -C 18 -n-alkyl or C 3 -C 18 -isoalkyl, C s -C 6 -cycloalkyl, unsubstituted or substituted benzyl and substituted or unsubstituted phenyl,   R 2 =R 1 , —OR 3  or —NHR 3 , and   R 3 =H, C 1 -C 4 -n-alkyl or C 3 -C 4 -isoalkyl, and wherein   the OH groups in the general formula (I) which are bonded to the two phosphorus atoms independently of each other are protonated (OH) or deprotonated (O − ),   
       wherein the liquid furthermore optionally comprises an additive of the general formula (II):
   R 10 —CHR 8 —CHR 9 —Z—(CHR 4 —CHR 5 —Z) n —CHR 6 —CHR 7 —R 10   (II)
 
 
       wherein:
 n=an integer from 1 to 11, 
 Z=S or O, 
 R 4 =H, C 1-4 -alkyl or phenyl, 
 R 5 =H, C 1-4 -alkyl or phenyl, 
 R 6 =H, C 1-4 -alkyl or phenyl, 
 R 7 =H, C 1-4 -alkyl or phenyl, 
 R 8 =H, C 1-4 -alkyl or phenyl, 
 R 9 =H, C 1-4 -alkyl or phenyl, 
 R 10 =OH, COOH or COOR 11  and 
 R 11 =C 1-4 -alkyl, Li, Na, or K. 
 
     
     
         23 . The liquid according to  claim 22  wherein X=CR 1 R 2 . 
     
     
         24 . The liquid according to  claim 22  wherein Z is S. 
     
     
         25 . The liquid according to  claim 22  wherein n is 1, 2, or 3. 
     
     
         26 . The liquid according to  claim 22 , wherein the metal is Cu, Zn, Mn, In, Sn, Sb, Bi, Fe, Ni, Co, Ti, Zr, Nb, or mixtures thereof, said metal being optionally doped with Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or mixtures thereof. 
     
     
         27 . The liquid according to  claim 26  wherein the metal is Cu. 
     
     
         28 . The liquid according to  claim 26 , wherein the metal is Fe, Ni, Co or mixtures thereof, wherein the metal is doped with Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or mixtures thereof. 
     
     
         29 . The liquid according to  claim 28  wherein the metal is doped with Sm, Gd, Dy, Er or mixtures thereof. 
     
     
         30 . The liquid according to  claim 22 , wherein the additive is present in an amount of 1 wt % or less based on the weight of the total solution. 
     
     
         31 . The liquid according to  claim 30 , wherein the additive is present in an amount ranging from 0.05 to 0.7 wt %, based on the weight of the total solution. 
     
     
         32 . The liquid according to  claim 30 , wherein the additive is present in an amount ranging from 0.1 to 0.5 wt %, based on the weight of the total solution. 
     
     
         33 . The liquid according to claim  1 , wherein the liquid comprises an additive of the formula (II), wherein
 n=an integer from 1 to 3,   Z=S,   R 4 =H, methyl, ethyl, n-propyl or n-butyl,   R 5 =H, methyl, ethyl, n-propyl or n-butyl,   R 6 =H, methyl, ethyl, n-propyl or n-butyl,   R 7 =H, methyl, ethyl, n-propyl or n-butyl,   R 8 =H, methyl, ethyl, n-propyl or n-butyl,   R 9 =H, methyl, ethyl, n-propyl or n-butyl,   R 10 =OH, COOH or COOR 11 , and   R 11 =K, methyl, ethyl or n-propyl.   
     
     
         34 . The liquid according to  claim 33 , wherein the additive is 1,8-dihydroxy-3,6-dithiaoctane. 
     
     
         35 . The liquid according to  claim 22 , wherein the metal is Cu and the additive is 1,8-dihydroxy-3,6-dithiaoctane. 
     
     
         36 . The liquid according to  claim 22 , wherein the liquid is substantially free from sulphate, nitrate, halogenate and halide ions. 
     
     
         37 . The liquid according to  claim 22 , wherein the liquid comprises no additional buffer in addition to the ligand of the formula (I). 
     
     
         38 . A method for the electrolytic surface modification of a flat metal workpiece, comprising:
 (a) anodically polarizing at least one surface of the flat metal workpiece in a treatment liquid, whereby an anodic dissolving process is thereby induced, and then   (b) cathodically polarizing said at least one surface of the flat metal workpiece in a treatment liquid, whereby a cathodic deposition process is thereby induced for the deposition of one or more metals on the at least one surface of the flat metal workpiece,   said treatment liquid being a liquid according to  claim 22 .   
     
     
         39 . The method according to  claim 38 , wherein the flat metal workpiece is anodically polarized by at least one cathode without direct contacting for the induction of the dissolving process, the flat metal workpiece is cathodically polarized by at least one anode without direct contacting for the induction of the deposition process, and the cathode and the anode are arranged in such a way that treatment liquid is located between anode and metal workpiece and between cathode and metal workpiece. 
     
     
         40 . The method according to  claim 38 , wherein the treatment liquid in the anodic dissolving process and the treatment liquid in the cathodic deposition process are different treatment liquids and the treatment liquid in the anodic dissolving process and the treatment liquid in the cathodic deposition process are separated by a non-conductive separating liquid which has contact to the flat metal workpiece. 
     
     
         41 . The method according to  claim 38 , wherein layers of host metals doped with doping metals are deposited by varying the average current density of the deposition and the concentration ratio between the doping metal(s) and host metal(s) between 1:5 and 150:1 in the treatment liquid, wherein the host metals are selected from Cu, Zn, Mn, In, Sn, Sb, Bi, Fe, Ni, Co and mixtures thereof, and the doping metals are selected from Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Nb or mixtures thereof, and are present in the layer in an amount ranging from 1 ppm to 20,000 ppm. 
     
     
         42 . The method according to  claim 38 , wherein ferromagnetic closed layers of the metals Cu, Zn, Mn, In, Sn, Sb, Bi, Fe, Ni, Co, Nb or mixtures thereof which are doped with Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or mixtures thereof are deposited in a thickness ranging from 10 nm to 1 μm and have a greater layer thickness of the changeover between the in-plane and the out-of-plane orientation of the domains than in the case of ferromagnetic, pure metal layers deposited by vacuum. 
     
     
         43 . The method according to  claim 38 , wherein corrosion-stable iron and/or tin surfaces and recrystallization-inhibited tin surfaces are produced. 
     
     
         44 . A flat metal workpiece obtained from the method according to  claim 38 . 
     
     
         45 . A flat metal workpiece having a surface which comprises uniformly distributed discrete metal aggregates which protrude therefrom, wherein 90% or more of the metal aggregates have a size ranging from 0.05 to 1 μm, said metal aggregates being comprised of metals selected from Cu, Zn, Mn, In, Sn, Sb, Bi, Fe, Ni, Co, Nb and mixtures thereof, said surface having an average roughness values Ra and Rz values, as determined in accordance with DIN EN ISO 4288:1998, range from 0.22 to 0.32 μm and 1.4 to 2.1 μm, respectively. 
     
     
         46 . The flat metal workpiece according to  claim 45  wherein the metals are doped with one or more doping metal(s) selected from Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr and mixtures thereof, and the doping metal(s) is (are) present in the metal aggregate in an amount ranging from 1 ppm to 20,000 ppm. 
     
     
         47 . The flat metal workpiece according to  claim 45 , wherein the surface of the flat metal workpiece comprises metal aggregates, wherein 90% or more of the metal aggregates have a size ranging from 0.3 to 0.7 μm. 
     
     
         48 . The flat metal workpiece according to  claim 47 , wherein the surface of the flat metal workpiece comprises metal aggregates, wherein 90% or more of the metal aggregates have a size ranging from 0.35 to 0.65 μm. 
     
     
         49 . The flat metal workpiece according to  claim 48 , wherein the surface of the flat metal workpiece comprises metal aggregates, wherein 99% or more of the metal aggregates have a size ranging from 0.3 to 0.7 μm. 
     
     
         50 . The flat metal workpiece according to  claim 44 , wherein the surface of the flat metal workpiece is comprised of metal aggregates, wherein the metal aggregates are comprised of Cu, Zn, Mn, In, Sn, Sb, Bi, Fe, Ni, Co, Nb or mixtures thereof. 
     
     
         51 . A composition of matter comprised of the flat metal workpiece of  claim 44 . 
     
     
         52 . A composition of matter comprised of the flat metal workpiece of  claim 45 . 
     
     
         53 . The composition of matter of  claim 52  bonded to materials selected from thermoplastics, synthetic resins, adhesives, lacquers and pastes. 
     
     
         54 . The flat metal workpiece according to  claim 45  comprised of a metal selected from copper, tin, zinc, aluminium, iron and nickel or a metal alloy comprised of copper, iron, silver or tin. 
     
     
         55 . The flat metal workpiece according to  claim 45  comprised of copper upon which copper aggregates are deposited on the surface thereof. 
     
     
         56 . The flat metal workpiece according to  claim 45  wherein the average roughness values Ra and Rz range from 0.24 to 0.28 μm and from 1.6 to 1.9 μm, respectively.