Colloidal metal dispersion, and a colloidal metal complex

Claim 1

A colloidal metal complex comprising: colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table; amino group-containing compound or polymer; and a protective polymer adsorbed on said colloidal particles, said protective polymer comprising 1 to 100 mol percent, based on the total of units (i), (ii) and (iii), of units (i) represented by the formula [I] ##STR39## wherein R 1 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group ##STR40## --CO--R and --O--R', wherein R is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and --(CH 2 ) n1 --X n2 --(CH 2 ) n1 --X n2 --(CH 2 ) n3 --Y n4 --(CH 2 )n5--CO--R 7 , (CH 2 ) n5 --CO--R 7 wherein X and Y are each independently selected from the group consisting of --O-- and --NH--, --A--R 8 and --NH 2 , R 7 is selected from the group consisting of --NH--NH 2 , --A--R 8 and --NH 2 , wherein A is selected from the group consisting of --O--and --S--, and R 8 is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group and a substituted or unsubstituted succinimido group, n1, n3 and n5 each independently represent an integer of 0 to 6, and n2 and n4 each independently represent an integer of 0 or 1, and R' has the same meaning as R, and R 2 represents --(CH 2 ) n1'--X'n2' --(CH 2 ) n3' --Y' n4' --(CH 2 ) n5' --CO--R 7' wherein X', Y', R 7' , n1', n2', n3', n4' and n5' respectively have the same meanings as X, Y, R 7 , n1, n2, n3, n4 and n5; 0to 99 mol percent, based on total of units (i), (ii) and (iii), of units (ii) represented by the formula [II] ##STR41## wherein R 3 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group ##STR42## --CO--R and --O--R' wherein R and R' are as defined above, and R 4 represents--(CH 2 ) n1"--X" n2" --(CH 2 ) n3" --Y" n4' --(CH 2 ) n5" --CO--R--R 9 wherein X", Y", n1", n2", n3", n4" and n5" respectively have the same meanings as X, Y, n1, n2, n3, n4 and n5, and R 9 represents --A'--R 10 , wherein A' has the same meaning as A, and R 10 is selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group and a substituted or unsubstituted succinimido group; and 0to 99 mol percent, based on total of units (i), (ii) and (iii), of units (iii) represented by the formula [III] ##STR43## wherein R 5 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group ##STR44## --CO--R and --O--R' wherein R and R' are as defined above, and R 6 is selected from the group consisting of a hydroxyl group, ##STR45## --CO--R and --O--R' wherein R and R' are as defined above; said protective polymer being bonded to said amino group-containing compound or polymer directly or through the residue of a bifunctional compound reactive to an amino group, thereby binding said colloidal particles to said amino group-containing compound or polymer; provided that where R 1 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, the proportions of units (i), (ii) and (iii) are respectively 1 to 95 mol percent, 0 to 90 mol percent and 5 to 99 mol percent, based on the total of units (i), (ii) and (iii); where R 7 is --NH--NH 2 , the --NH--NH 2 groups or part or all of the --NH--NH 2 groups are modified to form --N 3 groups; where R 7 is --A--R 8 , said colloidal particles are bound to said amino group-containing compound or polymer directly; and where said protective polymer is a copolymer of acrylamide and N-vinyl-2-pyrrolidone and said amino group-containing compound or polymer is aminoethylated polyacrylamide, said protective polymer is bonded to said amino group-containing compound through the residue of a bifunctional compound reactive to an amino group.

Claim 11

A method for the preparation of a colloidal metal complex comprising: colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table; an amino group-containing compound or polymer; and a protective polymer adsorbed on said colloidal particles, said protective polymer being bonded to said amino group-containing compound or polymer directly, thereby binding said colloidal particles to said amino group-containing compound or polymer; said protective polymer comprising 1 to 100 mol percent, based on the total of units (i), (ii) and (iii), of units (i) represented by the formula [I] ##STR46## wherein R 1 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR47## --CO--R and --O--R', wherein R is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and --(CH 2 ) n1 --X n2 --(CH 2 ) n3 --Y n4 --(CH 2 ) n5 --CO--R 7 , --CO--R 7 , wherein X and Y are each independently selected from the group consisting of --O-- and --NH--, R 7 is selected from the group consisting of --NH--NH 2 , --A--R 8 and --NH 2 , wherein A is selected from the group consisting of --O-- and --S--, and R 8 is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group and a substituted or unsubstituted succinimido group, n1, n3 and n5 each independently represent an integer of 0 to 6, and n2 and n4 each independently represent an integer of 0 or 1, and R' has the same meaning as R, and R 2 represents --(CH 2 ) n1' --X' n2' --(CH 2 ) n3' --Y' n4' --(CH 2 ) n5' --CO--R 7' wherein X', Y', R 7' , n1', n2', n3', n4' and n5' respectively have the same meanings as X, Y, R 7 , n1, n2, n3, n4 and n5; 0to 99 mol percent, based on the total of units (i), (ii) and (iii), of units (ii) represented by the formula [II] ##STR48## wherein R 3 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR49## --CO--R and --O--R' wherein R and R' are as defined above, and R 4 represents --(CH 2 ) n1" --X" n2" --(CH 2 ) n3" --Y" n4" --(CH 2 ) n5" --CO--R 9 wherein X", Y", n1", n2", n3", n4" and n5" respectively have the same meanings as X, Y, n1, n2, n3, n4 and n5, and R 9 represents --A'--R 10 , wherein A' has the same meaning as A, and R 10 is selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group and a substituted or unsubstituted succinimido group; and 0to 99 mol percent, based on the total of units (i), (ii) and of units (iii) represented by the formula [III] ##STR50## wherein R 5 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR51## --CO--R and --O--R' wherein R and R' are as defined above, and R 6 is selected from the group consisting of a hydroxyl group, ##STR52## --CO--R and --O--R' wherein R and R' are as defined above; which comprises contacting an amino group-containing compound or polymer with a polymer-protected colloidal metal dispersion comprising (a) a dispersion medium; (b) colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table, said colloidal particles being dispersed in said dispersion medium; and (c) a protective polymer adsorbed on said colloidal particles, said protective polymer being as defined above, provided that where R 1 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, the proportions of units (i), (ii) and (iii) are respectively 1 to 95 mol percent, 0 to 90 mol percent and 5 to 99 mol percent, based on the total of units (i), (ii) and (iii), and where said protective polymer is a copolymer of acrylamide and N-vinyl-2-pyrrolidone, said amino group-containing compound or polymer is exclusive of aminoethylated polyacrylamide.

Claim 12

A method for the preparation of a colloidal metal complex comprising: colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table; an amino group-containing compound or polymer; and a protective polymer adsorbed on said colloidal particles, said protective polymer being bonded to said amino group-containing compound or polymer directly, thereby binding said colloidal particles to said amino group-containing compound or polymer; said protective polymer comprising 1 to 100 mol percent, based on the total of units (i), (ii) and (iii), of units (i) represented by the formula [I] ##STR46## wherein R 1 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR47## --CO--R and --O--R', wherein R is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and --(CH 2 ) n1 --X n2 --(CH 2 ) n3 --Y n4 --(CH 2 ) n5 --CO--R 7 , --CO--R 7 , wherein X and Y are each independently selected from the group consisting of --O-- and --NH--, R 7 is selected from the group consisting of --NH--NH 2 , --A--R 8 and --NH 2 , wherein A is selected from the group consisting of --O-- and --S--, and R 8 is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group and a substituted or unsubstituted succinimido group, n1, n3 and n5 each independently represent an integer of 0 to 6, and n2 and n4 each independently represent an integer of 0 or 1, and R' has the same meaning as R, and R 2 represents --(CH 2 ) n1' --X' n2' --(CH 2 ) n3' --Y' n4' --(CH 2 ) n5' --CO--R 7' wherein X', Y', R 7' , n1', n2', n3', n4' and n5' respectively have the same meanings as X, Y, R 7 , n1, n2, n3, n4 and n5; 0to 99 mol percent, based on the total of units (i), (ii) and (iii), of units (ii) represented by the formula [II] ##STR48## wherein R 3 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR49## --CO--R and --O--R' wherein R and R' are as defined above, and R 4 represents --(CH 2 ) n1" --X" n2" --(CH 2 ) n3" --Y" n4" --(CH 2 ) n5" --CO--R 9 wherein X", Y", n1", n2", n3", n4" and n5" respectively have the same meanings as X, Y, n1, n2, n3, n4 and n5, and R 9 represents --A'--R 10 , wherein A' has the same meaning as A, and R 10 is selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group and a substituted or unsubstituted succinimido group; and 0to 99 mol percent, based on the total of units (i), (ii) and of units (iii) represented by the formula [III] ##STR50## wherein R 5 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR51## --CO--R and --O--R' wherein R and R' are as defined above, and R 6 is selected from the group consisting of a hydroxyl group, ##STR52## --CO--R and --O--R' wherein R and R' are as defined above; which comprises contacting an amino group-containing compound or polymer with a polymer-protected colloidal metal dispersion comprising (a) a dispersion medium; (b) colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table, said colloidal particles being dispersed in said dispersion medium; and (c) a protective polymer adsorbed on said colloidal particles, said protective polymer being as defined above, provided that where R 1 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, the proportions of units (i), (ii) and (iii) are respectively 1 to 95 mol percent, 0 to 90 mol percent and 5 to 99 mol percent, based on the total of units (i), (ii) and (iii), and where said protective polymer is a copolymer of acrylamide and N-vinyl-2-pyrrolidone, said amino group-containing compound or polymer is exclusive of aminoethylated polyacrylamide.

Claim 20

A method for the preparation of a colloidal metal complex comprising: colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table; an amino group-containing compound or polymer; and a protective polymer adsorbed on said colloidal particles, said protective polymer being bonded to said amino group-containing compound or polymer through the residue of a bifunctional compound reactive to an amino group, thereby binding said colloidal particles to said amino group-containing compound or polymer said protective polymer comprising 1 to 100 mol percent, based on the total of units (i), (ii) and (iii), of units (i) Represented by the formula [I] ##STR53## wherein R 1 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR54## --CO--R and --O--R', wherein R is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and --(CH 2 ) n1 --X n2 --(CH 2 ) n3 --Y n4 --(CH 2 ) n5 --CO--R 7 , wherein X and Y are each independently selected from the group consisting of --O-- and --NH--, R 7 is selected from the group consisting of --NH--NH 2 , and --NH 2 , n1, n3 and n5 each independently represent an integer of 0 to 6, and n2 and n4 each independently represent an integer of 0 or 1, and R' has the same meanings as R, and R 2 represents --(CH 2 ) n1' X' n2' --(CH 2 ) n3' --Y' n4' --(CH 2 ) n5' --CO--R 7' wherein X', Y', R 7' , n1', n2', n3', n4' and n5' respectively have the same meanings as X, Y, R 7 , n1, n2, n3, n4 and n5; 0to 99 mol percent, based on the total of units (i), (ii) and (iii), of units (ii) represented by the formula [II] ##STR55## wherein R 3 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR56## --CO--R and --O--R' wherein R and R' are as defined above, and R 4 represents --(CH 2 ) n1" --X" n2" --(CH 2 ) n3" --Y" n4" --(CH 2 ) n5" --CO--R 9 wherein X", Y", n1", n2", n3", n4" and n5" respectively have the same meanings as X, Y, n1, n2, n3, n4 and n5, and R 9 represents --A'--R 10 , wherein A' is selected from the group consisting of --O-- and --S--, and R 10 is selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group and a substituted or unsubstituted succinimido group; and to 99 mol percent, based on the total of units (i), (ii) and (iii), of units (iii)represented by the formula [III] ##STR57## wherein R 5 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR58## --CO--R and --O--R' wherein R and R' are as defined above, and R 6 is selected from the group consisting of a hydroxyl group ##STR59## --CO--R and --O--R' wherein R and R' are as defined above; provided that where R 1 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, the proportions of units (i), (ii) and (iii) are respectively 1 to 95 mol percent, 0 to 90 mol percent and 5 to 99 mol percent, based on the total of units (i), (ii) and (iii), which comprises reacting a polymer-protected colloidal metal dispersion comprising (a) a dispersion medium; (b) colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table, said colloidal particles being dispersed in said dispersion medium; and (c) a protective polymer adsorbed on said colloidal particles, said protective polymer being as defined above; with a bifunctional compound reactive to an amino group to obtain a reaction product, and contacting the reaction product with an amino group-containing compound or polymer; or which comprises contacting said polymer-protected colloidal metal dispersion with an amino group-containing compound or polymer in the presence of a bifunctional compound or polymer reactive to an amino group.

Claim 21

A method for the preparation of a colloidal metal complex comprising: colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table; an amino group-containing compound or polymer; and a protective polymer adsorbed on said colloidal particles, said protective polymer being bonded to said amino group-containing compound or polymer through the residue of a bifunctional compound reactive to an amino group, thereby binding said colloidal particles to said amino group-containing compound or polymer said protective polymer comprising 1 to 100 mol percent, based on the total of units (i), (ii) and (iii), of units (i) Represented by the formula [I] ##STR53## wherein R 1 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR54## --CO--R and --O--R', wherein R is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and --(CH 2 ) n1 --X n2 --(CH 2 ) n3 --Y n4 --(CH 2 ) n5 --CO--R 7 , wherein X and Y are each independently selected from the group consisting of --O-- and --NH--, R 7 is selected from the group consisting of --NH--NH 2 , and --NH 2 , n1, n3 and n5 each independently represent an integer of 0 to 6, and n2 and n4 each independently represent an integer of 0 or 1, and R' has the same meanings as R, and R 2 represents --(CH 2 ) n1' X' n2' --(CH 2 ) n3' --Y' n4' --(CH 2 ) n5' --CO--R 7' wherein X', Y', R 7' , n1', n2', n3', n4' and n5' respectively have the same meanings as X, Y, R 7 , n1, n2, n3, n4 and n5; 0to 99 mol percent, based on the total of units (i), (ii) and (iii), of units (ii) represented by the formula [II] ##STR55## wherein R 3 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR56## --CO--R and --O--R' wherein R and R' are as defined above, and R 4 represents --(CH 2 ) n1" --X" n2" --(CH 2 ) n3" --Y" n4" --(CH 2 ) n5" --CO--R 9 wherein X", Y", n1", n2", n3", n4" and n5" respectively have the same meanings as X, Y, n1, n2, n3, n4 and n5, and R 9 represents --A'--R 10 , wherein A' is selected from the group consisting of --O-- and --S--, and R 10 is selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group and a substituted or unsubstituted succinimido group; and to 99 mol percent, based on the total of units (i), (ii) and (iii), of units (iii)represented by the formula [III] ##STR57## wherein R 5 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR58## --CO--R and --O--R' wherein R and R' are as defined above, and R 6 is selected from the group consisting of a hydroxyl group ##STR59## --CO--R and --O--R' wherein R and R' are as defined above; provided that where R 1 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, the proportions of units (i), (ii) and (iii) are respectively 1 to 95 mol percent, 0 to 90 mol percent and 5 to 99 mol percent, based on the total of units (i), (ii) and (iii), which comprises reacting a polymer-protected colloidal metal dispersion comprising (a) a dispersion medium; (b) colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table, said colloidal particles being dispersed in said dispersion medium; and (c) a protective polymer adsorbed on said colloidal particles, said protective polymer being as defined above; with a bifunctional compound reactive to an amino group to obtain a reaction product, and contacting the reaction product with an amino group-containing compound or polymer; or which comprises contacting said polymer-protected colloidal metal dispersion with an amino group-containing compound or polymer in the presence of a bifunctional compound or polymer reactive to an amino group.

Claim 29

A method for the preparation of a colloidal metal complex comprising: colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table; an amino group-containing compound or polymer; and a protective polymer adsorbed on said colloidal particles, said protective polymer being bonded to said amino group-containing compound or polymer directly, thereby binding said colloidal particles to said amino group-containing compound or polymer; said protective polymer comprising 1 to 100 mol percent, based on the total of units (i), (ii) and (iii), of units (i) represented by the formula [I] ##STR60## wherein R 1 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR61## --CO--R and --O--R', wherein R is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and --(CH 2 ) n1 --X n2 --(CH 2 ) n3 --Y n4 --(CH 2 ) n5 --CO--NH--NH 2 , wherein X and Y are each independently selected from the group consisting of --O-- and --NH--, n1, n3 and n5 each independently represent an integer of 0 to 6, and n2 and n4 each independently represent an integer of 0 or 1, and R' has the same meaning as R, and R 2 represents --(CH 2 ) n1' --X' n2' --(CH 2 ) n3' --Y' n4' --(CH 2 ) n5' --CO--NH--NH 2 wherein X', Y', n1', n2', n3', n4' and n5' respectively have the same meanings as X, Y, n1, n2, n3, n4 and n5; 0to 99 mol percent, based on the total of units (i), (ii) and (iii), of units (ii)represented by the formula [II] ##STR62## wherein R 3 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR63## --CO--R and --O--R' wherein R and R' are as defined above, and R 4 represents --(CH 2 ) n1" --X" n2" --(CH 2 ) n3" --Y" n4" --(CH 2 ) n5" --CO--R 9 wherein X", Y", n1", n2", n3", n4" and n5" respectively have the same meanings as X, Y, n1, n2, n3, n4 and n5, and R 9 represents --A'--R 10 , wherein A' is selected from the group consisting of --O-- and --S--, and R 10 is selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group and a substituted or unsubstituted succinimido group; and 0to 99 mol percent, based on the total of units (i), (ii) and (iii), of units (iii) represented by the formula [III] ##STR64## wherein R 5 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR65## --CO--R and --O--R' wherein R and R' are as defined above; R 6 is selected from the group consisting of a hydroxyl group, ##STR66## CO--R and --O--R' wherein R and R' are as defined above; provided that where R 1 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, the proportions of units (i), (ii) and (iii) are respectively 1 to 95 mol percent, 0 to 90 mol percent and 5 to 99 mol percent, based on the total of units (i), (ii) and (iii), which comprises reacting a polymer-protected colloidal metal dispersion comprising (a) a dispersion medium; (b) colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table, said colloidal particles being dispersed in said dispersion medium; and (c) a protective polymer adsorbed on said colloidal particles, said protective polymer being as defined above; with nitrous acid or a nitrite to obtain a reaction product, and contacting the reaction product with an amino group-containing compound or polymer; or which comprises contacting said polymer-protected colloidal metal dispersion with an amino group-containing compound in the presence of nitrous acid or a nitrite.

Claim 30

A method for the preparation of a colloidal metal complex comprising: colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table; an amino group-containing compound or polymer; and a protective polymer adsorbed on said colloidal particles, said protective polymer being bonded to said amino group-containing compound or polymer directly, thereby binding said colloidal particles to said amino group-containing compound or polymer; said protective polymer comprising 1 to 100 mol percent, based on the total of units (i), (ii) and (iii), of units (i) represented by the formula [I] ##STR60## wherein R 1 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR61## --CO--R and --O--R', wherein R is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and --(CH 2 ) n1 --X n2 --(CH 2 ) n3 --Y n4 --(CH 2 ) n5 --CO--NH--NH 2 , wherein X and Y are each independently selected from the group consisting of --O-- and --NH--, n1, n3 and n5 each independently represent an integer of 0 to 6, and n2 and n4 each independently represent an integer of 0 or 1, and R' has the same meaning as R, and R 2 represents --(CH 2 ) n1' --X' n2' --(CH 2 ) n3' --Y' n4' --(CH 2 ) n5' --CO--NH--NH 2 wherein X', Y', n1', n2', n3', n4' and n5' respectively have the same meanings as X, Y, n1, n2, n3, n4 and n5; 0to 99 mol percent, based on the total of units (i), (ii) and (iii), of units (ii)represented by the formula [II] ##STR62## wherein R 3 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR63## --CO--R and --O--R' wherein R and R' are as defined above, and R 4 represents --(CH 2 ) n1" --X" n2" --(CH 2 ) n3" --Y" n4" --(CH 2 ) n5" --CO--R 9 wherein X", Y", n1", n2", n3", n4" and n5" respectively have the same meanings as X, Y, n1, n2, n3, n4 and n5, and R 9 represents --A'--R 10 , wherein A' is selected from the group consisting of --O-- and --S--, and R 10 is selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group and a substituted or unsubstituted succinimido group; and 0to 99 mol percent, based on the total of units (i), (ii) and (iii), of units (iii) represented by the formula [III] ##STR64## wherein R 5 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxyl group, ##STR65## --CO--R and --O--R' wherein R and R' are as defined above; R 6 is selected from the group consisting of a hydroxyl group, ##STR66## CO--R and --O--R' wherein R and R' are as defined above; provided that where R 1 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, the proportions of units (i), (ii) and (iii) are respectively 1 to 95 mol percent, 0 to 90 mol percent and 5 to 99 mol percent, based on the total of units (i), (ii) and (iii), which comprises reacting a polymer-protected colloidal metal dispersion comprising (a) a dispersion medium; (b) colloidal particles of at least one metal selected from the group consisting of metals belonging to Groups Ib, VIIb and VIII of the Periodic Table, said colloidal particles being dispersed in said dispersion medium; and (c) a protective polymer adsorbed on said colloidal particles, said protective polymer being as defined above; with nitrous acid or a nitrite to obtain a reaction product, and contacting the reaction product with an amino group-containing compound or polymer; or which comprises contacting said polymer-protected colloidal metal dispersion with an amino group-containing compound in the presence of nitrous acid or a nitrite.