US3793037A - Electroless copper plating solution and process - Google Patents
Electroless copper plating solution and process Download PDFInfo
- Publication number
- US3793037A US3793037A US3793037DA US3793037A US 3793037 A US3793037 A US 3793037A US 3793037D A US3793037D A US 3793037DA US 3793037 A US3793037 A US 3793037A
- Authority
- US
- United States
- Prior art keywords
- copper
- composition
- amine
- ferrous metal
- ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 46
- 239000010949 copper Substances 0.000 title claims abstract description 46
- 238000007747 plating Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 36
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 iodide ions Chemical class 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 25
- 150000001412 amines Chemical class 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical group C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 claims description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000008199 coating composition Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 42
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001431 copper ion Inorganic materials 0.000 abstract description 11
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 6
- 239000003929 acidic solution Substances 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 230000001464 adherent effect Effects 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 125000001475 halogen functional group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229940035422 diphenylamine Drugs 0.000 description 3
- 235000011167 hydrochloric acid Nutrition 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QYXCMECSRMQWNS-UHFFFAOYSA-N 2-phenyl-n,n-bis(2-phenylethyl)ethanamine Chemical compound C=1C=CC=CC=1CCN(CCC=1C=CC=CC=1)CCC1=CC=CC=C1 QYXCMECSRMQWNS-UHFFFAOYSA-N 0.000 description 1
- AGNFWIZBEATIAK-UHFFFAOYSA-N 4-phenylbutylamine Chemical compound NCCCCC1=CC=CC=C1 AGNFWIZBEATIAK-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- PUHAKHQMSBQAKT-UHFFFAOYSA-L copper;butanoate Chemical compound [Cu+2].CCCC([O-])=O.CCCC([O-])=O PUHAKHQMSBQAKT-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- ZQLBQWDYEGOYSW-UHFFFAOYSA-L copper;disulfamate Chemical class [Cu+2].NS([O-])(=O)=O.NS([O-])(=O)=O ZQLBQWDYEGOYSW-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940068917 polyethylene glycols Drugs 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000006617 triphenylamine group Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- ABSTRACT A plating solution suitable for the electroless deposition of copper on ferrous metal surfaces which comprises an aqueous acidic solution containing copper ions; chloride, bromide, or iodide ions; 3 polyalkylene glycol; and a tertiary amine compound of the structure:
- a is zero or 1;
- b is 2 or 3;
- a b is 3;
- n is 0 to 4, inclusive; or substituted alkyl R is alkyl/of 1 to 4 carbon atoms where the substituent may be hydroxy or halo; and,
- R is phenyl or substituted phenyl where the substituent may be mono-, di-, or trihalo or alkyl of 1 to 4 carbon atoms.
- This invention relates to a novel composition and process for the treatment of metal surfaces and more particularly it relates to a composition and process for the electroless copper plating of ferrous metal surfaces.
- compositions and processes which I have heretofore been developed have been generally satisfactory, some difficulties have been encountered where different types and grades of ferrous metal surfaces have been treated.
- variations in the type of ferrous metal being treated have resulted in similar variations in the quality of the copper coating which has been produced.
- these cooper coating solutions have been used for treating steel wire, prior to wire drawing operations, it has often been found to be difficult to consistently obtain a bright, adherent coating.
- the compositions of the prior art have had relatively low tolerance for ferrous iron. With these solutions, as the quantity of ferrous iron in the bath has increased, the quality of the copper coating produced has decreased.
- an object of the present invention to provide an improved coating solution from which bright, adherent copper coatings may be obtained on a variety of ferrous metal surfaces, without the use of electric current.
- v r r a A further object of the present invention is to provide an improved process for forming a bright, adherent copper coating on a variety of ferrous metal surfaces without the use of electric current.
- Another object of the present invention is to provide an improved composition and process for forming a bright, adherent copper coating on ferrous metal surfaces, which composition and process will tolerate the build-up of appreciable quantities of ferrous iron in the coating solution without adversely affecting the quality of the copper coating which is produced.
- the present invention includes an aqueous acidic solution containing copper ions; halide ions selected from chloride, bromide and iodide ions; a polyalkylene glycol; and a tertiary amine compound having the formula:
- a is zero or l
- b is 2 or 3;
- a b is 3;
- n is 0 to 4, inclusive; or substituted alkyl R is alkyl/of l to 4 carbon atoms where the substituent may be hydroxy or halo; and
- R is phenyl or substituted phenyl where the substituent may be mono-, di-, or tri-halo or alkyl of l to 4 carbon atoms.
- the novel plating solutions are aqueous acidic 30 solutions containing copper ions, which solutions desirably have a pH within the range of about 0 to 2, and preferably within the range of about 0.2 to 0.4.
- the copper ions are desirably present in the plating solutions in amounts within the range of about 0.1 to 3.0 percent by weight of the solution and preferably in an amount within the range of about 0.3 to 0.8 percent by weight of this solution.
- the copper ions may be incorporated in the plating solutions in any suitable form, such as copper metal, and/or various copper salts.
- the bath pI-I may be maintained within the desired range by the addition of sulfuric acid.
- the aqueous acidic plating baths used contain such sulfate ions, they are typically present in amounts within the range of about 0.1 to 30. percent by weight of the solution.
- copper salts may also be used as the source of copper ions, such as copper chloride, copper bromide, copper acetate, copper citrate, copper benzoate, copper metaborate, copper butyrate, copper formate, copper sulfamates, and the like, and that other acids may be used for the pH adjustment of the bath. It is to be appreciated, however, that in using such other salts or acids, particularly those containing halide ions, care should be taken that the amounts of ,such latter ions introduced do not exceed the maximum amounts which can be present in the solution without detrimental effect.
- the plating solutions of the present invention contain halide ions, selected from chloride, bromide, and iodide ions.
- the chloride ions are preferred; Where chloride ions are used, they are desirably present in amounts within the range of about 0.001 to about percent by weight of the solution and preferably in amounts within the range of about 0.01 to 0.5 percent.
- bromide ions are used, they are desirably present in amounts within the range of about 0.001 to 5 percent weight and preferably in amounts within the range of about 0.02 to 0.5 percent by weight of the solution, while the iodide ions, if ,used, are desirably present in amounts within the range of about 0.001 to 5 percent by weight and preferably in amounts within the range of about 0.01 to 0.2 percent by weight of the solution. These are desirably added as the alkali metal salts.
- the polyalkylene glycol used'in the plating baths of the present invention desirably has a molecular weight in excess of about 600 and preferably has a molecular weight within the range of about 1,000 to 20,000 with a more preferred range of from about 1,500 to about 10,000.
- the amount of the polyalkylene glycol in the treating solutions will vary, depending upon the particular molecular weight of the polyalkylene glycol which,
- the polyalkylene glycol is present in the treating bath in amounts within the range of about 0.001 percent by weight of the solution up to its saturation concentration in the bath, with amounts within the range of about 0.006 to 1.0 percent by weight of the solution being preferred, the higher concentrations typically being used with the lower molecular weight materials, and vice versa.
- various polyalkylene glycols may be used, such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like. Of these, the polyethyleneglycols are generally preferred and, hence, particular reference will be made to these materials'hereinafter.
- the plating solutions of the present invention also contain at least one tertiary amine compound of the structural formula that has been indicated above.
- the amine compound used will be present in an amount within the range of 0.001 percent by weight of the solution up to their saturation content in the solution.
- amounts of the amine compound within the range of about 0.002 to 0.1 percent b weight of the solution will be used.
- amine compounds that may be used are as follows: triphenyl amine; tribenzyl amine; triphenethyl amine; N,N,N (4-phenyl butyl) amine; hydroxy methyl dibenzyl amine; 2-hydroxy ethyl dibenzyl amine; 4- chlorobutyl diphenyl amine; 4-iodobutyl diphenyl amine; 3-bromopropyl diphenyl amine; mono-, dior trimethyl substituted triphenyl amine; mono-, di-, or trichloro substituted tribenzyl amine, and the like.
- the aqueous acidic plating baths of the present invention arefound to give excellent plating results even where the baths contain appreciable quantities of ferrous iron.
- the plating baths of the present invention may also contain ferrous iron ions in amounts up to the saturation point of the ferrous iron in the bath, with amounts of ferrous iron ions within the range of about 5 to grams per liter being typical. Where such typical amounts of ferrous iron are present in the bath, and even where the ferrous iron content is greater than the saturation point of the path, it is still found that excellent quality copper coatings can be produced.
- the ferrous metal surface to be treated such as a length of steel wire
- this cleaning may include acid pickling, such as .with muriatic acid, alkaline cleaning, such as with alkali metal hydroxide and/or alkali metal permanganate containing cleaners, and may include a combination of several of these cleaning or pre-treating steps.
- acid pickling such as .with muriatic acid
- alkaline cleaning such as with alkali metal hydroxide and/or alkali metal permanganate containing cleaners
- these cleaning or pre-treating steps Following the 'cleaning or pretreating of the steel surface, it is brought into contact with the copper plating bath of the present invention.
- various contacting techniques may be utilized such as immersion, spraying, flooding, and the like.
- the ferrous surface treated is steel wire
- the wire is immersed in the copper plating bath.
- the copper plating bath of the present invention is desirably maintained at a temperature within the range of about 15 to C. and preferably 24 66C. and under these preferred conditions, immersion times of from about 10 seconds to 10 minutes are typical.
- the ferrous metal surface may then be rinsed with water and dried.
- a suitable lubricant may be applied to the coated wire to facilitate a subsequent drawing operation.
- Various lubricant materials such as numerous soap containing compositions, may be applied to the copper plated wire and this lubricant coating then dried thereon.
- the wire may then be subjected to the desired drawing operation and it is found that following the drawing, the copper finish on the wire is very bright and uniform and shows good adhesion.
- the solutions of the present invention may also be used to form a copper coating which is useful as a lubricant material for warm forming operations, as well as a decorative copper coating.
- EXAMPLE I A two liter solution was made up containing 48 grams of CuSO, 5H O, 6 grams of NaCl, 60 mls of H 80 h grams of polyethylene glycol (molecular weight 4000) and 1 percent F++ added as FeSo 7H O. Cleaned mild steel wire was processed through the bath before and after additions of N, N, N, tribenzylamine were made to the bath. The wire was processed in the bath at 100F. for two minutes. After treatment in the copper solution the wire was rinsed then dried with forced air. The N, N, N, tribenzylamine was added so that the total concentration varied from 10 mg per liter to 2000 mg per liter. Very light colored coatings with excellent adhesion were obtained at N, N, N, tribenzylamine concentrations between and 500 mg per liter. Above and below theseconcentrations the coatings were darker in color.
- EXAMPLE 11 A four liter solution was made up containing 96 g of CuSO, 511 0, 120 mils. of H SO 120 mg. of N, N, N, tribenzylamine, 12 gm. of NaCl, and 1 percent Fe-las FeSO, 7H O.
- Polyethylene glycol (molecular weight 4000) was added to the bath in increments of gm up to a total concentration of 1 gm.
- Cleaned mild steel wire was processed through the bath at each increment of polyethylene glycol. The processing time was 2 minutes at 100F.
- the resulting-coating was examined for color and adhesion. The coatingsobtained at polyethylene glycol concentrations below 3/16 g per liter were brownish orange in color and quite porous. Adhesion was marginal. However at a concentration of g per liter of polyethylene glycol, the resulting coating was very light in color and adhesion was excellent.
- EXAMPLE 111 A four liter aqueous bath containing 24 grams per liter of CuSO, 51-1 0, 30 ml/] H 80 400 g/l FeSO, 187F1 0 (8 percent Fe-H-), 3 g/l NaCl and 0.25 g/l polyethylene glycol (molecular weight 4000) was prepared. To the bath were added varying concentrations of dibenzylethanol amine such as 0, 6 g/l, 0.23 g/l and g/l.
- the wire was given the following coating cycle:
- An aqueous acidic solution suitable for forming a copper plate on ferrous metal surfaces without the application of electric current which comprises copper ions, halide ions, selected from chloride, bromide and iodide ions; a polyalkylene glycol selected from the group consisting of polyethylene, polypropylene and polybutylene glycols having a molecular weight in excess of about 600; and a tertiary amine of the formula:
- a is zero or 1;
- b is 2 or 3;
- a b is 3;
- n 0 to 4, inclusive
- R is alkyl or substituted alkyl of l to 4 carbon atoms where the substituent may be hydroxy or halo;
- R is phenyl or substituted phenyl where the substituent may be mono-, di-, or trihalo or alkyl of 1 to 4 carbon atoms wherein the copper ions are present in an amount of about 0.1 to 3 percent by weight, the halide ions are present in an. amount within the range of about 0.001 to 10 percent by weight, the polyalkylene glycol is present in an amount of at least about 0.001 percent by weight, and the amine material is present in an amount of at least 0.001 percent by weight to saturation.
- composition as claimed in claim 1 wherein the polyalkylene glycol has a molecular weight within the range of about 600 to 20,000.
- composition as claimed in claim 1 wherein the halide ions are chloride ions.
- composition of claim 4 wherein b is 3.
- composition of claim 1 wherein R is hydroxyl alkyl of from 1 to 4 carbon atoms.
- composition of claim 1 wherein the amine is N, N, N-tribenzyl'amine 9.
- composition of'claim 1 wherein the amine is N, N dibenzylhydroxyethyl' amine.
- a process for forming a copper coating on ferrous metal surfaces which comprises treating the ferrous metal surface to be coated with the coating com- 13. The process of claim 10 wherein b is 3.
- R is hydroxy alkyl of from 1 to 4 carbon atoms.
Abstract
Description
Claims (19)
- 2. The composition as claimed in claim 1 wherein the polyalkylene glycol has a molecular weight within the range of about 600 to 20,000.
- 3. The composition as claimed in claim 1 wherein the halide ions are chloride ions.
- 4. The composition of claim 4 wherein b is 3.
- 5. The composition of claim 1 wherein R is hydroxyl alkyl of from 1 to 4 carbon atoms.
- 6. The composition of claim 1 wherein n is 1.
- 7. The composition of claim 1 wherein R'' is phenyl.
- 8. The composition of claim 1 wherein the amine is N, N, N-tribenzyl amine.
- 9. The composition of claim 1 wherein the amine is N, N dibenzylhydroxyethyl amine.
- 10. A process for forming a copper coating on ferrous metal surfaces which comprises treating the ferrous metal surface to be coated with the coating composition as claimed in claim 1 and maintaining this composition in contact with the ferrous metal surface for a period sufficient to effect the formation of a copper coating.
- 11. The process as claimed in claim 10 wherein the polyalkylene glycol in the copper plating composition has a molecular weight from about 600 to 20,000.
- 12. The process as claimed in claim 11 wherein the halide ions in the copper composition are chloride ions.
- 13. The process of claim 10 wherein b is 3.
- 14. The process of claim 10 wherein R is hydroxy alkyl of from 1 to 4 carbon atoms.
- 15. The process of claim 10 wherein n is 1.
- 16. The process of claim 10 wherein R'' is phenyl.
- 17. The process of claim 10 wherein the amine is N, N, N -tribenzyl amine.
- 18. The process of claim 10 wherein the amine is N, N -dibenzylhydroxyethyl amine.
- 19. A ferrous metal surface having a copper coating formed thereon in accordance with the method of claim 16.
- 20. A ferrous metal surface having a copper coating formed thereon in accordance with the method of claim 12.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US23430272A | 1972-03-13 | 1972-03-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3793037A true US3793037A (en) | 1974-02-19 |
Family
ID=22880806
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US3793037D Expired - Lifetime US3793037A (en) | 1972-03-13 | 1972-03-13 | Electroless copper plating solution and process |
Country Status (10)
Country | Link |
---|---|
US (1) | US3793037A (en) |
JP (1) | JPS5518782B2 (en) |
AR (1) | AR197980A1 (en) |
AU (1) | AU467404B2 (en) |
BE (1) | BE793376A (en) |
CA (1) | CA989105A (en) |
ES (1) | ES410196A1 (en) |
FR (1) | FR2175729B1 (en) |
GB (1) | GB1373895A (en) |
ZA (1) | ZA731439B (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4259113A (en) * | 1976-05-26 | 1981-03-31 | Kollmorgen Technologies Corporation | Composition for sensitizing articles for metallization |
US4758025A (en) * | 1985-06-18 | 1988-07-19 | Mobil Oil Corporation | Use of electroless metal coating to prevent galling of threaded tubular joints |
US4981725A (en) * | 1972-07-11 | 1991-01-01 | Amp-Akzo Corporation | Process and composition for sensitizing articles for metallization |
US5776231A (en) * | 1994-11-11 | 1998-07-07 | Metallgesellschaft Aktiengesellschaft | Concentrate for the electroless deposition of copper coatings on iron and iron alloy surfaces |
WO2002053801A2 (en) * | 2000-12-29 | 2002-07-11 | Chemetall Gmbh | Electroless copper plating of ferrous metal substrates |
US20040072423A1 (en) * | 2001-01-12 | 2004-04-15 | Jacob Jorne | Methods and systems for electro-or electroless-plating of metal in high-aspect ratio features |
WO2012022660A1 (en) * | 2010-08-17 | 2012-02-23 | Chemetall Gmbh | Process for the electroless copper plating of metallic substrates |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52144901A (en) * | 1976-05-28 | 1977-12-02 | Shin Shirasuna Electric Corp | Device for monitoring power supply voltage |
JPS546731U (en) * | 1977-06-16 | 1979-01-17 | ||
JPS645617Y2 (en) * | 1981-05-29 | 1989-02-13 | ||
KR960003723B1 (en) * | 1986-05-19 | 1996-03-21 | 하라마 카세이 고오교오 가부시끼가이샤 | Method for forming a metal film on the surface of a substrate metal |
JPH0332385U (en) * | 1989-08-07 | 1991-03-28 | ||
JP2009001872A (en) * | 2007-06-22 | 2009-01-08 | Kobe Steel Ltd | Copper-plating method of wire-like material, and copper-plated wire |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2049517A (en) * | 1934-06-06 | 1936-08-04 | American Chem Paint Co | Method of and material for inhibiting or retarding acid corrosion of ferrous metals |
US2217921A (en) * | 1938-03-23 | 1940-10-15 | American Chem Paint Co | Art of drawing ferrous metal |
US3141780A (en) * | 1962-03-30 | 1964-07-21 | Minnesota Mining & Mfg | Copper coating compositions |
-
0
- BE BE793376D patent/BE793376A/en unknown
-
1972
- 1972-03-13 US US3793037D patent/US3793037A/en not_active Expired - Lifetime
- 1972-11-22 FR FR7241497A patent/FR2175729B1/fr not_active Expired
- 1972-12-29 ES ES72410196A patent/ES410196A1/en not_active Expired
-
1973
- 1973-02-28 AU AU52697/73A patent/AU467404B2/en not_active Expired
- 1973-02-28 CA CA164,876A patent/CA989105A/en not_active Expired
- 1973-03-01 ZA ZA731439A patent/ZA731439B/en unknown
- 1973-03-09 GB GB1147673A patent/GB1373895A/en not_active Expired
- 1973-03-12 JP JP2890973A patent/JPS5518782B2/ja not_active Expired
- 1973-03-13 AR AR24702373A patent/AR197980A1/en active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2049517A (en) * | 1934-06-06 | 1936-08-04 | American Chem Paint Co | Method of and material for inhibiting or retarding acid corrosion of ferrous metals |
US2217921A (en) * | 1938-03-23 | 1940-10-15 | American Chem Paint Co | Art of drawing ferrous metal |
US3141780A (en) * | 1962-03-30 | 1964-07-21 | Minnesota Mining & Mfg | Copper coating compositions |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4981725A (en) * | 1972-07-11 | 1991-01-01 | Amp-Akzo Corporation | Process and composition for sensitizing articles for metallization |
US4259113A (en) * | 1976-05-26 | 1981-03-31 | Kollmorgen Technologies Corporation | Composition for sensitizing articles for metallization |
US4758025A (en) * | 1985-06-18 | 1988-07-19 | Mobil Oil Corporation | Use of electroless metal coating to prevent galling of threaded tubular joints |
US5776231A (en) * | 1994-11-11 | 1998-07-07 | Metallgesellschaft Aktiengesellschaft | Concentrate for the electroless deposition of copper coatings on iron and iron alloy surfaces |
US6261644B1 (en) | 1994-11-11 | 2001-07-17 | Metallgesellschaft Aktiengesellschaft | Process for the electroless deposition of copper coatings on iron and iron alloy surfaces |
WO2002053801A2 (en) * | 2000-12-29 | 2002-07-11 | Chemetall Gmbh | Electroless copper plating of ferrous metal substrates |
WO2002053801A3 (en) * | 2000-12-29 | 2003-11-20 | Chemetall Gmbh | Electroless copper plating of ferrous metal substrates |
US20040052961A1 (en) * | 2000-12-29 | 2004-03-18 | Kevin Brown | Electroless copper plating of ferrous metal substrates |
US20040072423A1 (en) * | 2001-01-12 | 2004-04-15 | Jacob Jorne | Methods and systems for electro-or electroless-plating of metal in high-aspect ratio features |
WO2012022660A1 (en) * | 2010-08-17 | 2012-02-23 | Chemetall Gmbh | Process for the electroless copper plating of metallic substrates |
Also Published As
Publication number | Publication date |
---|---|
AU5269773A (en) | 1974-08-29 |
AU467404B2 (en) | 1975-11-27 |
BE793376A (en) | 1973-04-16 |
JPS5518782B2 (en) | 1980-05-21 |
ES410196A1 (en) | 1976-01-01 |
CA989105A (en) | 1976-05-18 |
AR197980A1 (en) | 1974-05-24 |
ZA731439B (en) | 1973-11-28 |
FR2175729A1 (en) | 1973-10-26 |
GB1373895A (en) | 1974-11-13 |
FR2175729B1 (en) | 1976-08-20 |
JPS492726A (en) | 1974-01-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3793037A (en) | Electroless copper plating solution and process | |
US4578122A (en) | Non-peroxide trivalent chromium passivate composition and process | |
US4204013A (en) | Method for treating polymeric substrates prior to plating employing accelerating composition containing an alkyl amine | |
SE7907373L (en) | PROCEDURE KIT FOR CONTINUOUS ELECTROPHERIC COPPER PREPARATION UNDER THE USE OF A HYPOPHOSPHITE REDUCING AGENT IN THE PRESENT OF COBOLK AND NICKELION AND COMPOSITION FOR EXERCISE OF PROCEDURAL KIT | |
US3817774A (en) | Preparation of plastic substrates for electroless plating | |
US3966502A (en) | Zirconium rinse for phosphate coated metal surfaces | |
US3684572A (en) | Electroless nickel plating process for nonconductors | |
US3368913A (en) | Process for the treatment of metal surfaces prior to enameling | |
US3140203A (en) | Method of and composition for treating aluminum and aluminum alloys | |
US3850732A (en) | Zirconium rinse for phosphate coated metal surfaces | |
US3664852A (en) | Electroless copper plating solution and process | |
US3775265A (en) | Method of plating copper on aluminum | |
US2548420A (en) | Method of producing lustrous zinc | |
US2958610A (en) | Pre-plating treatment of aluminous surfaces | |
US3769061A (en) | Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating | |
US3736157A (en) | Electroless copper tin plating solution and process | |
GB2144773A (en) | Non-peroxide trivalent chromium passivation | |
JP2965569B2 (en) | Etching pretreatment of plastic substrate | |
US2850417A (en) | Composition for and methods of forming oxalate coatings on metallic surfaces | |
JPH0734254A (en) | Electroless plating method to aluminum material | |
US3338725A (en) | Novel plating process and composition | |
US3575826A (en) | Method and composition for electroplating tin | |
US3726707A (en) | Porcelain enameling of steel | |
CA1236252A (en) | Compositions and processes for coating ferrous surfaces with copper | |
US3795622A (en) | Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP 32100 STEPHENSON Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:003942/0016 Effective date: 19810317 |
|
AS | Assignment |
Owner name: OXY METAL INDUSTRIES CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084 Effective date: 19741220 |
|
AS | Assignment |
Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |
|
AS | Assignment |
Owner name: PARKER CHEMICAL COMPANY, 32100 STEPHENSON HWY., MA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004194/0047 Effective date: 19830928 |