US2986498A - Process for the production of metal electrodeposits - Google Patents
Process for the production of metal electrodeposits Download PDFInfo
- Publication number
- US2986498A US2986498A US714687A US71468758A US2986498A US 2986498 A US2986498 A US 2986498A US 714687 A US714687 A US 714687A US 71468758 A US71468758 A US 71468758A US 2986498 A US2986498 A US 2986498A
- Authority
- US
- United States
- Prior art keywords
- acid
- sulfonic acid
- bis
- electrodeposits
- propane
- 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
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- 239000002659 electrodeposit Substances 0.000 title claims description 26
- 229910052751 metal Inorganic materials 0.000 title claims description 26
- 239000002184 metal Substances 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 18
- 230000008569 process Effects 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title description 13
- 238000009713 electroplating Methods 0.000 claims description 38
- 239000012535 impurity Substances 0.000 claims description 32
- -1 CARBOXYL GROUPS Chemical group 0.000 claims description 27
- 238000005282 brightening Methods 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000008233 hard water Substances 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 150000004027 organic amino compounds Chemical class 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 41
- 229910052757 nitrogen Chemical group 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 27
- 229940032330 sulfuric acid Drugs 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 23
- 229910052802 copper Inorganic materials 0.000 description 23
- 239000010949 copper Substances 0.000 description 23
- 239000002253 acid Substances 0.000 description 19
- 239000004215 Carbon black (E152) Substances 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 18
- 229910052708 sodium Inorganic materials 0.000 description 16
- 239000011734 sodium Substances 0.000 description 16
- 230000002452 interceptive effect Effects 0.000 description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 229910000365 copper sulfate Inorganic materials 0.000 description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 8
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 7
- 230000002411 adverse Effects 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- IHPYMWDTONKSCO-UHFFFAOYSA-N 2,2'-piperazine-1,4-diylbisethanesulfonic acid Chemical compound OS(=O)(=O)CCN1CCN(CCS(O)(=O)=O)CC1 IHPYMWDTONKSCO-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 3
- VOPSFYWMOIKYEM-UHFFFAOYSA-N 2,5-diaminobenzene-1,4-disulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=C(N)C=C1S(O)(=O)=O VOPSFYWMOIKYEM-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000272534 Struthio camelus Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Chemical group 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 1
- MBIZXFATKUQOOA-UHFFFAOYSA-N 1,3,4-thiadiazole Chemical compound C1=NN=CS1 MBIZXFATKUQOOA-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ZIRURAJAJIQZFG-UHFFFAOYSA-N 1-aminopropane-1-sulfonic acid Chemical compound CCC(N)S(O)(=O)=O ZIRURAJAJIQZFG-UHFFFAOYSA-N 0.000 description 1
- IDIICHZCEIGXGB-UHFFFAOYSA-N 1-piperazinecarbodithioic acid Chemical compound SC(=S)N1CCNCC1 IDIICHZCEIGXGB-UHFFFAOYSA-N 0.000 description 1
- QMKCLGXQVZCWOT-UHFFFAOYSA-N 2,2-dihydroxyethylcarbamodithioic acid Chemical compound OC(O)CNC(S)=S QMKCLGXQVZCWOT-UHFFFAOYSA-N 0.000 description 1
- YTQQIHUQLOZOJI-UHFFFAOYSA-N 2,3-dihydro-1,2-thiazole Chemical compound C1NSC=C1 YTQQIHUQLOZOJI-UHFFFAOYSA-N 0.000 description 1
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 description 1
- MMLBEXXDOLIGCR-UHFFFAOYSA-N 2-hydroxyethylcarbamodithioic acid Chemical compound OCCNC(S)=S MMLBEXXDOLIGCR-UHFFFAOYSA-N 0.000 description 1
- QGZSANLMUAESBT-UHFFFAOYSA-N 3-piperazin-1-ylpropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCN1CCNCC1 QGZSANLMUAESBT-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- GWXMDJKGVWQLBZ-UHFFFAOYSA-N di(propan-2-yl)carbamodithioic acid Chemical compound CC(C)N(C(C)C)C(S)=S GWXMDJKGVWQLBZ-UHFFFAOYSA-N 0.000 description 1
- SZRLKIKBPASKQH-UHFFFAOYSA-N dibutyldithiocarbamic acid Chemical compound CCCCN(C(S)=S)CCCC SZRLKIKBPASKQH-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- MIHRVCSSMAGKNH-UHFFFAOYSA-N ethylcarbamodithioic acid Chemical compound CCNC(S)=S MIHRVCSSMAGKNH-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- HYVVJDQGXFXBRZ-UHFFFAOYSA-N metam Chemical compound CNC(S)=S HYVVJDQGXFXBRZ-UHFFFAOYSA-N 0.000 description 1
- WREDNSAXDZCLCP-UHFFFAOYSA-N methanedithioic acid Chemical compound SC=S WREDNSAXDZCLCP-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WEDQZAOZTZPJOU-UHFFFAOYSA-N octylcarbamodithioic acid Chemical compound CCCCCCCCNC(S)=S WEDQZAOZTZPJOU-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- KMKHWFHJIBBSBB-UHFFFAOYSA-N phenylsulfanylmethanedithioic acid Chemical compound SC(=S)SC1=CC=CC=C1 KMKHWFHJIBBSBB-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UCPWEJNQKVUTLV-UHFFFAOYSA-N propan-2-ylcarbamodithioic acid Chemical compound CC(C)NC(S)=S UCPWEJNQKVUTLV-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- OZLQPIXHRUVBEU-UHFFFAOYSA-K trisodium;2-hydroxy-3-[4-(2-hydroxy-3-sulfonatopropyl)piperazin-1-yl]propane-1-sulfonate;2-hydroxy-3-[4-(2-hydroxy-3-sulfopropyl)piperazin-1-yl]propane-1-sulfonate Chemical compound [Na+].[Na+].[Na+].OS(=O)(=O)CC(O)CN1CCN(CC(O)CS([O-])(=O)=O)CC1.[O-]S(=O)(=O)CC(O)CN1CCN(CC(O)CS([O-])(=O)=O)CC1 OZLQPIXHRUVBEU-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- This invention relates to a process for producing metal Patent F 2,986,498 Patented May .30, 1961 4 if tached either on the X or R groups, and may be provided,
- N-ethyl-N-fi-aminoethyl-aminoethane-sulfonic acid electrodeposits and more particularly to additives for electroplating baths which are capable of eliminating the adverse efiects of impurities in such baths upon the quality of the metal deposits produced by means of such baths.
- Impurities which adversely affect the qualities of metal electrodeposits include those which cause the 1 hardness of tap water as well as those contained in technically pure metal salts usually employed to make up the electroplating solution. The adverse effect of these impurities is particularly noticeable in electroplating processes for depositiing copper on metal objects, and
- drocarbon radicals may also have substituen'ts 'containiug Oxygen, sulfur or nitrogen atoms.
- electrodeposits produced thereby are bright and lustrous despite the fact that the bath contains impurities of the type described above, such as impurities which cause hardness, etc. Such bright deposits are ob tained over the entire effective range of current densities.
- these additives have the further advantage that they increase the ductility of the electrodeposits.
- the above-mentioned additives are entrained with the metal electroplates to a substantially lesser degree than the corresponding compounds vof the principal patent, which results in a much more economical consumption.
- the amounts in which the additives in accordance with our invention can be added to produce the desired eifect range from about-0.01 gn1./liter of bath to about 15 gm./ liter of bath, but the preferred amount is from 3 to 12 gnu/liter of bath.
- the precise amounts required vary from one additive to the other and are also dependent upon the type of brightening agent employed and the amount and kind of inorganic impurities present in the bath.
- objects can be electroplated in such baths at temperatures ranging from 20 C. to 60 C., and
- the use of the additives in accordance with our invention does not require any change in the composition of the electroplating baths commonly use, nor does it require any change in the conditions under which objects are usually electroplated, particularly with respect to the temperature of the plating bath and the current densities usually employed.
- the additives we use are soluble in the usual acid metal salt baths, and particularly in copper-plating baths containing the usual copper salts in an acid aqueous solution. The additives are not decomposed during the electroplating-process.
- additives for electroplating baths in accordance with our invention can be used in conjunction with any electroplating bath containing a brightening agent and in which the quality of the metal electrodeposits produced therefrom are adversely afiected by impurities of the type described, such as, for example, in zinc-, chromiurn-, precious metal-, and particularly copperplating baths which contain brightening agents, and in particular sulfonic acid brightening agents.
- Brightening agents usable for the process according to the above noted invention are listed in the following table:
- Example 11 When 1.5 gm./liter N,N,N,N' tetra n butyl 1,3- diaminopropanol-2-mono-sulfonic acid ester are added to an acid copper-plating bath containing 250 gm./liter technical-grade copper sulfate, 70 gm./liter concentrated sulfuric acid and 0.3 gm./liter N,N-diethyl-dithiocarbamic acid-ethylester-w-sodium sulfonate, as brightening agent, electroplating of sheet iron preplated in a cyanide bath is provided with a full bright copper electroplate. The best copper electroplates are obtained when the electroplating step is carried out at C.
- Example 111 sodium sulfonate, as brightening agents, and 1 gm./liter,
- ZQS-diarnino-benzene-1,4-disulfonic acid At temperatures between 20 and 45 C., objects may be electroplated at current densities up to 13 amp./dm. Without the addition of 2,5-diaminobenzene-1,4-disulfonic acid the copper electroplates are much less bright.
- Examples 1 V-XX V1 In the table some compositions for copper plating baths are listed.
- the copper baths contain 100-240 gmJliter CuSO .5H O, 20-120 gm./liter concentrated sulfuric acid and the following amounts of brightening agents according to the above noted list and the following amounts of sulfonic acid or sulfuric acid ester derivatives respectively of the diamino compounds free from carboxyl groups according to the above noted list:
- a process of producing bright metal electrodeposits said metal being selected from the group consisting of copper, Zinc, chromium and precious metals, from electroplating baths containing impurities found in hard water and in technical grade metal salts; and containing a brightening agent, the step which comprises adding to such electroplating baths 0.01 to -15 gm./liter of an amino compound free from carboxyl groups having the general structural formula wherein X is an organic radical selected from the group consisting of bivalent acyclic'hydrocarbon radicals, bivalent cyclic hydrocarbon radicals, and heterocyclic hydrocarbon radicals which include at least one of the nitrogen atoms, and R R R R and R are selected from the group consisting of hydrogen, substituted hydrocarbon radicals and unsubstituted hydrocarbon radicals, wherein at least one of the radicals selected from the group consisting of R R R R and X is substituted with a sulfonic acid group, X being free of said substituent when said substituent is on one of said radical
- step 4 which comprises adding to such electroplating baths 0.01 to 15 gm./liter of piperazine-N,N-bis-(Z-hydroxypropane-sulfonic acid) whereby said impurities are prevented from interfering with the production of bright copper electrodeposits.
- step 5 which comprises adding to such electroplating baths 0.01 to 15 gm./liter of piperazine-N,N-bis(2-hydroxypropane-sulfonic acid), whereby said impurities are prevented from interfering with the production of bright copper electrodeposits.
- step 6 which comprises adding to such electroplating baths 0.01 to 15 gut/liter of N,N,N'N'-tetra-n-butyl-1,3-diaminopropanol- 8 Z-mOno-suifuricacid ester, whereby said impurities are prevented from interfering with the production of bright copper electrodeposits.
- step 7 which comprises adding 0.01 to 15 gm.-/liter of N, N,N"N'- tetra-n-b'utyl-1,3-diaminopropanol-2-monosulfuric acid ester to such electroplating baths, whereby said impurities are prevented from interfering with the production .of bright copper electrodeposits.
- an acid copper electroplating bath comprising technical grade copper salts and hard tap water
- the improvement which comprises a component for rendering impurities in said bath harmless, comprising 0.01 to 15 gm./liter of an organic amino compound free from carboxyl groups having the general structural formula wherein X is an organic radical selectedfrom the group consisting of bivalent acyclic hydrocarbon radicais, bivalent cyclic hydrocarbon radicals and heterocyclic hydrocarbon radicals which include at least one of the nitrogen atoms, and R R R and R are radicals selected from the group consisting of hydrogen, substituted hydrocarbon radicals and unsubstituted hydrocarbon radicals, wherein at least one of the radicals selected from the group consisting of R R R R and X is substituted with a substituent selected from the group consisting of sulfonic and sulfuric acid ester groups, X being free of said substituent when said substituent is on one of said radicals selected from the group consisting of R R R and R whereby said impurities are prevented from interfering with the
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED17304A DE1000204B (de) | 1954-03-13 | 1954-03-13 | Verfahren zur Herstellung galvanischer Kupferueberzuege |
| DED24913A DE1030133B (de) | 1954-03-13 | 1957-02-13 | Verfahren zur Herstellung galvanischer Kupferueberzuege |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2986498A true US2986498A (en) | 1961-05-30 |
Family
ID=25970685
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US714687A Expired - Lifetime US2986498A (en) | 1954-03-13 | 1958-02-12 | Process for the production of metal electrodeposits |
| US735360A Expired - Lifetime US3030283A (en) | 1954-03-13 | 1958-05-15 | Process for the production of metal electrodeposits |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US735360A Expired - Lifetime US3030283A (en) | 1954-03-13 | 1958-05-15 | Process for the production of metal electrodeposits |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US2986498A (enrdf_load_stackoverflow) |
| BE (2) | BE563647A (enrdf_load_stackoverflow) |
| CH (2) | CH340395A (enrdf_load_stackoverflow) |
| DE (1) | DE1030133B (enrdf_load_stackoverflow) |
| FR (1) | FR1118019A (enrdf_load_stackoverflow) |
| GB (2) | GB807574A (enrdf_load_stackoverflow) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3787297A (en) * | 1971-10-26 | 1974-01-22 | Conversion Chem Corp | Zinc plating bath and method |
| NL7413010A (nl) * | 1973-11-07 | 1975-05-12 | Degussa | Galvanisch glansgoudbad met hoge afscheidings- snelheid. |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| CN104428452A (zh) * | 2012-05-25 | 2015-03-18 | 麦克德米德尖端有限公司 | 用于制备具有低氧含量的铜电沉积物的添加剂 |
| CN111465720A (zh) * | 2017-12-22 | 2020-07-28 | 安美特德国有限公司 | 提高包含铬合金最外层的基材的耐腐蚀性的方法 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE534101A (enrdf_load_stackoverflow) * | 1954-03-13 | |||
| DE1235101B (de) * | 1959-08-21 | 1967-02-23 | Langbein Pfanhauser Werke Ag | Elektrolyt mit Glanzzusatz zur galvanischen Abscheidung spiegelglaenzender, eingeebneter, duktiler Nickelniederschlaege |
| WO2025114220A1 (en) * | 2023-11-30 | 2025-06-05 | Basf Se | Non-acidic composition for copper electroplating comprising a defect reduction agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1118019A (fr) * | 1954-03-13 | 1956-05-30 | Dehydag | Procédé de préparation de revêtements métalliques galvaniques |
| US2837472A (en) * | 1953-09-19 | 1958-06-03 | Dehydag Gmbh | Brighteners for electroplating baths |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2355070A (en) * | 1937-07-03 | 1944-08-08 | Little Inc A | Electrolytic deposition of metal |
| GB503095A (en) * | 1937-10-04 | 1939-03-31 | Bruno Friedrich Schweig | Improvements in the production of electrodeposits of copper |
| US2195454A (en) * | 1939-01-07 | 1940-04-02 | Louis Weisberg Inc | Electrodeposition of copper |
| DE888493C (de) * | 1951-11-03 | 1953-09-03 | Hydrierwerke A G Deutsche | Verfahren zur Herstellung festhaftender und glaenzender galvanischer Kupferueberzuege |
-
0
- BE BE534101D patent/BE534101A/xx unknown
- BE BE563647D patent/BE563647A/xx unknown
-
1954
- 1954-12-28 CH CH340395D patent/CH340395A/de unknown
-
1955
- 1955-01-20 FR FR1118019D patent/FR1118019A/fr not_active Expired
- 1955-03-11 GB GB7161/55A patent/GB807574A/en not_active Expired
-
1957
- 1957-02-13 DE DED24913A patent/DE1030133B/de active Pending
-
1958
- 1958-01-07 CH CH5441958A patent/CH370612A/de unknown
- 1958-02-12 US US714687A patent/US2986498A/en not_active Expired - Lifetime
- 1958-02-12 GB GB4550/58A patent/GB884035A/en not_active Expired
- 1958-05-15 US US735360A patent/US3030283A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2837472A (en) * | 1953-09-19 | 1958-06-03 | Dehydag Gmbh | Brighteners for electroplating baths |
| US2849351A (en) * | 1953-09-19 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
| FR1118019A (fr) * | 1954-03-13 | 1956-05-30 | Dehydag | Procédé de préparation de revêtements métalliques galvaniques |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3787297A (en) * | 1971-10-26 | 1974-01-22 | Conversion Chem Corp | Zinc plating bath and method |
| NL7413010A (nl) * | 1973-11-07 | 1975-05-12 | Degussa | Galvanisch glansgoudbad met hoge afscheidings- snelheid. |
| US3929595A (en) * | 1973-11-07 | 1975-12-30 | Degussa | Electrolytic burnished gold bath with higher rate of deposition |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| CN104428452A (zh) * | 2012-05-25 | 2015-03-18 | 麦克德米德尖端有限公司 | 用于制备具有低氧含量的铜电沉积物的添加剂 |
| CN111465720A (zh) * | 2017-12-22 | 2020-07-28 | 安美特德国有限公司 | 提高包含铬合金最外层的基材的耐腐蚀性的方法 |
| US10961634B2 (en) * | 2017-12-22 | 2021-03-30 | Atotech Deutschland Gmbh | Method for increasing corrosion resistance of a substrate comprising an outermost chromium alloy layer |
| CN111465720B (zh) * | 2017-12-22 | 2023-08-22 | 安美特德国有限公司 | 提高包含铬合金最外层的基材的耐腐蚀性的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1118019A (fr) | 1956-05-30 |
| GB807574A (en) | 1959-01-21 |
| CH370612A (de) | 1963-07-15 |
| BE534101A (enrdf_load_stackoverflow) | |
| US3030283A (en) | 1962-04-17 |
| GB884035A (en) | 1961-12-06 |
| DE1030133B (de) | 1958-05-14 |
| CH340395A (de) | 1959-08-15 |
| BE563647A (enrdf_load_stackoverflow) |
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