Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
  • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
  • C07D295/21—Radicals derived from sulfur analogues of carbonic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D233/30—Oxygen or sulfur atoms
  • C07D233/42—Sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/08—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
• • 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

• organic sulfonic acids or their salts which contain at least one thiourea radical and at least one dithiocarbamic acid radical in the molecule, produce simultaneously excellent brightening and leveling eifects in acid metal electroplating baths, especially in copper electroplating baths.
• the employment of the agents according to the invention provides a substantial simplification of the baths with simultaneous improvement of the quality of the metal electroplates.
• These products possess excellent -full brightening and strong leveling properties, coupled with a temperature tolerance which is suificient tor all practical requirements, so that with the aid of these products the preparation and upkeep Of metal electroplating baths, especially of highsperformance bright copper electroplating baths, becomes substantial-1y simpler.
• the above-mentioned sulfonic acids can not only be employed in copper electroplating baths, in which they or their salts produce a particularly remarkable effect, but also to good advantage in electroplating baths which contain the salts of the metals zinc, lead, tin and cadmium or mixtures thereof.
• Another object is to provide a method and bath for electroplating wherein a single additive compound produces bright, level and non-porous electrodeposits of metals.
• the sulfonic acids or their salts which are employed in accordance with the present invention may be prepared in simple fashion by well known methods. In general, they are characterized by at least one dithiocarbamic acid group of the general formula in which R and R represent hydrogen or hydrocarbon radicals. Suitable such radicals are identical or different alkyl radicals which may possibly be substituted or, with inclusion of the nitrogen atom, may also together form a heterocyclic ring, such as a monpholine or piperazine ring, or also cycloalkyl radicals.
• the sul fonic acids according to the present invention "Ice are also characterized by at least one thiourea group of the general formula in which R and R represent hydrogen, alkyl radicals, cycloalkyl radicals, substituted or unsubstituted aryl radicals or also dithiocarbamic acid radicals attached to the nitrogen through an acyclic or cyclic intermediate mem her, as already described above.
• the sulfonic acids according to the present invention contain an alkyl sul-fonic acid group of the general formula in which R, is a low molecular alkyl radical with 1 to 4 carbon atoms. 7
• R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyiclic radicals wherein -R may be a tree valence; R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals; R is a lower alkyl radical; R is selected from the group consisting of hydrogen and aliphatic radicals .
• R and R may join to fiorm a heterocyclic ring; R is selected from the group consisting of aliphatic, dialkylamino, cycloaliphatic and heterocyclic radicals; Y is a member selected from the group consisting of :8 and X is selected from the group consisting of hydrogen and cation: n is a number at least 1.
• the R radical is 3 joined to an atom selected from the group consisting of nitrogen and sulfur atoms having free valences. As indicated by the brackets, the R radical may be joined at more than one point in the molecule, such as to the R radical when it represents a free valence, or to the R radical when it is a dialky'larnino radical with a free valence on the nitrogen. R is also being joined to both open sulfur valences in Formula IV It is to be understood that the R radical always carries the sulfonic acid or sulfonate group.
• 0.5 mol of phenyl mustard oil was added dropwise at 30-35 C. to a solution of 0.5 mol of diethylene triamine in 300 cc. of ethanol, and the mixture was stirred for an additional two hours. Thereafter, 1 mol of sodium hydroxide dissolved in 150 cc. of water was added, and then 1 mol of carbon dis-ulfide was added dropwise to the solution at 40 C. The mixture was then stirred for twenty minutes while increasing the temperature to 60 C., and thereafter 1 mol of molten propane suiltone was added dropwise. After a few hours of boiling under reflux, the mixture was evaporated in vacuo.
• a further example of the sulfionic acids according to the present invention is 4-thiohexahydrod,3,5-triazinyll-ethyldithiocarbamic acid propylester-w-sultoni'c acid
• the sodium salt of this sulfionic acid was obtained by condensation of the sodium salt of aminoethyldithiocarbarnic acid propylesterw-sulfonic acid with thiourea and [formaldehyde with good yields in the for-m of a yellowish powder which had no melting point.
• This compound was prepared in the following manner: 13.6 gm. of the inner salt of Z-aminoethyldithio'carbamic acid were dissolved in 100 cc. of water. The resulting solution was admixed with 4 gm. of sodium hydroxide dissolved in 50 ml. of water, 7.6 gm. of thiourea were added and after the latter had dissolved 17.2 gm. of 35% formaldehyde solution were added over a period of evaporated in vacuo. The residue thus obtained was stirred for forty-five minutes and was then allowed to stand overnight, after which the clear green solution was evaporated in vacuo. The resldue thus obtained was taken up in 200 cc.
• This product was prepared as follows: a solution of 73 gm. of l-(B-aminoethyl)-2-cimidazolinethione, which had been prepared from thiourea and .diethy-lene triamine according to United States Patent No. 2,613,212, in 500 cc. of ethanol was admixed with a solution of 20.2 gm. of sodium hydroxide in cc. of water, 38.3 gm. of carbon di-sulfide were added dl'OPtWElSC in a temperature range of 35-40 C. and then 6 1.5 gm. of molten propane sultone were added slowly over a .period of twenty-five minutes at 6570 C.
• sulfonic acids or their salts which may be employed in accordance with the present invention are those in which the dithiocarbamic acid group is connected with that portion of the molecule which contains the thiourea and the sulfonic acid radical through an ester bond.
• An example of such a substance is the reaction product of N,N' bis (diethylthiocarbamyl-mercaptomethyl)-thiourea with propane sultone, which has the following formula:
• the linkage between the dithiocarbamic acid radical and the thiourea radical, which in the case of the above compound (No. 4) is formed by a methylene group, may also be formed by other groups, such as by an ethylene or propylene group or by another hydrocarbon radical, which may also be substituted or interrupted by hetero atoms or may be closed into a heterocyclic ring including the two nitrogen atoms, such as a piperazine ring.
• alkyl sulfonic acid radicals are attached to the.
• suitable sulfonic acids also include the following compounds which comprise the gm. per liter of N,N,N',N-tetraethyl-1,3-diaminopropanel-2.
• a bath having this composition produces uniformly full bright and satisfactory level copper electroplates in a current density range of 0.3 to 8 amp/dm. and at a temperature tolerance of 10 to 38 C.
• the copper electroplates are ductile and free from pores. They completely level a 280-grain etched area with a thickness of 20,11. without further additives.
• Example 11 0.1 gm. per liter of compound No. 8 are added to an acid copper plating bath which contains 210 gm. per liter of copper sulfate, CuSO -5H O, 60 gm. per liter of sulfuric acid, 1 gm. per liter of the addition product of mols of ethylene oxide to 1 mol of a coconut fatty alcohol mixture and 0.02 gm. per liter of thioflavin.
• a bath of this composition produces ductile, pore-free, uniformly full bright and satisfactorily leveling copper electroplates in a current density range of 0.2 to 8 amp/dm. at a temperature tolerance of 10 to 38 C.
• the agents according to the present invention are added to the electroplating bath in amounts of 50 mg. to 5 gm. per liter, preferably in amounts of 100 to 500 mg. per liter of bath fluid.
• the employment of the additives does not require special measures; they are readily soluble in the acid metal salt baths in the required quantity and also .exhibit satisfactory stability during the operation of the electroplating bath. If necessary, they may also be employed in combination with other known electroplating chemicals.
• Example I 0.2 gm. per liter of compound No. 4 are added to an acid copper plating bath which contains 210 gm. per liter of copper sulfate, CuSO -5H O, 80 gm. per liter of sulfuric acid, 2 gm. per liter of the addition product of 18 mols of ethylene oxide to 1 mol of nonylphenol and 0.25
• Example II When the acid electroplating bath described in Example II is modified with 0.11 gm. per liter of compound No. 7 as the brightening and leveling agent, the same good results as described in Example H are obtained.
• Example IV 0.20 gm. per liter of compound No. 2 are added to an acid copper plating bath which contains 220 gm. per liter of copper sulfate, CuSO -5H O, 60 gm. per liter of sulfuric acid and 1 gm. per liter of the addition product of 18 mols of ethylene oxide to 1 mol of nonylphenol.
• the addition of a further'component is not'necessary.
• the copper electroplates obtained thereby are ductile, free from pores, have a uniform full brightness and a good leveling efliect in the current density range of 0.2 to 8 amp/din. and at a temperature tolerance of 10 to 38 C.
• a 250-grain etching is completely leveled by a cop, per deposit 201:. thick.
• Example V 0.10 gm. per liter of compound No. 3 are added to an acid copper plating bath which contains 210 gm. per liter of copper sulfate, CuSO -5H O, 60 gm. per liter of sulfuric acid and 1 gm. per liter of the addition product of 20 mols of ethylene oxide to 1 mol of a coconut fatty alcohol mixture.
• the addition of a further component is not necessary.
• Ductile, pore-free, uniformly full bright and satisfactorily leveling copper deposits are obtained in a current density range of 0.5 to 10 amp/dm. and rat a temperature tolerance of 10 to 38 C.
• a 280-grain etched area is completely leveled by a copper deposit of 20p thickness.
• Example V1 0.5 gm. per liter of compound No. 1 are added to an acid copper electroplating bath which contains 210 gm. per liter of copper sulfate, CuSO -5H O, and 60 gm. per liter of sulfuric acid.
• the addition of further assistants is not necessary because the bath having this simple composition already furnishes ductile, pore-free, uniformly tull bright and satisfactorily leveling copper electroplates (in a current density range of 0.5 to 8 amp/dm. at a temperature tolerance of 1-0 to 35 C.
• a ZZO-grain etched area is completely leveled by a copper deposit having a thickness of 20p. -A further advantage of this 'bath resides in that it can be operated without difiiculties with air.
• Example VII 0.4 gm. per liter of the compound No. 5 are added to an acid copper electroplating bath which contains 210 gm. per liter of copper sulfate, CuSO *5H O, and 60 gm. per liter of sulfuric acid. The addition of a further component is also unnecessary in this case. Ductile, pore-free, uniformly full bright and satisfactorily leveling copper electroplates are obtained in a current density range of 0.5 to 8 amp/dm. and at a temperature tolerance of 10 to 35 C. A 220-grain etched area is completely leveled by a copper deposit having a thickness of This bath can also be operated with air in an advantageous manner.
• Example VIII 0.15 gm. per liter of compound No. 5 is added to an acid zinc electroplating bath which contains 300 gm. per liter of zinc sulfate, 10 gm. per liter of aluminum sulfate
• R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyclic radicals wherein R may be a free valence
• R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals
• R is a lower alkyl radical
• R is selected from the group consisting of hydrogen and aliphatic radicals wherein R and R may join to form a heterocyclic ring
• R is selected from the group consisting of aliphatic, dia'lkylamino, cycloaliphatic and lheterocyclic radicals
• Y is a member selected from the group consisting of Q and X is selected from the group consisting of hydrogen and
• the bath is operated in a pH range between 3 and 5 and furnishes bright, ductile, very fine-grained zinc electrodeposits which adhere well to the iron surface in a current density range of 0.5 to 8 amp/dm. at a temperature tolerance of 15 to 30 C.
• a process for producing bright, smooth deposits of metals capable of being electrodeposited selected from the group consisting of copper, zinc, lead, tin and cadmium which comprises depositing the metal from a bath containing the metal to be deposited in the form of an aqueous solution of an inorganic salt thereof in the presence of an additive compound having a structural formula selected from the group consisting of:
• Y is a member selected from the group consisting of S and X is selected from the group consisting of hydrogen and cations; and n is a number at least :1; said R radical being joined to an atom selected from the group consisting of nitrogen and sulfur atoms having free valences; said additive compound being present in sufficient amount to eifect said brightening and smoothing.
• a process for producing bright, smooth deposits of metals capable of being electrodeposited selected from the group consisting of copper, zinc, lead, tin and cadmium which comprises depositing the metal from a bath containing the metal to be deposited in the form of an aqueous solution of an inorganic saltthereof in the presence of about 100 to 500 rug/l. of bath of an additive compound having a structural formula selected from th group consisting of:
• R and R are selected from the group consisting 'lower alkyl radical;
• R is selected from the group consisting of hydrogen and aliphatic radicals wherein R and R may join to form a heterocyclic ring;
• R is selected from the group consisting of aliphatic, dialkylamino, cycloaliphatic and heterocyclic radicals;
• Y is a member selected from the group consisting of :S and SR 4O X
• X is selected from the group consisting of hydrogen and cations; and
• n is a number at least 1; said R radical being joined to an atom selected from the group consisting of nitrogen and sulfur atoms having free valences; said additive compound being present in sufficient amount to effect said brightening and smoothing.
• a process for producing bright, smooth deposits of copper which comprises depositing said copper from a bath containing an aqueous solution of an inorganic salt of copper in the presence of an additive compound having a structural formula selected from the group conll 2 nitrogen and sulfur atoms having free valences; said additive compound being present in suflicient amount to efiect said brightening and smoothing.
• R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyclic radicals wherein R may be a free valence;
• R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals;
• R is a lower alkyl radical;
• R is selected from the group consisting of hydrogen and aliphatic radicals wherein R and R may join to form a heterocyclic ring;
• R is selected from the group consisting of aliphatic, dialkylamino, cycloaliphatic and heterocyclic radicals;
• Y is a member selected from .the group consisting of 8 and --SR SO X,,;
• X is selected from the group consisting of hydrogen and cations; and
• n is a number at least 1; said R radical being joined to an atom selected from the group consisting of nitrogen and sulfur atoms having free valences; said additive comp'ound
• R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyclic radicals wherein R may be a free valence; R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals; R is a lower alkyl radical; R is selected from the group consisting of hydrogen and aliphatic radicals wherein R and R may join to form a heterocyclic ring; R is selected from the group consisting of aliphatic, dialkylamino, cycloaliphatic and heterocyclic radicals; Y is a member selected from the group consisting of :8 and -S--R SO X X is selected from the group consisting of hydrogen and cations; and n is a number at least 1; said R radical being joined to an valence; R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyclic radicals wherein R may
• the bath of claim 18 wherein the additivecompound is: r 1 v wherein R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyclic radicals wherein R may be a free valence; R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals; R is a lower alkyl radical; R is selected from the group consisting of hydrogen and aliphatic radicals wherein R aud R may join to form a heterocyclic ring; R is selected from the group consisting of aliphatic, dialkylamino, cycloaliphatic and heterocyclic radicals;
• additive com- I Y is a member selected from the group consisting of Q and SR SO X X is selected from the group CH OH2 j I onr-on,
• An electroplating bath for producing bright, smooth electrodeposits of metals capable of being electrodeposited selected from the group consisting of copper, zinc, lead, tin and cadmium comprising an aqueous solution of an inorganic salt of the metal to be deposited and about mg. to 5 g./l. of bath of an additive compound having a structural formula selected from the group consisting of:
• An electroplating bath for producing bright, smooth electrodeposits of metals capable of being electrodeposited selected from the group consisting of copper, zinc, lead, tin and cadmium comprising an aqueous solution of an inorganic salt of the metal to be deposited and about to 500 mg./1. of bath of an additive compound having a structural formula selected from the group consisting of:
• R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocylic radicals wherein R may be a free valence;
• R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals;
• R; is a lower alkyl radical;
• R is selected from the group consisting of hydrogen and aliphatic radicals wherein R and R may join to form a heterocyclic ring;
• R is selected from the group consisting of aliphatitic, dialkylamino, cycloaliphatic and heterocyclic radicals;
• Y is a member selected from the group consisting of :8 and S-,R SO X,,;
• X is selected from the group consisting of hydrogen and cations; and
• n is a number at least 1; said R -radical being joined to an atom selected from the group consisting of nitrogen and sulfur atoms having free val
• An electroplating bath for producing bright, smooth electrodeposits of copper comprising an aqueous solution of an inorganic salt of copper and an additive compound having a structural formula selected from .the group consisting of:
• R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyclic radicals wherein R may be a free valence;
• R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals;
• R is a lower alkyl radical;
• R is selected from the group consisting of hydrogen and aliphatic radicals wherein R and R may join to form a heterocyclic ring;
• R is selected from the group consisting of aliphatic, dialkylamino, cycloaliphatic and heteroeyclic radicals;
• Y is a member selected from .the group consisting of :S and -S--'R ---S0 X X is selected from the group consisting of hydrogen and cat-ions; and
• n is a number at least 1, said R radical being joined to an atom selected from the group consisting of nitrogen and sulfur atoms having free valences;

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Citations (4)

• 0
  • NL NL134137D patent/NL134137C/xx active
  • NL NL274211D patent/NL274211A/xx unknown
• 1961
  • 1961-02-02 DE DED35328A patent/DE1146322B/de active Pending
  • 1961-12-16 CH CH1462561A patent/CH427447A/de unknown
  • 1961-12-28 GB GB46401/61A patent/GB928011A/en not_active Expired
• 1962
  • 1962-02-01 DK DK46962AA patent/DK103053C/da active
  • 1962-02-01 US US170522A patent/US3203878A/en not_active Expired - Lifetime
  • 1962-02-01 BE BE613365A patent/BE613365A/fr unknown

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