US2837472A - Brighteners for electroplating baths - Google Patents

Brighteners for electroplating baths Download PDF

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US2837472A
US2837472A US552699A US55269955A US2837472A US 2837472 A US2837472 A US 2837472A US 552699 A US552699 A US 552699A US 55269955 A US55269955 A US 55269955A US 2837472 A US2837472 A US 2837472A
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copper
structural formula
nickel
bath
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Gundel Wolfgang
Haas Hermann
Strauss Wennemar
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Dehydag Deutsche Hydrierwerke GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D277/58—Nitro radicals
    • 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
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/02—Slide fasteners

Definitions

  • Another object of the present invention is to provide brightening additives for electroplating baths which may advantageously be used as sole brightening additives or with other additives to produce bright and lustrous electrodeposits.
  • Still another object of this invention is to provide electroplating baths which will produce bright and lustrous electrodeposits which, in many instances, may be used for their intended purpose without further polishing or buffing.
  • Yet another object of this invention is to provide various methods for producing the above brighteners.
  • Z is a radical comprising a carbon atom directly attached to two atoms at least one of which is a sulfur atom and the other is selected from the group consisting eners in electroplating baths according to the present invention fall into four basic groups:
  • Sulfonic acid derivatives of this type are, tor example, the products of a reaction between 2-mercaptothiazole-S-alkylethers and sultones, such as the reaction product of 2-mercaptobenzothiazole-S-methylether and propanesultone, and also derivatives of dithiocarbarnic acid-S-alkylesters which have an alkylsulfonic acid group attached to the nitrogen atom.
  • Compounds of this group may be produced by first reacting a primary amine with a sultone to form the corresponding amino-sulfonic acids,
  • dithiocarbamic acid salts thereafter reacting the amino-sulfonic acids with carbon disulfide in an alkaline medium to form dithiocarbamic acid salts, andfinally alkylating the dithiocarbamic acid salts according to known methods, for example by reactmg them with dimethylsulfate.
  • halogenated alkanesulfonic acids may also be used.
  • the dithiocarbamic acid derivatives obtained in this manner have the general structural formula o-Na'-soin u s I I wherein R, R' and R" are hydrocarbon radicals of the character described.
  • R is a hydrogen atom or an aliphatic, cycloaliphatic, or aromatic-aliphatic radical
  • R and R are bivalent aliphatic, cycloaliphatic or aromatic radicals.
  • the dithiocarbamic compounds of this group may readily be produced by first reacting salts of aminoalkane sulfonic acids which have at least one hydrogen atom attached to the nitrogen atom with carbon disulfide in the presence of equimolar amounts of a.
  • a strong base such as sodium hydroxide
  • salts of dithiocarbamic acid-N-alkylsulfonic acids are formed, and thereafter reacting the dithiocarbamic acid-N-alkylsulfonic acid salt with a sulfonating agent, for example with an aliphatic, cycloaliphatic or aromatic sultone.
  • the four groups of sulfonic acid derivatives set forth above may be used in conjunction with all types of electroplating baths, such as in baths for electrodepositing copper, nickel, zinc, silver, cadmium, bronze or brass. They produce very bright, firmly adhering and ductile metal deposits.
  • the brighteners can be used alone or together with already known brighteners, smoothing agents, antiporosity agents, wetting agents or salts which increase the conductivity of the electroplating bath.
  • the concentration of the brightening agents in accordance with the invention in the electroplating bath may range from 0.1 to gm. per liter of bath and the optimum current densities may be from 0.5 to 12 arnp./drn. at a bath temperature below 60 C. Since the brightening agents disclosed herein are, for all practical purposes, not consumed during the electroplating process, baths modified therewith remain operative for long periods of time.
  • Example I 1 gm. dithiocarbamic acid-S-methylester-N-ethyl-N- butyl-w-sodium sulfonate having the general structural formula
  • Example 11 1 gm. dithiocarbamic acid-S-ethylester-N-butyl-N- propyl-w-sodium sulfonate having the structural formula was added to each liter of the aqueous acid copper sulfate solution described in Example I.
  • Sheet iron objects provided. with a copper base-coat and electroplated in this bath, under the temperature and current density conditions described in the preceding example, were provided with very bright and well adhering copper deposits having a high ductility.
  • Example III 1 to 2 gm. of dithiocarbamic acid-S-methylester-N- 4. butyl-N-butyl-w-sodium sulfonate having the structural formula S GiHs C-N(GHz)4-SOgNt1 HaC-S were added to each liter of an aqueous nickel electroplating solution containing 60 gm./liter nickel chloride, 220 gm./liter nickel sulfate and 3S gn1./liter boric acid. iron objects were then electroplated in the modified bath at room temperature and at current densities from 1 to 10 amp/(1m. The objects were provided with firmly adhering, very bright nickel electrodeposits which required no polishing or buffing subsequent to rinsing.
  • Example IV 1 gm. dithiocarbamic acid-S-ethylester-N-butyl-N- propyl-w-sodium sulfonate having the structural formula shown in Example 11, was added to each liter of an aqueous zinc plating solution containing 260 gm./liter zinc sulfate and l gm./liter glacial acetic acid. Thereafter, sheet steel objects were electroplated in this modified bath at room temperature and a current density from 4 to 9 amp./drn. The objects were provided with a verybright zinc electroplate which required no buffing
  • Example V 3 gm. 2-amino-5-methylthiazole N-propane-w-sodium sulfonate having the structural formula W H Hag /O-hI-(OE);-S0:Na
  • Example II Example II
  • sheet steel objects which had previously been provided with a copper base-coating in an alkaline copper cyanide bath, were electroplated in the above modified bath at room temperature and a current density range of 2 to 8 amp./drn.
  • the objects were provided with a very bright firmly adhering copper electrodeposit which required no polishing or bufiing subsequent to rinsing.
  • Example VI 2 gm. of thiourea-N-phenylt-sodium sulfonate were added to each liter of the acid aqueous nickel-plating solution described in Example III. Iron objects electro plated in this modified bath at room temperature and a current density range of 1 to 10 amp./dm. were provided with very bright, firmly adhering nickel electrodeposits which required no bufling or polishing subsequent to rinsing.
  • Example VII 1 to 2 gm. of N-butyl-dithiocarbamic acid-NS-bispropane-w-sodium sulfonate having the structural formula I S ⁇ C4H9 were added to each liter of the aqueous acid nickel electroplating solution described in Example HI. Iron objects electroplated in this modified bath at room temperature and current densities between 1 and 10 ampJdm. were provided with very bright, firmly adhering, nonporous nickel electrodeposits.
  • Z is a radical comprising a carbon atom directly attached to a sulfur atom, to an atom selected from the group consisting of sulfur, oxygen and nitrogen atoms and to the nitrogen atom of the group
  • R is a bivalent organic radical selected from the group consisting of aliphatic and aromatic radicals
  • R is selected from the group consisting of hydrogen and aliphatic radicals, said organic compound being dissolved in said bath in suflicient quantity to produce bright metal-plating deposits therefrom.
  • An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an aqueous acid solution of an inorganic salt of the metal to be electrodeposited and 0.01 to 20 grams per liter of a compound selected from the group consisting of organic sulfonic acids having the structural formula and their salts,-Wherein X is selected from the group consisting of oxygen, nitrogen and sulfur atoms, R is selected from the group consisting of bivalent aliphatic and aromatic radicals, R is selected from the group consisting of hydrogen and aliphatic radicals, and R is selected from the group consisting of hydrogen, alkyl and alkylsulfonic radicals.
  • An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an aqueous acid solution of an inorganic salt of the metal to be electrodeposited and 0.01 to 20 grams per liter of a compound having the structural formula 5.
  • An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an aqueous acid solution of an inorganic salt of the metal to be electrodeposited and '6 0.01 to 20 grams per liter of a compound having the structural formula HaN 6.
  • An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an aqueous acid solution of an inorganic salt of the metal to be electrodeposited and 0.01 to 20 grams per liter of a compound having the structural formula ⁇ C-N
  • An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an aqueous acid solution of an inorganic salt of the metal to he electrodeposited and 0.01 to 20 grams per liter of a compound having the structural formula C-N-(OHs) 4-3 0 aNa CHt-S 8.
  • An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an aqueous acid solution of an inorganic salt of the metal to be electrodeposited and 0.01 to 20 grams per liter of a compound having the structural formula S C4H9 CN(O 2)t aN 02 5- 9.
  • An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an aqueous acid solution of an inorganic salt of the metal to be electrodeposited and 0.01 to 20 grams per liter of a compound having the structural formula C-N-(OHgh-SOaNa 0113-8 10.
  • a brightener selected from the group consisting of organic sul
  • R is selected from .the,gr01 1p consisting of lbivalentaliphatic and aromatic radicals, R is selected from the group consisting of hydrogen and aliphatic radicals, and "R” is selected from the group consisting "of hydrogen, alkyl and alkylsulfonic radicals.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Paints Or Removers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electroplating Methods And Accessories (AREA)

Description

United States i BRIGHTENERS FOR ELECTROPLATING BATES Wolfgang Gnndel, Dusseldorf-Oberkassel, and Herman Haas and Wennemar Strauss, Dusseldorf-Holthausen, Germany, assignors to Dehydag, Deutsche Hydrierwerke G. m. b. ll-L, Dusseldorf, Germany, a corporation of Germany No Drawing. Application December 13, 1955 Serial No. 552,699
Ciaims priority, application Germany December 13, 1954 14 Claims. (Cl. 204-49) provement in the characteristics of the electrodeposits produced from baths modified therewith, these brighteners individually have not been suflicient to produce commercially desirable electrodeposits and had to be used with another and sometimes with even two or more supplemental brighteners to achieve the desired brightening effect.
It is an object of the present invention to provide electroplating compositions of improved character.
Another object of the present invention is to provide brightening additives for electroplating baths which may advantageously be used as sole brightening additives or with other additives to produce bright and lustrous electrodeposits.
Still another object of this invention is to provide electroplating baths which will produce bright and lustrous electrodeposits which, in many instances, may be used for their intended purpose without further polishing or buffing. V I
Yet another object of this invention is to provide various methods for producing the above brighteners.
Still further objects and advantages will become apparant as the description of the invention proceeds.
We have found that bright, highly lustrous and welladhering electrodeposits can be obtained by modifying electroplating baths, containing the metal to be deposited primarily in the form of an acid solution of an inorganic salt of the metal, with organic sulfonic acids or their salts having the general structural formula.
wherein Z is a radical comprising a carbon atom directly attached to two atoms at least one of which is a sulfur atom and the other is selected from the group consisting eners in electroplating baths according to the present invention fall into four basic groups:
(a) Compounds having the general structural formula S\ I CNRS 03H S v or their salts. Compounds of this type are, for exam ple, the reaction products of ,2 aminothiazoles with sultones, such as the product of a reaction between 2 amino- 4-methylthiazole or 2-amino-6-methylbenzothiazole and propanesultone or butanesultone, and also thiourea-N- phenylsulfonic acids and their derivatives, such as thiourea-N-pheny1-4-sulfonic acid.
(b) Compounds having the structural formula .S p or their salts. Sulfonic acid derivatives of this type are, tor example, the products of a reaction between 2-mercaptothiazole-S-alkylethers and sultones, such as the reaction product of 2-mercaptobenzothiazole-S-methylether and propanesultone, and also derivatives of dithiocarbarnic acid-S-alkylesters which have an alkylsulfonic acid group attached to the nitrogen atom. Compounds of this group may be produced by first reacting a primary amine with a sultone to form the corresponding amino-sulfonic acids,
thereafter reacting the amino-sulfonic acids with carbon disulfide in an alkaline medium to form dithiocarbamic acid salts, andfinally alkylating the dithiocarbamic acid salts according to known methods, for example by reactmg them with dimethylsulfate. In place of the sultones, halogenated alkanesulfonic acids may also be used. The dithiocarbamic acid derivatives obtained in this manner have the general structural formula o-Na'-soin u s I I wherein R, R' and R" are hydrocarbon radicals of the character described.
(c) Compounds having the general structural formulas or their salts. Compounds of this type are, for example,
the products of a reaction between 2-oxythiazoles and sultones.
Pa tented June 3, 1958 or their salts, wherein R is a hydrogen atom or an aliphatic, cycloaliphatic, or aromatic-aliphatic radical, R and R are bivalent aliphatic, cycloaliphatic or aromatic radicals. The dithiocarbamic compounds of this group may readily be produced by first reacting salts of aminoalkane sulfonic acids which have at least one hydrogen atom attached to the nitrogen atom with carbon disulfide in the presence of equimolar amounts of a. strong base, such as sodium hydroxide, whereby salts of dithiocarbamic acid-N-alkylsulfonic acids are formed, and thereafter reacting the dithiocarbamic acid-N-alkylsulfonic acid salt with a sulfonating agent, for example with an aliphatic, cycloaliphatic or aromatic sultone.
The four groups of sulfonic acid derivatives set forth above may be used in conjunction with all types of electroplating baths, such as in baths for electrodepositing copper, nickel, zinc, silver, cadmium, bronze or brass. They produce very bright, firmly adhering and ductile metal deposits. The brighteners can be used alone or together with already known brighteners, smoothing agents, antiporosity agents, wetting agents or salts which increase the conductivity of the electroplating bath.
The concentration of the brightening agents in accordance with the invention in the electroplating bath may range from 0.1 to gm. per liter of bath and the optimum current densities may be from 0.5 to 12 arnp./drn. at a bath temperature below 60 C. Since the brightening agents disclosed herein are, for all practical purposes, not consumed during the electroplating process, baths modified therewith remain operative for long periods of time.
The following examples will further illustrate the present invention and enable others skilled in the art to understand the invention more completely. It is understood, however, that we do not intend to limit the invention to the particular examples given below.
Example I 1 gm. dithiocarbamic acid-S-methylester-N-ethyl-N- butyl-w-sodium sulfonate having the general structural formula Example 11 1 gm. dithiocarbamic acid-S-ethylester-N-butyl-N- propyl-w-sodium sulfonate having the structural formula was added to each liter of the aqueous acid copper sulfate solution described in Example I. Sheet iron objects provided. with a copper base-coat and electroplated in this bath, under the temperature and current density conditions described in the preceding example, were provided with very bright and well adhering copper deposits having a high ductility.
Example III 1 to 2 gm. of dithiocarbamic acid-S-methylester-N- 4. butyl-N-butyl-w-sodium sulfonate having the structural formula S GiHs C-N(GHz)4-SOgNt1 HaC-S were added to each liter of an aqueous nickel electroplating solution containing 60 gm./liter nickel chloride, 220 gm./liter nickel sulfate and 3S gn1./liter boric acid. iron objects were then electroplated in the modified bath at room temperature and at current densities from 1 to 10 amp/(1m. The objects were provided with firmly adhering, very bright nickel electrodeposits which required no polishing or buffing subsequent to rinsing.
Example IV 1 gm. dithiocarbamic acid-S-ethylester-N-butyl-N- propyl-w-sodium sulfonate having the structural formula shown in Example 11, was added to each liter of an aqueous zinc plating solution containing 260 gm./liter zinc sulfate and l gm./liter glacial acetic acid. Thereafter, sheet steel objects were electroplated in this modified bath at room temperature and a current density from 4 to 9 amp./drn. The objects were provided with a verybright zinc electroplate which required no buffing Example V 3 gm. 2-amino-5-methylthiazole N-propane-w-sodium sulfonate having the structural formula W H Hag /O-hI-(OE);-S0:Na
were added to each liter of the aqueous acid copper plating solution described in Example I. Thereafter, sheet steel objects which had previously been provided with a copper base-coating in an alkaline copper cyanide bath, were electroplated in the above modified bath at room temperature and a current density range of 2 to 8 amp./drn. The objects were provided with a very bright firmly adhering copper electrodeposit which required no polishing or bufiing subsequent to rinsing.
Example VI 2 gm. of thiourea-N-phenylt-sodium sulfonate were added to each liter of the acid aqueous nickel-plating solution described in Example III. Iron objects electro plated in this modified bath at room temperature and a current density range of 1 to 10 amp./dm. were provided with very bright, firmly adhering nickel electrodeposits which required no bufling or polishing subsequent to rinsing.
Example VII 1 to 2 gm. of N-butyl-dithiocarbamic acid-NS-bispropane-w-sodium sulfonate having the structural formula I S\ C4H9 were added to each liter of the aqueous acid nickel electroplating solution described in Example HI. Iron objects electroplated in this modified bath at room temperature and current densities between 1 and 10 ampJdm. were provided with very bright, firmly adhering, nonporous nickel electrodeposits.
While we have disclosed certain specific embodiments of our invention, it will be obvious to persons skilled in the art that various changes and modifications can be and their salts, wherein Z is a radical comprising a carbon atom directly attached to a sulfur atom, to an atom selected from the group consisting of sulfur, oxygen and nitrogen atoms and to the nitrogen atom of the group, R is a bivalent organic radical selected from the group consisting of aliphatic and aromatic radicals, and R is selected from the group consisting of hydrogen and aliphatic radicals, said organic compound being dissolved in said bath in suflicient quantity to produce bright metal-plating deposits therefrom.
2. An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc, comprising an aqueous acid solution of an inorganic salt of the metal to be electrodeposited and 0.01 to 20 grams per liter of a compound selected from the group consisting of organic sulfonic acids having the structural formula and their salts,-Wherein X is selected from the group consisting of oxygen, nitrogen and sulfur atoms, R is selected from the group consisting of bivalent aliphatic and aromatic radicals, R is selected from the group consisting of hydrogen and aliphatic radicals, and R is selected from the group consisting of hydrogen, alkyl and alkylsulfonic radicals.
4. An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc, comprising an aqueous acid solution of an inorganic salt of the metal to be electrodeposited and 0.01 to 20 grams per liter of a compound having the structural formula 5. An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc, comprising an aqueous acid solution of an inorganic salt of the metal to be electrodeposited and '6 0.01 to 20 grams per liter of a compound having the structural formula HaN 6. An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc, comprising an aqueous acid solution of an inorganic salt of the metal to be electrodeposited and 0.01 to 20 grams per liter of a compound having the structural formula \C-N|'(CH2) a-S OaNa NaSOs'-(CHz)3s 7. An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc, comprising an aqueous acid solution of an inorganic salt of the metal to he electrodeposited and 0.01 to 20 grams per liter of a compound having the structural formula C-N-(OHs) 4-3 0 aNa CHt-S 8. An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc, comprising an aqueous acid solution of an inorganic salt of the metal to be electrodeposited and 0.01 to 20 grams per liter of a compound having the structural formula S C4H9 CN(O 2)t aN 02 5- 9. An electroplating bath for producing electrodeposits of metals selected from the group consisting of copper, nickel and zinc, comprising an aqueous acid solution of an inorganic salt of the metal to be electrodeposited and 0.01 to 20 grams per liter of a compound having the structural formula C-N-(OHgh-SOaNa 0113-8 10. The process of producing bright and lustrous electrodeposits of metals selected from the group consisting of copper, nickel and zinc, which comprises electrodepositing the metal from a bath containing said metal principally in the form of an acid "aqueous solution of an inorganic salt of the metal in the presence of a brightener selected from the group consisting of organic sulfonic acid compounds having the general structural formula IRI Z-N-R-SOaH and Z=N-RSO H and their salts, wherein Z is a radical comprising a carbon atom directly attached to a sulfur atom, to an atom selected from the group consisting of sulfur, oxygen and nitrogen atoms, and to the nitrogen atom of the group, R is a bivalent organic radical selected from the group consisting of aliphatic and aromatic radicals and R is selected from the group consisting of hydrogen and aliphatic radicals, said organic compound being dissolved in said bath in sufficient quantity to produce bright metal-plating deposits therefrom.
11, The process of producing bright and lustrous elech-geavm-a group consisting of organic sulfonic :acids -having the structural formula o lsa-sosn -X and their salts, wherein R is a.bivalent aliphatic radical, R is an aliphatic radical and X is selected from the group consisting ofsulfur, oxygen and nitrogen.
12. The process of producinghrightiandtlustrous electrodeposits of metals selected .from.the .group consisting of copper, .nickel .and .zinc, which comprises .electrodepositing the metal from .a hath remaining said ;metal principally in theform .of an ..acid agueous ESOIIltiOH ,of an inorganic salt .of .the metal ;in .the,pr.esence of 0.01 to 20 grams per liter of a brightener selectedtfrom the group consisting of sulfonic acids having the structural formula and their salts, wherein .X .is :selected from .the group consisting of oxygen, nitrogen -and. sulfur, R ,is selected from .the,gr01 1p consisting of lbivalentaliphatic and aromatic radicals, R is selected from the group consisting of hydrogen and aliphatic radicals, and "R" is selected from the group consisting "of hydrogen, alkyl and alkylsulfonic radicals.
21.3. electroplating ;bat.h "for producing ffilBCtIQdC- posits of metals selectedfrom-the group consisting of copper, nickel and zinc, said hath comprisingz'anwacid :EIQIRGHSJSOlUfiOH.OfJflIl inorganic salt of .the metal to be deposile'dtand ta compound selected .from the group-teensistinggof-organic sulfonic acids having the structural formulas and .ofisubstituted-and unsubstituted sulfur, oxygen and nitrogen atoms, R is abivalent organic radical selectedffrorn the I group consisting of aliphatic and aromatic radicals,
andrRis selected from the group consisting of hydrogen and-aliphatic radicals, said organic ,compoundheing dissolved in said bath in sufiicientquantity to produce bright metakplating deposits therefrom.
.14. The electroplating bath of claim 13, wherein the substituted X and Y atoms of the brightenercompound are joined to form a heterocyclic compound.
References Cited inthefile of this patent UNITED STATES PATENTS Brown Aug. 4, 1953 Pierce Dec. 22, 1953

Claims (1)

1. AN ELECTROPLATING BATH FOR PRODUCING ELECTRODEPOSITS OF METALS SELECTED FROM THE GROUP CONSISTING OF COPPER, NICKLE AND ZINC, COMPRISING AND ACID AQUEOUS SOLUTION OF AN INORGANIC SALT OF THE METAL TO BE DEPOSITED AND A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ORGANIC SULFONIC ACIDS HAVING THE STRUCTURAL FORMULAS
US552699A 1953-09-19 1955-12-13 Brighteners for electroplating baths Expired - Lifetime US2837472A (en)

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DE327298X 1953-09-19
DED19318A DE1207177B (en) 1953-09-19 1954-12-13 Process for the production of shiny galvanic metal coatings
DE2907786X 1955-01-05

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2986498A (en) * 1954-03-13 1961-05-30 Dehydag Gmbh Process for the production of metal electrodeposits
US3017333A (en) * 1959-04-06 1962-01-16 Mcgean Chem Co Inc Self-leveling bright nickel plating bath and process
US3051634A (en) * 1957-11-30 1962-08-28 Dehydag Gmbh Baths for the production of copper electroplates
US3075899A (en) * 1958-04-26 1963-01-29 Dehydag Gmbh Baths for the production of metal electroplates
US3203878A (en) * 1961-02-02 1965-08-31 Dehydag Deutsche Hydriewerke G Acid metal electroplating bath containing an organic sulfonic acid-thioureadithiocarbamic acid reaction product
US3276979A (en) * 1961-08-31 1966-10-04 Dehydag Gmbh Baths and processes for the production of metal electroplates
US3322657A (en) * 1964-04-28 1967-05-30 Langbein Pfanhauser Werke Ag Electrodeposition of bright copper
US3787297A (en) * 1971-10-26 1974-01-22 Conversion Chem Corp Zinc plating bath and method
US3876513A (en) * 1972-06-26 1975-04-08 Oxy Metal Finishing Corp Electrodeposition of bright cobalt plate
US4376685A (en) * 1981-06-24 1983-03-15 M&T Chemicals Inc. Acid copper electroplating baths containing brightening and leveling additives
US4549942A (en) * 1981-07-06 1985-10-29 Omi International Corporation Process for electrodepositing composite nickel layers
US4786746A (en) * 1987-09-18 1988-11-22 Pennsylvania Research Corporation Copper electroplating solutions and methods of making and using them
US4948474A (en) * 1987-09-18 1990-08-14 Pennsylvania Research Corporation Copper electroplating solutions and methods
US20120015911A1 (en) * 2004-12-22 2012-01-19 Bellus Health Inc. Method and compositions for treating amyloid-related diseases
DE202015003382U1 (en) 2014-05-09 2015-06-16 Dr. Hesse GmbH & Cie. KG Electrolytic deposition of copper from water-based electrolytes
US9499480B2 (en) 2006-10-12 2016-11-22 Bhi Limited Partnership Methods, compounds, compositions and vehicles for delivering 3-amino-1-propanesulfonic acid
CN111910222A (en) * 2020-08-21 2020-11-10 九江德福科技股份有限公司 Electrolytic copper foil additive with brightening and leveling functions and application thereof

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE534701A (en) * 1954-03-22
BE565994A (en) * 1957-04-16
US3084163A (en) * 1958-04-29 1963-04-02 Dehydag Gmbh Heterocyclic thioalkane sulfonic acids and methods for their production
DE1155432B (en) * 1960-02-27 1963-10-10 Dehydag Gmbh Process for the preparation of thiourea pellets
US3165456A (en) * 1960-11-21 1965-01-12 Minnesota Mining & Mfg Developer
US3180791A (en) * 1960-12-28 1965-04-27 Montedison Spa Method of controlling fungi with organic sulfur ester compounds
US3156717A (en) * 1960-12-28 1964-11-10 Montedison Spa Organic sulfur compounds having fungicidal activity
DE1177142B (en) * 1961-07-08 1964-09-03 Dehydag Gmbh Process for the preparation of dithiocarbamic acid ester derivatives containing sulfonic acid groups
NL281922A (en) * 1961-08-10
US3151123A (en) * 1962-06-19 1964-09-29 Keystone Chemurgic Corp Acid-soluble chlorophyllins and their production
DE1180140B (en) * 1962-07-20 1964-10-22 Dehydag Gmbh Process for the separation of fine-grained deposits in the refining and reduction electrolysis of nickel, zinc, silver, tin, lead and especially copper
US3414493A (en) * 1965-10-19 1968-12-03 Lea Ronal Inc Electrodeposition of copper
SE322956B (en) * 1966-08-20 1970-04-20 Schering Ag
US3956079A (en) * 1972-12-14 1976-05-11 M & T Chemicals Inc. Electrodeposition of copper
US3966565A (en) * 1972-12-14 1976-06-29 M & T Chemicals Inc. Electrodeposition of copper
US3956078A (en) * 1972-12-14 1976-05-11 M & T Chemicals Inc. Electrodeposition of copper
US3956120A (en) * 1972-12-14 1976-05-11 M & T Chemicals Inc. Electrodeposition of copper
US3940320A (en) * 1972-12-14 1976-02-24 M & T Chemicals Inc. Electrodeposition of copper
US3956084A (en) * 1972-12-14 1976-05-11 M & T Chemicals Inc. Electrodeposition of copper
US4036710A (en) * 1974-11-21 1977-07-19 M & T Chemicals Inc. Electrodeposition of copper
US4014760A (en) * 1974-11-21 1977-03-29 M & T Chemicals Inc. Electrodeposition of copper
US4036711A (en) * 1975-12-18 1977-07-19 M & T Chemicals Inc. Electrodeposition of copper
US4134803A (en) * 1977-12-21 1979-01-16 R. O. Hull & Company, Inc. Nitrogen and sulfur compositions and acid copper plating baths
GB2109815B (en) * 1981-11-18 1985-09-04 Ibm Electrodepositing chromium
US5656148A (en) * 1995-03-02 1997-08-12 Atotech Usa, Inc. High current density zinc chloride electrogalvanizing process and composition
CN103422079B (en) * 2012-05-22 2016-04-13 比亚迪股份有限公司 A kind of chemical bronze plating liquid and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2647866A (en) * 1950-07-17 1953-08-04 Udylite Corp Electroplating of nickel
US2663684A (en) * 1952-06-02 1953-12-22 Houdaille Hershey Corp Method of and composition for plating copper

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1972961A (en) * 1931-05-26 1934-09-11 Du Pont Disinfectant
FR753080A (en) * 1932-11-02 1933-10-06 Manufacturing process for whitening, wetting, spumescent, dispersing and impregnating products
US2127375A (en) * 1935-07-17 1938-08-16 Du Pont Esters of dithiocarbamic acids
US2313871A (en) * 1938-09-15 1943-03-16 Du Pont Polythiourea
US2389181A (en) * 1941-05-15 1945-11-20 Udylite Corp Electrodeposition of metals
US2424887A (en) * 1941-10-11 1947-07-29 Houdaille Hershey Corp Method and electrolyte for the electrodeposition of metals
GB628397A (en) * 1945-10-05 1949-08-29 Goodrich Co B F Improvements in or relating to beta-dithiocarbamyl carboxylic compounds and method of preparing same
US2491772A (en) * 1945-12-29 1949-12-20 Standard Oil Dev Co Extreme pressure lubricants
US2648627A (en) * 1950-05-24 1953-08-11 Wagner Brothers Inc Bright nickel plating composition and process
US2673839A (en) * 1951-04-28 1954-03-30 Standard Oil Dev Co Lubricating oil composition
DE888493C (en) * 1951-11-03 1953-09-03 Hydrierwerke A G Deutsche Process for the production of firmly adhering and shiny galvanic copper coatings
DE924489C (en) * 1953-04-28 1955-03-03 Degussa Bath for the galvanic deposition of metals

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2647866A (en) * 1950-07-17 1953-08-04 Udylite Corp Electroplating of nickel
US2663684A (en) * 1952-06-02 1953-12-22 Houdaille Hershey Corp Method of and composition for plating copper

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2986498A (en) * 1954-03-13 1961-05-30 Dehydag Gmbh Process for the production of metal electrodeposits
US3030283A (en) * 1954-03-13 1962-04-17 Dehydag Gmbh Process for the production of metal electrodeposits
US3051634A (en) * 1957-11-30 1962-08-28 Dehydag Gmbh Baths for the production of copper electroplates
US3075899A (en) * 1958-04-26 1963-01-29 Dehydag Gmbh Baths for the production of metal electroplates
US3017333A (en) * 1959-04-06 1962-01-16 Mcgean Chem Co Inc Self-leveling bright nickel plating bath and process
US3203878A (en) * 1961-02-02 1965-08-31 Dehydag Deutsche Hydriewerke G Acid metal electroplating bath containing an organic sulfonic acid-thioureadithiocarbamic acid reaction product
US3276979A (en) * 1961-08-31 1966-10-04 Dehydag Gmbh Baths and processes for the production of metal electroplates
US3322657A (en) * 1964-04-28 1967-05-30 Langbein Pfanhauser Werke Ag Electrodeposition of bright copper
US3787297A (en) * 1971-10-26 1974-01-22 Conversion Chem Corp Zinc plating bath and method
US3876513A (en) * 1972-06-26 1975-04-08 Oxy Metal Finishing Corp Electrodeposition of bright cobalt plate
US4376685A (en) * 1981-06-24 1983-03-15 M&T Chemicals Inc. Acid copper electroplating baths containing brightening and leveling additives
US4549942A (en) * 1981-07-06 1985-10-29 Omi International Corporation Process for electrodepositing composite nickel layers
US4786746A (en) * 1987-09-18 1988-11-22 Pennsylvania Research Corporation Copper electroplating solutions and methods of making and using them
US4948474A (en) * 1987-09-18 1990-08-14 Pennsylvania Research Corporation Copper electroplating solutions and methods
US20120015911A1 (en) * 2004-12-22 2012-01-19 Bellus Health Inc. Method and compositions for treating amyloid-related diseases
US8835654B2 (en) * 2004-12-22 2014-09-16 Bhi Limited Partnership Method and compositions for treating amyloid-related diseases
US9499480B2 (en) 2006-10-12 2016-11-22 Bhi Limited Partnership Methods, compounds, compositions and vehicles for delivering 3-amino-1-propanesulfonic acid
US10238611B2 (en) 2006-10-12 2019-03-26 Bellus Health Inc. Methods, compounds, compositions and vehicles for delivering 3-amino-1-propanesulfonic acid
US10857109B2 (en) 2006-10-12 2020-12-08 Bellus Health, Inc. Methods, compounds, compositions and vehicles for delivering 3-amino-1-propanesulfonic acid
US11020360B2 (en) 2006-10-12 2021-06-01 Bellus Health Inc. Methods, compounds, compositions and vehicles for delivering 3-amino-1-propanesulfonic acid
DE202015003382U1 (en) 2014-05-09 2015-06-16 Dr. Hesse GmbH & Cie. KG Electrolytic deposition of copper from water-based electrolytes
DE102014208733A1 (en) 2014-05-09 2015-11-12 Dr. Hesse Gmbh & Cie Kg Process for the electrolytic deposition of copper from water-based electrolytes
CN111910222A (en) * 2020-08-21 2020-11-10 九江德福科技股份有限公司 Electrolytic copper foil additive with brightening and leveling functions and application thereof
CN111910222B (en) * 2020-08-21 2022-08-23 九江德福科技股份有限公司 Electrolytic copper foil additive with brightening and leveling functions and application thereof

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US2907786A (en) 1959-10-06
NL298381A (en)
NL109804C (en)
FR1097123A (en) 1955-06-29
DE1207177B (en) 1965-12-16
FR69683E (en) 1958-11-18
US2849351A (en) 1958-08-26
DE923407C (en) 1955-02-10
NL110737C (en)
CH344715A (en) 1960-02-29
NL202744A (en)
CH327298A (en) 1958-01-31
BE543413A (en)
FR68292E (en) 1958-04-28
GB823152A (en) 1959-11-04

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