Classifications

• • 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

• This invention relates to an improvement in electroplating and more particularly to electroplating baths modified with an organic sulfonic acid addition agent which will produce a bright and lustrous electro deposit.
• Electroplating baths have heretofore been modified by the inclusion of organic sulfonic acids or organic sulfation products of various compounds. While the prior art addition agents have usually effected some improvement in the characteristics of the electro deposit produced from such modified baths, the additives individually have not been sufficient to produce commercially desirable deposits and had to be used with another and sometimes with even two or more supplemental addition agents.
• Another object of the invention is to provide an electroplating bath which will produce bright and lustrous electro deposits which in many instances may be used for their intended purpose without further polishing or buffing.
• Still another object of the invention is to provide addition agents for electroplating baths which may advantageously be used as sole addition agents or with other addition agents to produce bright and lustrous deposits.
• the brightening agents used in accordance with the present invention are organic sulfonic acids or salts thereof which have the general structural States Patent Patented Aug. 26, 1958 lCe CS--RSOsH Y and their salts, wherein X and Y are selected from the group consisting of nitrogen, sulfur and oxygen atoms.
• Typical sulfonic acids or their salts which can a dvantageously be used, either individually or in combination with each other, as brightening agents in electroplating baths in accordance with the present invention are the following:
• Dithiocarbamic acid-n-propylester-ammonium sulfonate S-phenyl-trithiocarbonic acid-n-propylester-w-sodium sulfonate;
• Trithiocarbonic acid-bis-propylester-w-sodium sulfonate Isopropyl-xanthic acid-n-butylester-w-sulfonate of sodium; n-butyl-xanthic acid-n-propylester-w-sodium sulfonate; Carbamino-thiol acid-n-propylester-potassium sulfonate; and the like.
• the specific sulfonic acid salts listed above for the purpose of illustrating the invention, but not of limiting the invention thereof, can be used as brightening agents in all types of electroplating baths, and particularly in electroplating baths for electrodepositing nickel, copper, zinc, silver, bronze and brass. They are capable of producing bright and lustrous deposits either individually or in conjunction with other well-known brightening agents, salts which improve the conductivity of the electroplating bath, wetting agents, or agents which tend to reduce the porosity of the deposit. above brightening agents are suitable for use in conjunction with those additives disclosed in German Patents No. 863,159 and No. 871,392.
• the amount of brightening agent added to an electroplating bath in order to produce a bright and lustrous deposit lies between certain limits within which the desired results will be obtained. These limits are different for each individual agent. It is also known that the range of current densities which will produce a bright and lustrous deposit lies between certain limits and those limits depend large- 1y upon the type and amount of agent used and the temperature of the electroplating bath. We have found that the addition of organic sulfonic acids in accordance with the invention as brightening agents for electroplating baths will increase the range of current densities over which deposits of satisfactory character can be produced. The amounts in which compounds of the invention are added to electroplating baths to produce bright and lustrous deposits vary between 0.01 and gm.
• the current density limit within which the above amounts will produce bright and lustrous deposits lies between 0.5 and 12 amp./drn. at a temperature below 60 C.
• Non-precious metals to be electroplated such as, for example, iron, steel or zinc, to mention only a few, are usually first provided with a base coating of copper in a potassium cyanide bath before being finally electroplated with the desired metal.
• the brightening agents of this invention are suitable for use in electroplating objects pro-coated in this manner as well as in electroplating objects not so pre-coated.
• Metal electro deposits produced from baths modified with the sulfonic acid additives of this invention are bright, highly lustrous and adhere very firmly to the base. In most cases the luster of the electro deposit so produced is so high that the electroplated object requires no further polishing or buffing after rinsing, whereby this additional time-consuming and costly step can be omitted in the production of electroplated articles.
• the sulfonic acid brightening agents of this invention have the additional advantage that they are chemically resistant to acid conditions, so that electroplating baths modified with such additives can remain in use virtually continuously, even at high temperatures, without losing their intended effectiveness.
• Example I 0.5 to 1 gm. of N,N-diethyl-dithiocarbarnic acid-npropylester-w-sodium sulfonate was added to each liter of an acid copper sulfate bath which contains 60 gm. sulfuric acid and gm. crystallized copper sulfate per liter of solution.
• Sheet steel provided with a preliminary copper coating in the presence of potassium cyanide was electroplated in the above bath.
• a current density range of from 1 to 10 amp./dm. at room temperature, both flat and highly profiled sheet steel objects were provided with a highly lustrous and well-adhering copper plate which did not require any further polishing or buffing treatment after rinsing.
• Example II 0.5 to 1.5 gm. 2-rnercaptobenzenethiazole-S-propanew-sodium sulfonate are added to each liter of the electroplating bath of Example I.
• An object electroplated in this solution at room temperature within current density limits of 7.5 to 10 amp./dm. was provided with a copper coating which was highly lustrous and did not need any further polishing treatment.
• Example III 1 gm. of betaine salt of isothiourea-S-propane-w-sulfonic acid was added to each liter of the electroplating bath of Examples I and II. An object electroplated in this solution at room temperature and current densities between 6 and 7.5 amp./dm. was provided with a highly lustrous copper coating which required no further polishing treatment after rinsing.
• Example V The same effect as in Example IV was obtained by adding 1 gm. of n-butylxanthic acid-n-propylester-w-sodium sulfonate per liter of acid copper sulfate solution of Example IV to such a solution and electroplating at the same temperature, but with a current density of 4 to 6 amp./dm.
• Example V1 0.5 to 1 gm. of the betaine salt of isothiourea-S-butanew-SlllfOHlC acid was dissolved in each liter of a nickelplating bath containing 60 gm. nickel chloride, 220 gm. crystallized nickel sulfate and 35 gm. boric acid per liter of solution.
• An object electroplated in such a solution at room temperature and current densities between 1 and amp./dm. was provided with a well-adhering and highly lustrous nickel coating which required no further polishing treatment.
• Example VII Effects similar to those of Example VI were obtained by adding to the nickel-plating bath of that example 0.5-1 gm. N,N-pentamethylene-dithiocarbamic acid-n-propylesteem-sodium sulfonate and electroplating at room temperature and current densities between 4 and 8 amp./dm. 1
• Example VIII The same highly lustrous nickel plate was obtained by substituting an equal amount of unsubstituted dithiocarbamic acid-n-propylester-w-sodium sulfonate for the sulfonate of Example VII, and electroplating at the same conditions of temperature and current densities as those stated in Example VII.
• Example IX v 0.5 to 1 gm. of N,N-dimethyl-dithiocarbamic acid-npropylester-w-sodium sulfonate was dissolved in each liter of a zinc electroplating bath containing 200 gm. zinc sulfate and 1 gm. glacial acetic acid per liter of solution. Sheet steel electroplated in such a solution at room temperature and current densities between 4 and 9 amp./dm. was plated With a highly lustrous zince coating which did not need to be polished after rinsing. Without the addition of the above sulfonate, the zinc coating was dull and required polishing to give it luster.
• An electroplating bath for producing deposits of metals selected from the group consisting of nickel, copper, zinc, silver, bronz and brass comprising an acid 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 general structural formula and their salts, wherein G is an organic radical which includes a carbon atom bonded exclusively with three hetero atoms, one of which is a sulfur atom through which said organic radical G is linked to the radical R-SO H, the other two hetero atoms being selected from the group consisting of nitrogen, sulfur and oxygen atoms, and R is a bivalent aliphatic radical, said compound being added in a quantity sufficient to produce a bright metal deposit.
• An electroplating bath for producing deposits of and their salts wherein X and Y each represent an atom selected from the group consisting of oxygen, nitrogen and sulfur, and R is a bivalent aliphatic radical.
• An electroplating bath for producing deposits of metals selected from the group consisting of nickel, copper, zinc, silver, bronze and brass comprising an acid solution of an inorganic salt of the metal to be deposited and 0.01 to 20 gm. per liter of a compound selected from the group consisting of organic sulfonic acids having the general structural formula and their salts, wherein X and Y each represent an atom selected from the group consisting of nitrogen, oxygen and sulfur, and R is a bivalent aliphatic radical.

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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)

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Citations (4)

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• 0
  • NL NL110737D patent/NL110737C/xx active
  • BE BE543413D patent/BE543413A/xx unknown
  • NL NL109804D patent/NL109804C/xx active
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  • NL NL298381D patent/NL298381A/xx unknown
• 1953
  • 1953-10-20 DE DEO3231A patent/DE923407C/de not_active Expired
• 1954
  • 1954-01-20 CH CH327298D patent/CH327298A/de unknown
  • 1954-03-24 FR FR1097123D patent/FR1097123A/fr not_active Expired
  • 1954-07-08 US US442199A patent/US2849351A/en not_active Expired - Lifetime
  • 1954-12-13 DE DED19318A patent/DE1207177B/de active Pending
• 1955
  • 1955-08-18 FR FR68292D patent/FR68292E/fr not_active Expired
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  • 1955-12-12 FR FR69683D patent/FR69683E/fr not_active Expired
  • 1955-12-13 US US552699A patent/US2837472A/en not_active Expired - Lifetime
• 1956
  • 1956-01-04 US US557422A patent/US2907786A/en not_active Expired - Lifetime

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