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
  • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

• the present invention relates to improved extender compositions used in copper electroplating comprising a sulfurized sulfonated aromatic compound, an amino derivative of a triarylmethane, and as a leveling agent a compound containing the radical i e
• the combination of the ingredients of the type specified gives synergistic results in the form of improved brightness and leveling properties over a wider range of current density than previous compositions used in copper electroplating baths.
• My invention relates to the electroplating of copper on metal bases from acidic electrolyte solutions, and to compositions for use therein. More particularly, it relates to the production of copper plated objects of improved physical characteristics by the incorporation in the electrolyte of addition agents containing the radical where X is S or N, and particularly, in combination with sulfurized sulfonated aromatic or hydroaromatic compounds, and substitution products thereof, and amino derivatives of a triarylmethane, and to compositions containing such materials.
• a neW type of additive composition for copper plating operations consisting of a mixture of agents which gives copper deposits of improved properties and which at the same time is relatively free from most of the previous plating difliculties.
• the incorporation in this mixed additive of a new type of leveling agent has given especially good leveling characteristics, with the result that much less buffing is required than has been necessary with previously known types of additives and leveling agents. This is of particular importance in reducing the cost of preparing plates for secondary plating.
• the copper plates obtained with my new additive composition have excellent brightness and ductility, thus improving their suitability for secondary plating.
• the use of my new additive composition permits the plating operation to be satisfactorily carried out over a wider operating range than is possible with previous additives, thus reducing the percentage of rejects as well as over-all operating costs.
• My new additive composition for use in copper electroplating electrolytes essentially comprises a mixture of sulfurized sulfonated aromatic or hydroaromatic hydrocarbons, and substitution products thereof; amino derivatives of a triarylmethane; and compounds containing the radical 3 used in his claimed combination, these compounds serve their function as brighteners in an effective manner and without the operating difliculties incurred when the materials are used alone. Also, much less of the material is required when used in my claimed combination.
• suitable compounds of this type include sulfurized sulfonated benzene, sulfurized sulfonated toluene, sulfurized sulfonated xylene, sulfurized sulfonated naphthalene, sulfurized sulfonated anthracene, sulfurized sulfonated phenanthrene, sulfurized sulfonated diphenyl, and hydrogenated derivatives of the same.
• These materials comprise the colloidal sulfonated reaction products of an aromatic or hydroaromatic hydrocarbon, or substitution product thereof, with a sulfurizing agent such as, for example, sulfur chloride, sulfuryl chloride or thionyl chloride.
• a sulfurizing agent such as, for example, sulfur chloride, sulfuryl chloride or thionyl chloride.
• the sulfurized aromatic or hydroaromatic or hydroaromatic hydrocarbon, or substitution derivative thereof may be sulfonated by conventional means, as by fuming sulfuric acid. Or, the sulfonation may first be effected and followed by sulfurization.
• the product in either case is water soluble or water dispersible.
• Sulfurized sulfonated benzene suitable for use in the present invention may, for example, be
• the amino derivatives of triarylmethane are dyestuffs soluble in the plating solutions to the specified amounts.
• Suitable amino derivatives of this type include dyestuffs commonly known as Guinea Green B, Brilliant Milling Green B, Patent Blue V, Light Green SFA, Neptune Blue, Erioglycine or Alphazurine F.
• G. Chromoxane Brilliant Violet 5R, Soluble Blue, Methyl Blue or Helvetia Blue, Brilliant Indocyanine 6B, Acid Violet 6B, and Wool Fast Blue FBL.
• the structural formula of these dyes are shown in United States patent application Ser. No. 279,006 filed May 8, 1963, now abandoned.
• the addition agents serving primarily as leveling agents, used in my addition compositions are compounds wherein X is selected from and where A is The following are examples of typical compounds of the above types which have given excellent results as leveling agents in my new additive compositions for copper plating:
• chlorornercurithio-2,3 -diphenyl-2H-tetrazolium chloride can be prepared by adding a mixture of mercuric chloride to a suspension of diphenylthiocarbazone in benzene, using a molar ratio respectively of 1:2. After refluxing this mixture for a number of hours a reaction product is obtained from which the desired product can be produced by washing with a suitable solvent such as chloroform, benzene, Xylene, chlorobenzene, carbontetrachloride, acetone, ethyl acetate, or other suitable solvent for removal of the undesired compounds of the reaction.
• a suitable solvent such as chloroform, benzene, Xylene, chlorobenzene, carbontetrachloride, acetone, ethyl acetate, or other suitable solvent for removal of the undesired compounds of the reaction.
• suitable solvent such as chloroform, benzene, Xylene, chlorobenzene
• My new leveling agents of the above types can be used in plating compositions with satisfactory results in concentrations ranging from 0.0005 to 0.1 gm./1., although I prefer to use concentrations ranging from 0.001 to 0.04 gm./l.
• the sulfurized sulfonated aromatic and hydroaromatic hydrocarbons are used in amounts ranging from 0.0015 to 0.5 gm./l., and preferably within the range of 0.01 to 0.04 gm./l.
• the concentration of the particular dye used can vary between 0.001 to 2.0 gm./l. with a preferred range of 0.015 to 0.5 gm./l.
• Example 2 In this experiment carried out as described in Example 1, the electrolyte had the following composition:
• Example 3 Gm./l. Copper sulfate 22S Sulfuric acid 60 Sulfurized sulfonated xylene 0.05 Bis (thiocarbohydrazido) mercury 0.01 Patent Blue V dye 0.04
• Example 4 In this experiment, carried out as described in Example I, the following electrolyte composition was used:
• Example 6 In this experiment, carried out as described in Example 1, the following electrolyte composition was used:
• Example 7 In this experiment, carried out as described in Example 1, the electrolyte used had the following composition:
• Example 8 In this experiment carried out as described in Example 1, the following electrolyte was used:
• Example 9 In this experiment, carried out as described in Example l, the following electrolyte was used:
• Ari electrolyte for electroplating copper consisting essentially of an aqueous acid solution of copper sulfate and free sulfuric acid and having dissolved therein an additive composition comprising a sulfurized sulfonated aromatic or hydroarornatic hydrocarbon or substitution product thereof, an amino derivative of triarylmethane and a compound containing the radical wherein X is selected from said additive composition being used in an amount sufiicient to give a bright, level deposit.
• sulfurized sulfonated aromatic compound is selected from the group consisting of sulfurized sult'onated benzene, sulfurized sulfonated toluene, sulfurized sulfonated xylene, sulfurized sulfonated naphthalene, sulfurized sulfonated anthracene, sulfurized sulfonated phenanthrene, sulfurized sultonated diphenyl, and hydrogenated derivatives of same.
• amino derivative of triarylmethane is selected from the group consisting of Guinea Green B, Brilliant Milling Green B, Patent Blue V, Light Green SFA, Neptune Blue, Erioglycine or Alphazurine F. G., Chromoxane Brilliant Violet 5R, Soluble Blue, Methyl Blue or Helvetia Blue, Brilliant Indocyanine 6B, Acid Violet 6B, and Wool Fast Blue FBL.
• the compound containing the radical i is selected from the group consisting of 5-chloromercurithio-2,3-diphenyl-2H-tctrazolium chloride; Z-thiazolidinethionomercuric chloride; bis (Z-thiazolidinethiono) mercury; thiocarbohydrazido mercuric chloride; bis (thiocarbohydrazido) mercury; 1-acetyl-2-hydrantointhionomercuric chloride; his (1-acetyl-2-hydrantointhiono) mercury; 2-imidazolidinethionomercuric chloride; bis (Z-imidazolidinethiono) mercury; 2-benzimidazolethionomercuric chloride; bis (2-benzimidaz0lethiono) mercury; bis (2-benzothiazolethiono)) mercury; bis (l-phenyl-Z- tetrazole-S-thiono) mercury; bis (l-phenyl-Z
• the method of electroplating copper comprising the step of electrodepositing copper from an aqueous acidic copper plating bath containing dissolved therein an additive composition comprising about 0.0015 to 0.5 gm./l. of a sulfurized sulfonated aromatic or hydroaromatic hydrocarbon or substitution product thereof, about 0.0015 to 1.0 gm./l. of an amino derivative of triarylmethane, and about 0.005 to 0.1 gin/1. of a compound containing the radical wherein X is selected from said additive composition serving to efiect the deposition of the copper in a bright, level form.
• an additive composition comprising about 0.0015 to 0.5 gm./l. of a sulfurized sulfonated aromatic or hydroaromatic hydrocarbon or substitution product thereof, about 0.0015 to 1.0 gm./l. of an amino derivative of triarylmethane, and about 0.005 to 0.1 gin/1. of a compound containing the radical wherein X is selected from
• the sulfurized sulfonated aromatic hydrocarbon compound is selected from the group consisting of sulfurized sulfonated benzene, sulfurized sulfonated toluene, sulfurized sulfonated Xylene, sulfurized sulfonated naphthalene, sulturized sulfonated anthracene, sulfurized sult'onated phenanthrene, sulfurized sulfonated diphenyl, and hydrogenated derivatives of same.
• amino derivative of triarylmethane is selected from the group consisting of Guinea Green B, Brilliant Milling Green B, Patent Blue V, Light Green SFA, Neptune Blue, En'oglycine or Alphazurine F. G., Chromoxane Brilliant Violet 5R, Soluble Blue, Methyl Blue or Helvetia Blue, Brilliant Indocyanine 6B, Acid Violet 6B, and Wool Fast Blue FBL.
• the compound containing the radical at I is selected from the group consisting of S-chlorornercurithio-2,3-diphenyl-2P-tetrazolium chloride; 2-thiazolidinethionomercuric chloride; bis (Z-thiazolidinethiono) mercury; thiocarbohydrazido mercuric chloride; bis (thiocarbohydrazido) mercury; 1-acetyl-2hydrantointhionomercuric chloride; bis (l-acetyl-Z-hydrantointhiono) mercury; 2-imidazolidinethionomercuric chlo ride; bis (Z-imidazolidinethiono) mercury; 2-benzirnidazolethionomercuric chloride; bis (Z-benzirnidazolethiono) mercury; bis (Z-benzothiazolethiono) mercury; bis (1-phenyl-2-tetrazole-5-thiono

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• 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)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (10)

Applications Claiming Priority (1)

Publications (1)

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Cited By (2)

Citations (6)

• 1967
  • 1967-06-05 US US643405A patent/US3373095A/en not_active Expired - Lifetime
• 1968
  • 1968-05-22 SE SE6974/68A patent/SE345879B/xx unknown
  • 1968-05-25 DE DE1771447A patent/DE1771447C2/de not_active Expired
  • 1968-05-27 AT AT505968A patent/AT278464B/de not_active IP Right Cessation
  • 1968-05-30 ES ES354519A patent/ES354519A1/es not_active Expired
  • 1968-06-04 NO NO2173/68A patent/NO120960B/no unknown
  • 1968-06-04 BE BE716104D patent/BE716104A/xx unknown
  • 1968-06-04 LU LU56200D patent/LU56200A1/xx unknown
  • 1968-06-05 NL NL6807883A patent/NL6807883A/xx unknown
  • 1968-06-26 FR FR1569546D patent/FR1569546A/fr not_active Expired

Patent Citations (6)

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