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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
  • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
  • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
  • C07D241/46—Phenazines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
  • C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines

Definitions

• the invention relates to new polymeric phenazonium compounds, methods for their production, as well as their use in acid electrolytes for the deposition of bright, leveling copper coatings.
• an acid copper electrolyte which is characterized by a content of at least one compound of the general formula wherein R R,, R R R R R R and R, are identical or different and represent hydrogen, a low alkyl or possibly substituted aryl, and R and R represent moreover monomeric or polymeric phenazonium radicals, A is an acid radical, and n an integer from 2 to 100, preferably from 4 to 20.
• An aryl radical may be, for example, phenyl, which may be substituted by methyl, ethyl, methoxy or ethoxy, etc.
• acid radicals there enter into consideration, for example, those of hydro-chloric acid (Cl'), sulfuric acid (HSOf), nitric acid (NO and acetic acid (Cl-[,coo), etc. a
• the radicals R and R may signify moreover, for example phenazonium radicals of the parent substance.
• the quantities in which the identified compounds must be added to the copper baths in order to obtain a clear improvement of the copper deposition are surprisingly very small and amount to about 0.0005 to 0.1 g/liter, preferably 0.0005 to 0.03 g/liter.
• Table l contains examples for substances according to the invention and data on the preferred concentrations in the electrolyte.
• the linkage points of the radicals are not fully clarified.
• the linkage may take place, besides through the 3-position of the phenazonium radical, also through the disadvantages of the known acid copper baths and S-and the 7-position.
• the invention therefore, further relates to a method for the production of the compounds identified above.
• A is an acid radical, from which then the desired reaction products are formed by diazotizing in acid solution and subsequent boiling down of the resulting diazonium salts.
• the diazotizing of the amino compounds is effected in sulfuric acid, hydrochloric acid, or acetic acid solution. These acids then form the above-mentioned acid radical A.
• diazotizing agents that are suitable are sodium nitrite or nitrosylsulfuric acid, etc.
• the so-called boiling down of the formed diazonium salts may take place at temperatures of about 5 to C, preferably about 10 to 25 C.
• reaction products precipitate from the acid reaction solution or can be precipitated therefrom by neutralization with bases, e.g., ammonia, soda or potash lye. Isolation is then effected by common methods.
• bases e.g., ammonia, soda or potash lye.
• Copper sulfate CuSo 5 H,O -260 g/liter Sulfuric'acid l-l SO 20-85 g/liter instead of copper sulfate, at least in part, other copper salts may be used.
• the sulfuric acid may be replaced partly or wholly by fluoroboric acid, phosphoric acid and/or other suitable acids.
• the electrolyte may be chloride-free, or this being usually advantageous for improving the luster and the leveling, it may contain chlorides, such as, alkali chlorides or hydrochloric acid, in quantities of 0.001 to 0.2 g/liter.
• the normally crystallinedull precipitate turns out bright in a wide current density range.
• the cathodic current density may be increased by about 50 percent without the formation of flaws, in particular budding, in the range of high current densities. To attain a certain layer thickness, therefore, the time of exposure may be reduced accordingly and in a unit of given size more merchandise can be put through.
• the substances according to the invention are also particularly suited for depositing haze-free and highbrighteners coatings in conjunction with other common luster-formers and/or wetting agents. Electrolytes containing the substances of Table I show also excellent ageing. Even after a current passage of 200-400 Ah/ltr and more, the copper coatings turn out just as highly lustrous, leveling and ductile as in a fresh batch of electrolyte. No harmful decomposition products of these substances are formed that would require purification, for example, with active carbon.
• Organic thio compounds with water solubilizing groups 0.0005-0.2 g/liter, preferably0.0l-0.l g/liter.
• Table II below contains examples of oxygencontaining, high-molecular compounds and their preferred concentrations.
• Table III contains examples of organic thio compounds with water-colubilizing groups and their preferred concentrations.
• the applicable cathodic current density is increased up to 50 percent
• the leveling effect i.e., the reduction of roughness of the ground material, is increased (measured at a layer thickness of 24 microns) from 40-50 percent to about 70-80 percent.
• the concentration ratios of the individual compounds in the copper electrolyte may vary within wide limits. It has proved favorable to have a weight ratio of the substances, listed by way of example in Tables I, II and Ill, of about I l 2 to about I 200 20.
• EXAMPLE 2 To a copper bath of the composition 200 g/liter copper sulfate (CuSO, 5 H 0) 60 g/liter sulfuric acid, concentrated 0.05 g/liter sodium chloride there are added as brighteners 0.6 g/liter polypropylene glycol and 0.02 g/liter sodium 3-mercaptopropane-l sulfonate.
• CuSO copper sulfate
• 5 H 0 sulfuric acid
• concentrated 0.05 g/liter sodium chloride there are added as brighteners 0.6 g/liter polypropylene glycol and 0.02 g/liter sodium 3-mercaptopropane-l sulfonate.
• an acid electrolyte for the deposition of bright copper coatings comprising (a) an oxygen containing high molecular weight compound selected from the group consisting of polyvinyl alcohol, carboxymethyl cellulose, polyethylene glycol, stearic acid polyglycol ester, oleic acid polycol ester, and nonylphenol polyglycol ester; (b) an organic thio compound selected from the group consisting of sodium salt of N N-diethyl-dithiocarbamic acid (sulfopropyl ester), sodium mercaptobenzothiazol-S-propanesulfonate, sodium S-mercapto-propane-l-sulfonate, bis-(S-sodium sulfopropyl)-disulfide, disodium salt of thiophosphoric acidacid-O-ethyl-bis-(sulfopropyl) ester, trisodium salt of thiophosphoric acid-tri-(sulfo
• An electrolyte according to claim 2 characterized in that it additionally contains oxygen-containing, highmolecular compounds and organic thio compounds with water-solubilizing groups.
• Electrolyte according to claim 3 characterized in that it contains the oxygen-containing, high-molecular compounds in quantities of 0.01 to 20.0 g/liter, preferably 0.02 to 8.0 g/liter and the organic thio compounds with water-solubilizlng groups in quantities of 0.0005 to 0.2 g/liter, preferably 0.01 to 0.1 g/liter.
• An electrolyte for the deposition of bright copper coatings comprising at least one compound of the wherein R through R, are individually selected from the group-consisting of hydrogen, lower alkyl, aryl, and substituted aryl, R and R being additionally a monomeric or polymeric phenazonium radical; A is an acid radical; and n is an integer from 2 to 100.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Electrochemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Electroplating And Plating Baths Therefor (AREA)
• Paints Or Removers (AREA)
• Detergent Compositions (AREA)

Applications Claiming Priority (2)

Publications (1)

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Cited By (15)

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Citations (5)

• 1970
  • 1970-06-06 DE DE2039831A patent/DE2039831C3/de not_active Expired
  • 1970-06-06 DE DE2028803A patent/DE2028803C3/de not_active Expired
• 1971
  • 1971-05-24 CH CH755871A patent/CH556347A/de not_active IP Right Cessation
  • 1971-06-02 CA CA114,600A patent/CA961494A/en not_active Expired
  • 1971-06-02 US US00149335A patent/US3743584A/en not_active Expired - Lifetime
  • 1971-06-03 FR FR7120152A patent/FR2095876A5/fr not_active Expired
  • 1971-06-03 AT AT482371A patent/AT302764B/de not_active IP Right Cessation
  • 1971-06-07 NL NLAANVRAGE7107804,A patent/NL173277C/xx not_active IP Right Cessation
  • 1971-06-07 GB GB1917271*[A patent/GB1357442A/en not_active Expired

Patent Citations (5)

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