WO1991007522A1 - Komplexverbindungen mit oligomerem bis polymerem charakter - Google Patents

Komplexverbindungen mit oligomerem bis polymerem charakter Download PDF

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Publication number
WO1991007522A1
WO1991007522A1 PCT/DE1990/000845 DE9000845W WO9107522A1 WO 1991007522 A1 WO1991007522 A1 WO 1991007522A1 DE 9000845 W DE9000845 W DE 9000845W WO 9107522 A1 WO9107522 A1 WO 9107522A1
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WO
WIPO (PCT)
Prior art keywords
metal
complex compounds
compounds according
complex
solution
Prior art date
Application number
PCT/DE1990/000845
Other languages
German (de)
English (en)
French (fr)
Inventor
Lutz Stamp
Elisabeth Zettelmeyer-Decker
Heinrich Meyer
Gonzalo Urrutia Desmaison
Original Assignee
Schering Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schering Aktiengesellschaft filed Critical Schering Aktiengesellschaft
Priority to KR1019920701144A priority Critical patent/KR100212370B1/ko
Priority to DE59010794T priority patent/DE59010794D1/de
Priority to CA002068992A priority patent/CA2068992C/en
Priority to EP90916236A priority patent/EP0500616B1/de
Publication of WO1991007522A1 publication Critical patent/WO1991007522A1/de

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Classifications

    • 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
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Definitions

  • the invention relates to new complex compounds, the solutions of which can be used to produce metal nuclei (after a corresponding reduction) on in particular non-metallic surfaces.
  • This germination of substrate surfaces is often used for the subsequent chemical metallization (possibly with galvanic amplification) of non-conductors. This process step is of great importance in particular in the production of printed circuits for the electronics industry.
  • the other process contains the metal in the form of a soluble compound and first brings the metal in this form to the surface.
  • the metal compound initially applied is reduced and the metal nuclei are formed directly on the surface.
  • a disadvantage of the known methods is, for example, that when using, for example, palladium chloride as the noble metal salt and tin (II) chloride as the reducing agent, only the activation of unclad, that is to say copper-metal-free carrier material, is possible, since otherwise a Failure (cementation) of the precious metal on the copper cladding was done.
  • simple metal salts and monomeric metal complexes do not adsorb particularly well on many materials, or only sufficiently if there are very high concentrations of the metal compound in the solutions.
  • adsorbates applied to a surface in this way desorb very easily (for example during rinsing processes) and therefore do not adhere very firmly to the surfaces.
  • Activation solutions which contain both the noble metal salt and the reducing agent have the disadvantage of being particularly sensitive to foreign ions and other impurities, which lead to irreversible coagulation of the noble metal.
  • colloidal activators such activating solutions in which tin (1) compounds simultaneously act as a reducing agent and protective colloid are unstable with respect to oxidation by atmospheric oxygen and require the controlled dosing of the reducing agent at all times.
  • the object of the invention is to show substances for a stable activation solution which does not damage the base materials to be metallized and in particular their connection points, which is easy to use and which has a pronounced adsorption capacity for all non-metallic base materials.
  • This object is achieved according to the invention by complex compounds according to the characterizing part of patent claim 1.
  • Monomeric complexes of palladium and other metals which, in addition to the ligands according to the invention, also contain other ligands, such as, for example, solvent molecules or ions derived therefrom by, for example, protonation or deprotonation, can surprisingly be converted into stable solutions of oligomeric metal complexes in the Implement form that a connection occurs via these molecules or ions derived therefrom.
  • the individual metal centers are therefore connected by individual molecules or ions coordinated as a bridge ligand. Accordingly, these complexes differ fundamentally in their chemical structure and in their properties from complexes in which metal atoms are bound to oligomeric / polymeric organic molecules, as described, for example, in EP 82.38.
  • the oligomeric metal complexes according to the invention have an exceptional adsorption capacity on almost all non-metallic materials, such as epoxy resin, polyimide and glass, which are important for the manufacture of printed circuit boards, but also on other plastics, such as acrylonitrile-butadiene-styrene copolymers (ABS), Polyamide, polycarbonate, polyphenylene oxide, polyether sulfone, polyethene and on ceramics made of, for example, aluminum oxide and aluminum nitride and on mixtures of these materials.
  • ABS acrylonitrile-butadiene-styrene copolymers
  • Polyamide polycarbonate
  • polyphenylene oxide polyphenylene oxide
  • polyether sulfone polyethene
  • ceramics made of, for example, aluminum oxide and aluminum nitride and on mixtures of these materials.
  • the complexes according to the invention can also be used excellently in processes for the metallization of non-metal-metal composite materials.
  • the activator used according to the invention thus avoids all the disadvantages that have to be accepted with the conventional systems. Due to its oligomeric structure, it shows a high affinity for different base materials, and the noble metal nuclei formed are highly active, so that very dense metal coatings can be achieved by this form of activation.
  • Such activators do not attack base materials and, in particular, their compounds, since they are produced without halogen and can be operated in a wide pH range from alkaline to slightly acidic.
  • Solutions of such oligomeric metal complexes are therefore particularly suitable for activating base materials for the construction of conductor tracks and for activating boreholes for the purpose of plated-through holes in the production of printed circuits.
  • the solutions of the oligomeric / polymeric metal complexes are used in such a way that the materials / objects to be germinated are usually first subjected to a pretreatment which serves to clean the surfaces and / or the readiness by mechanical or chemical influence to promote adsorption to this surface.
  • the materials / objects to be germinated are then treated in the actual activation step with a solution of the oligomeric / polymeric metal complexes according to the invention. This can be done for example by diving, but also by spraying or gushing or other methods.
  • the solution can act on the surface for between 10 sec and 30 min.
  • the metal complex is adsorbed onto the surface.
  • Excess solution is then removed in a rinsing step (for example in a standing rinse, flow spool or spray rinse).
  • the adsorbed metal complex remains firmly adhered to the surface of the substrate to be activated.
  • the substrate (approx. 10 sec to 30 min) is treated with a solution of a reducing agent. This can be done, for example, by diving, rinsing or gushing.
  • the adsorbed complex is destroyed by reduction, and highly active metal nuclei are formed that adhere firmly to the substrate surface. Excess reducing agent can then be rinsed off.
  • reducing agents for this are, for example, borohydrides such as NaBH or borane-amine complexes, in particular dimethylamine borane, phosphinic acid or its salts, formaldehyde, hydrazine or others and mixtures of these reducing agents.
  • borohydrides such as NaBH or borane-amine complexes, in particular dimethylamine borane, phosphinic acid or its salts, formaldehyde, hydrazine or others and mixtures of these reducing agents.
  • the reducing agent of the electroless electrolyte subsequently used can also be used for the reduction.
  • the complex breaks down into soluble constituents and highly active metal particles.
  • the degree of oligomerization of the respective metal complex has a considerable influence on the activity of the resulting metal particles, since the size and morphology of the metal particles formed during the reduction have a significant influence on this.
  • the degree of oligomerization of the complex compounds is 3 to 10,000 of the monomeric units; complex compounds with 5 to 500 monomeric units are particularly suitable.
  • the oligomeric character of the molecules formed can be demonstrated, for example, using scattered light measurements. It is also possible to determine an average degree of oligomerization in this way.
  • the size of the oligomeric molecules can be regulated by the reaction conditions used in their binding (time, temperature, concentration, pH) and the nature of the noble metal ion and its ligands.
  • the desired molecular weight can be achieved by a suitable combination of the parameters.
  • the activation baths prepared with these oligomeric complexes can then be used in a wide variety of conditions, depending on the requirements. They work over a wide working range (especially the pH value).
  • the activation of non-metallic substrates achieved with the aid of the activators which are produced from the complex compounds according to the invention can be used for electroless metallization with a wide variety of metal coatings, which in turn can be metallized by galvanic or external currentless means.
  • metal coatings which in turn can be metallized by galvanic or external currentless means.
  • gold, palladium, silver, cobalt, tin or their alloys with one another, or also with elements such as phosphorus or boron as in the Ni / P systems are metals which can be brought onto the substrates by the activation according to the invention and Ni / B.
  • the calculated amount of the ligand is added to a salt or a suitable starting complex compound of the respective metal in suitable solvents such as water or organic solvents such as aliphatic alcohols, alcohol ethers such as ethylene glycol monoethers or ethers such as ethylene glycol diethers or mixtures thereof .
  • suitable solvents such as water or organic solvents such as aliphatic alcohols, alcohol ethers such as ethylene glycol monoethers or ethers such as ethylene glycol diethers or mixtures thereof .
  • the monomeric complex can be isolated, for example, by evaporating the solvent.
  • the required reaction parameters in particular the pH, are set to the values required for the respective product and the solution is heated until the Equilibrium (usually a few hours) to about 50 to 70 C. It is generally not possible to separate the oligomeric / polymeric complexes formed from the solution.
  • the conditions to be used for the isolation of the complexes in solid form generally lead to a change in the size and chemical structure of the molecules.
  • Suitable metals are Cu, Ag, Au, Ni, Pd, Pt, Ru, Rh, Os, Ir.
  • the metals themselves, their salts or other complex compounds of the corresponding elements can be used as the starting complex compound for the preparation of the complex compounds according to the invention.
  • Compounds which typically form monomeric complexes with metal ions are used as ligands for the preparation of the complex compounds according to the invention.
  • Compounds having one or more N, O, S or P atoms or one or more multiple bonds or more than one of these elements are preferably used.
  • Compounds from the group of nitrogen heterocycles are particularly suitable, for example pyridines, py ⁇ dazines, pyrimidines, pyrazines, quinolines, cinnolines or phthalazines.
  • the complexes according to the invention are dissolved for use as activators in the solvents in concentrations of 1 to 10,000 mg / 1, preferably in concentrations between 20 and 500 mg / 1. Decisive for the optimal concentration is, depending on the application, choice of process parameters such as temperature, treatment time etc., type of substrate and type of complex, its sufficient absorption on the substrate to be activated.
  • solvents or solvent mixtures can be used as solvents for the use of the oligomeric / polymeric metal complexes according to the invention which have a solubility which is sufficient for the development of the effect. It is particularly preferred to use the same solvent as for the production; thus a solvent from the group of alcohols, glycols, alcohol ethers or ethers, but especially water.
  • the pH of the solutions used for activation can be between 1 and 14, preferably between 5 and 12. It can be adjusted to the desired value by adding acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or acetic acid or - depending on the desired pH value - by adding alkalis such as sodium hydroxide solution, potassium hydroxide solution or ammonia.
  • a solution of 1.05 g (4.7 mmol) of palladium acetate in 10 ml of 10 'hydrochloric acid is diluted to 2 l with water and with 0.75 g (5 mmol) of N-acetyl-6-methyl-2-aminopyridine moved and stirred. 5 g (0.042 mol) of sodium dihydrogen phosphate are added and dissolved with stirring. A pH of 7 is set by adding sodium hydroxide solution. The solution is ready for use after 5 hours at 60 ° C. UV: (275, 390 s).
  • a solution according to Example 9 is prepared, except that 0.63 g (5 mmol) of 2-amino-4-hydroxy-6-methyl-pyrimidine is used instead of dipyridyl. UV: (260 s. 305 s, 410 s).
  • a solution according to Example 11 is prepared, except that instead of pyridazine 0.56 g (5 mmol) of 5-amino-3,4-dimetl.yliso ⁇ azol UV: (240 s, 280 s, 440 s) or 0.45 g (5 mmol) DL-Alanine UV: (300 s) can be used.
  • the following example is for comparison purposes. It describes the preparation of a solution of a monomeric complex.
  • J 3 _. ⁇ _ i It shows the poor adsorption properties typical of monomeric complexes and does not result in a satisfactory metallization if it is used under conditions comparable to those of the oligomeric / polymeric complexes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemically Coating (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/DE1990/000845 1989-11-17 1990-11-06 Komplexverbindungen mit oligomerem bis polymerem charakter WO1991007522A1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1019920701144A KR100212370B1 (ko) 1989-11-17 1990-11-06 올리고머성 또는 중합체성 착화합물
DE59010794T DE59010794D1 (de) 1989-11-17 1990-11-06 Komplexverbindungen mit oligomerem bis polymerem charakter
CA002068992A CA2068992C (en) 1989-11-17 1990-11-06 Complex compounds of an oligomeric or polymeric nature
EP90916236A EP0500616B1 (de) 1989-11-17 1990-11-06 Komplexverbindungen mit oligomerem bis polymerem charakter

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3938710.0 1989-11-17
DE3938710A DE3938710A1 (de) 1989-11-17 1989-11-17 Komplexverbindungen mit oligomerem bis polymerem charakter

Publications (1)

Publication Number Publication Date
WO1991007522A1 true WO1991007522A1 (de) 1991-05-30

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PCT/DE1990/000845 WO1991007522A1 (de) 1989-11-17 1990-11-06 Komplexverbindungen mit oligomerem bis polymerem charakter

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EP (1) EP0500616B1 ( )
JP (1) JP3093259B2 ( )
KR (1) KR100212370B1 ( )
AT (1) ATE161899T1 ( )
CA (1) CA2068992C ( )
DE (2) DE3938710A1 ( )
ES (1) ES2111541T3 ( )
WO (1) WO1991007522A1 ( )

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4130135C2 (de) * 1991-09-07 1999-07-22 Atotech Deutschland Gmbh Verfahren zur Herstellung von Formkörpern für Mikroelektrodenarrays
US7252699B2 (en) 2000-12-15 2007-08-07 The Arizona Board Of Regents Method for patterning metal using nanoparticle containing precursors
US8591636B2 (en) * 2010-12-14 2013-11-26 Rohm And Haas Electronics Materials Llc Plating catalyst and method
JP6159205B2 (ja) * 2013-09-04 2017-07-05 ローム・アンド・ハース電子材料株式会社 無電解めっき用触媒液

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2116389A1 (de) * 1971-03-30 1972-10-26 Schering Ag, 1000 Berlin Und 4619 Bergkamen Lösung und Verfahren zur Aktivierung von Oberflächen für die Metallisierung
EP0317092A1 (en) * 1987-10-27 1989-05-24 OMI International Corporation Catalyst for electroless plating process

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3318891A (en) * 1963-08-30 1967-05-09 Engelhard Ind Inc Palladium diacetate and method for its preparation
US3560257A (en) * 1967-01-03 1971-02-02 Kollmorgen Photocircuits Metallization of insulating substrates
DE3025307A1 (de) * 1980-07-04 1982-01-28 Bayer Ag, 5090 Leverkusen Verfahren zur aktivierung von oberflaechen fuer die stromlose metallisierung
DE3148280A1 (de) * 1981-12-05 1983-06-09 Bayer Ag, 5090 Leverkusen Verfahren zur aktivierung von substratoberflaechen fuer die stromlose metallisierung
DE3150985A1 (de) * 1981-12-23 1983-06-30 Bayer Ag, 5090 Leverkusen Verfahren zur aktivierung von substratoberflaechen fuer die stromlose metallisierung
US4533502A (en) * 1983-02-22 1985-08-06 Rochon Fernande D Platinum (II) compounds and their preparation
EP0367885A1 (de) * 1988-11-08 1990-05-16 Schering Aktiengesellschaft Konditionierungsmittel für gedruckte Schaltungen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2116389A1 (de) * 1971-03-30 1972-10-26 Schering Ag, 1000 Berlin Und 4619 Bergkamen Lösung und Verfahren zur Aktivierung von Oberflächen für die Metallisierung
EP0317092A1 (en) * 1987-10-27 1989-05-24 OMI International Corporation Catalyst for electroless plating process

Also Published As

Publication number Publication date
DE3938710A1 (de) 1991-05-23
DE59010794D1 (de) 1998-02-12
CA2068992C (en) 1997-08-19
DE3938710C2 ( ) 1992-10-08
ATE161899T1 (de) 1998-01-15
JP3093259B2 (ja) 2000-10-03
EP0500616A1 (de) 1992-09-02
JPH05501572A (ja) 1993-03-25
KR100212370B1 (ko) 1999-08-02
EP0500616B1 (de) 1998-01-07
KR927003872A (ko) 1992-12-18
ES2111541T3 (es) 1998-03-16

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