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WO1995009255A1 - Procede de protection contre la corrosion de surfaces brasables en cuivre ou en alliage cuivreux - Google Patents

Procede de protection contre la corrosion de surfaces brasables en cuivre ou en alliage cuivreux Download PDF

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Publication number
WO1995009255A1
WO1995009255A1 PCT/EP1994/003140 EP9403140W WO9509255A1 WO 1995009255 A1 WO1995009255 A1 WO 1995009255A1 EP 9403140 W EP9403140 W EP 9403140W WO 9509255 A1 WO9509255 A1 WO 9509255A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
formula
compounds
solutions
sulfur compounds
Prior art date
Application number
PCT/EP1994/003140
Other languages
German (de)
English (en)
Inventor
Ulrich Schröder
Norbert Wagner
Harald Keller
Jürgen DEMBOWSKI
Veronika Kohl
Original Assignee
Basf 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 Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO1995009255A1 publication Critical patent/WO1995009255A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C23F11/161—Mercaptans
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0562—Details of resist
    • H05K2203/0591—Organic non-polymeric coating, e.g. for inhibiting corrosion thereby preserving solderability

Definitions

  • the present invention relates to an improved method for protecting solderable copper and copper alloy surfaces, the solderability of which is maintained or even improved after the implementation of this method and after storage under the influence of the atmosphere.
  • Exposed copper surfaces on printed circuit boards are usually protected mainly by hot tinning or by galvanic deposition of tin or a lead / tin alloy and are thus kept solderable. Following the galvanic deposition, however, a remelting process is generally necessary.
  • DE-A 20 03 175 (1) relates to the use of 2-alkylimidazoles with a long straight-chain alkyl group having 5 to 21 carbon atoms in the 2-position and hydrogen or a lower alkyl group in the 4-position or the like Acid addition salts as protective agents for copper and copper alloy surfaces to be protected from the effects of the atmosphere.
  • EP-A 178 864 (2) relates to a process for the production of printed circuit boards using aqueous solutions of acid addition salts of 2-alkylimidazoles, as described in (1).
  • the object of the present invention was to provide a method in which protection for copper and copper alloy surfaces is produced by treatment with the solution of a suitable active ingredient, the protective layer produced being temperature-stable and, after thermal stress, a Soldering on such a surface is prevented as little as possible.
  • R 1 denotes hydrogen or a radical of the formula -SA 2 -R 3 , A 1 and A 2 are straight-chain or branched C - to C 3 o-alkyl groups and
  • R 2 and R 3 represent hydrogen or hydroxyl groups
  • solderability is not impaired by the organic molecules or their degradation products covalently bonded as described in (3) and (4) after treatment of the coated copper and copper alloy surfaces at high temperatures.
  • the method according to the invention can even be used on unpurified, i.e. not pre-cleaned copper and copper alloy surfaces with good results.
  • the method according to the invention is preferably used for the corrosion protection of printed circuit boards.
  • Suitable sulfur compounds I are:
  • alkylene groups A 1 and A 2 are usually only slightly branched or preferably straight-chain alkyl groups with 4 to 30, preferably 6 to 24, in particular 7 to 18, especially 8 to 12 carbon atoms. With branched alkylene groups there are usually up to three methyl or ethyl side chains.
  • a 1 and A 2 are polymethylene groups of the formula - (CH) n -, i where n is 6 to 24, in particular 7 to 18, especially 8 to 12.
  • the alkylene groups A 1 and A 2 can be the same or different, but preference is given to the same groups A 1 and A 2 because the corresponding compounds I are easier to prepare.
  • Suitable solvents for the compounds I are, above all, alcohols, e.g. Methanol, ethanol, iso-propanol or ethylene glycol, ether, e.g. Tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether (butyl glycol), dipropylene glycol monomethyl ether or dipropylene glycol monoethyl ether, ketones, e.g. Acetone, butanone or N-methylpyrrolidone, carbonic acid esters, e.g. Carbonic acid propylene glycol esters, polyethylene glycols, carboxylic acid esters, e.g.
  • alcohols e.g. Methanol, ethanol, iso-propanol or ethylene glycol
  • ether e.g. Tetrahydrofuran
  • ethylene glycol monomethyl ether ethylene glycol monoethyl ether
  • Solvent systems with low vapor pressure in particular dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or ethylene glycol monobutyl ether (butyl glycol) are preferred.
  • the solutions are generally applied by setting these treatment solutions to a temperature of 15 to 60 ° C., preferably 15 to 55 ° C., in particular 20 to 40 ° C., and thereby the copper and copper alloy surfaces for a time of at least 5 sec, preferably 10 to 60 sec, in particular 15 to 40 sec, in contact.
  • the easiest way to bring them into contact is to immerse the object to be protected in the solution, but it is also possible to spray or brush the object with the solution.
  • the surface of the article can be rinsed after the treatment with the other suitable solvent or water used, but preferably with the solvent or water used. Rinsing is not absolutely necessary. Rinsing takes place, for example, by immersing the object in the solvent or water, or by transferring the solvent or water over the surface of the object. Then the surface of the object is Licher dried, for example at room temperature in air or in a drying cabinet at about 40 to 100 ° C.
  • the content of the compounds I in the solutions is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight, in particular 0.5 to 3% by weight. If the contents are less than 0.01% by weight, no protective effect can be demonstrated, and if the contents are greater than 10% by weight, an increased impairment of the solderability of the metal surfaces is observed after thermal stress.
  • the solutions described are suitable for the effective protection of all metal surfaces, which consist primarily of pure copper, but also of copper alloys, for example also of brass surfaces.
  • the method according to the invention is of particular importance for printed circuit board technology.
  • the protective layers produced on the objects with copper-containing surfaces are temperature stable and do not hinder the soldering processes even after thermal stress.
  • Drilled, copper-clad PCB base material pieces with a size of approx. 1 x 10 cm were 20 sec at 30 ° C in a solution consisting of 25 ml of conc. Sulfuric acid, 5 ml of 30% hydrogen peroxide, 1 drop of 5% by weight aqueous copper sulfate solution and 75 ml of water, etched, rinsed with water and compressed air dried.
  • An etched circuit board base material piece was immersed in the solution of the test substance at 30 ° C. for 20 seconds and, after dripping, was dried in air at room temperature.
  • Test A steam test
  • the dipped and dried base material piece was in a test tube with a diameter of about 3 cm and a volume of 100 ml, which contained about 5 ml of water and a boiling stone and immersed in a heating bath at a temperature of 110 ° C, using a Thread and a glass rod hung for 45 minutes without being immersed in the water.
  • the base piece of material was stored in the drying cabinet at 200 ° C. for 15 minutes after test A.
  • solderability of the copper-clad piece of base material was checked by tinning in a vertical hot-tinning machine (soldering temperature: 240 ° C; immersion time: 4 sec; flux: 85% by weight of a commercially available mixture of several alkoxylates / 0.45% by weight). -% glutamic acid hydrochloride / water ad 100 wt .-%).
  • H 2 0 / HOAc approx. 0.2 wt. -% aqueous acetic acid solution (pH 4 to 4, 5)
  • Grade 3 moderate defects (dewetting, very low non-wetting)
  • Grade 4 very strong defects (almost no wetting with solder).
  • the effect of the method according to the invention can also be shown on printed circuit boards themselves.
  • plated-through, tin-free printed circuit boards were used instead of copper-clad printed circuit board base material. As described above, these were etched, immersed and subjected to the tests mentioned. The circuit boards were then sent through a wave soldering machine (test D) without assembly (soldering temperature: 240 ° C; transport speed: 0.9 m / min). A 2% by weight solution of adipic acid in isopropanol was used as the activator.
  • Dewetting grade 3 soldering with defects; Solder does not rise in the solder eyes; SMD surfaces with clear dewetting
  • Grade 4 badly disturbed soldering; SMD surfaces and pads only partially wetted with solder.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

L'invention concerne un procédé de protection de surfaces brasables en cuivre ou en alliage cuivreux contre la corrosion due à l'influence de l'atmosphère, par mise en contact des surfaces de métal avec une solution d'un ou de plusieurs composés sulfurés de la formule (I): R?2-A1-S-R1¿, dans laquelle R1 désigne hydrogène ou un reste de la formule -S-A?2-R3, A1 et A2¿ désignent des groupes alkyle C¿4?-C30 linéaires ou ramifiés, R?2 et R3¿ désignent des atomes d'hydrogène ou des groupes hydroxyles, les surfaces de métal étant éventuellement rincées et ensuite séchées.
PCT/EP1994/003140 1993-09-29 1994-09-20 Procede de protection contre la corrosion de surfaces brasables en cuivre ou en alliage cuivreux WO1995009255A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4333127.0 1993-09-29
DE19934333127 DE4333127A1 (de) 1993-09-29 1993-09-29 Verfahren zum Schutz von lötfähigen Kupfer- und Kupferlegierungsoberflächen vor Korrosion

Publications (1)

Publication Number Publication Date
WO1995009255A1 true WO1995009255A1 (fr) 1995-04-06

Family

ID=6498931

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/003140 WO1995009255A1 (fr) 1993-09-29 1994-09-20 Procede de protection contre la corrosion de surfaces brasables en cuivre ou en alliage cuivreux

Country Status (2)

Country Link
DE (1) DE4333127A1 (fr)
WO (1) WO1995009255A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6365067B1 (en) * 1999-08-12 2002-04-02 Baker Hughes Incorporated Mercaptoalcohol corrosion inhibitors
US7396596B2 (en) 2004-06-23 2008-07-08 Ormecon Gmbh Article with a coating of electrically conductive polymer
US7547479B2 (en) 2004-06-25 2009-06-16 Ormecon Gmbh Tin-coated printed circuit boards with low tendency to whisker formation
US7947199B2 (en) 2005-03-02 2011-05-24 Ormecon Gmbh Conductive polymers consisting of anisotropic morphology particles
US7989533B2 (en) 2005-08-19 2011-08-02 Ormecon Gmbh Chemical compound comprising an indium-containing intrinsically conductive polymer
US8153271B2 (en) 2006-09-13 2012-04-10 Ormecon Gmbh Article with a coating of electrically conductive polymer and precious/semiprecious metal and process for production thereof
CN113737167A (zh) * 2021-09-22 2021-12-03 东莞市四辉表面处理科技有限公司 一种铜材的防氧化剂及其制备方法
CN116926552A (zh) * 2023-08-04 2023-10-24 宁波聚禾新材料科技有限公司 一种铜保护剂及其配置方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19757302A1 (de) 1997-12-22 1999-07-01 Siemens Ag Beschichtung von Metalloberflächen insbesondere für die Mikroelektronik
DE19836544C2 (de) * 1998-08-07 2001-06-28 Hahn Meitner Inst Berlin Gmbh Verwendung von Di-tert-Butyldisulfid (TBDS) und/oder tert-Butylmercaptan (TBM) als Korrosionsinhibitoren der mikrobiellen Korrosion von Metallen
DE102004003784B4 (de) 2004-01-23 2011-01-13 Ormecon Gmbh Dispersion intrinsisch leitfähigen Polyanilins und deren Verwendung

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1347705A (fr) * 1961-09-28 1964-01-04 Minnesota Mining & Mfg Composition empêchant le ternissement des surfaces à base de cuivre
DE1521919B1 (de) * 1962-04-10 1970-01-02 Du Pont Verwendung von Mercaptoverbindungen zum Entfernen und Verhindern von Anlaufschichten auf Metallen
US3503883A (en) * 1964-08-19 1970-03-31 Goddard & Sons Ltd J Metal surface protecting preparations
JPS59215490A (ja) * 1983-05-23 1984-12-05 Alps Electric Co Ltd 金属の変色防止剤
DE3905850A1 (de) * 1989-02-24 1990-08-30 Blasberg Oberflaechentech Verfahren zum schuetzen von blanken silberoberflaechen
EP0492487A1 (fr) * 1990-12-22 1992-07-01 DODUCO GMBH + Co Dr. Eugen DÀ¼rrwächter Produit de protection temporaire de surfaces nues en argent et en cuivre contre le ternissement et procédé d'utilisation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1347705A (fr) * 1961-09-28 1964-01-04 Minnesota Mining & Mfg Composition empêchant le ternissement des surfaces à base de cuivre
DE1521919B1 (de) * 1962-04-10 1970-01-02 Du Pont Verwendung von Mercaptoverbindungen zum Entfernen und Verhindern von Anlaufschichten auf Metallen
US3503883A (en) * 1964-08-19 1970-03-31 Goddard & Sons Ltd J Metal surface protecting preparations
JPS59215490A (ja) * 1983-05-23 1984-12-05 Alps Electric Co Ltd 金属の変色防止剤
DE3905850A1 (de) * 1989-02-24 1990-08-30 Blasberg Oberflaechentech Verfahren zum schuetzen von blanken silberoberflaechen
EP0492487A1 (fr) * 1990-12-22 1992-07-01 DODUCO GMBH + Co Dr. Eugen DÀ¼rrwächter Produit de protection temporaire de surfaces nues en argent et en cuivre contre le ternissement et procédé d'utilisation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 9, no. 82 (C - 275) 11 April 1985 (1985-04-11) *
YAMAMOTO Y.: "Self-assembled layers of Alkanethiols on Copper for Protection against Corrosion", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 140, no. 2, 1 February 1993 (1993-02-01), MANCHESTER, NEW HAMPSHIRE US, pages 436 - 443, XP000378181 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6365067B1 (en) * 1999-08-12 2002-04-02 Baker Hughes Incorporated Mercaptoalcohol corrosion inhibitors
US6645399B2 (en) 1999-08-12 2003-11-11 Baker Hughes Incorporated Mercaptoalcohol corrosion inhibitors
US7396596B2 (en) 2004-06-23 2008-07-08 Ormecon Gmbh Article with a coating of electrically conductive polymer
US7547479B2 (en) 2004-06-25 2009-06-16 Ormecon Gmbh Tin-coated printed circuit boards with low tendency to whisker formation
US7947199B2 (en) 2005-03-02 2011-05-24 Ormecon Gmbh Conductive polymers consisting of anisotropic morphology particles
US7989533B2 (en) 2005-08-19 2011-08-02 Ormecon Gmbh Chemical compound comprising an indium-containing intrinsically conductive polymer
US8153271B2 (en) 2006-09-13 2012-04-10 Ormecon Gmbh Article with a coating of electrically conductive polymer and precious/semiprecious metal and process for production thereof
CN113737167A (zh) * 2021-09-22 2021-12-03 东莞市四辉表面处理科技有限公司 一种铜材的防氧化剂及其制备方法
CN116926552A (zh) * 2023-08-04 2023-10-24 宁波聚禾新材料科技有限公司 一种铜保护剂及其配置方法

Also Published As

Publication number Publication date
DE4333127A1 (de) 1995-03-30

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