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EP0166327B1 - Procédé de fabrication de plaques pour circuits imprimés - Google Patents

Procédé de fabrication de plaques pour circuits imprimés Download PDF

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Publication number
EP0166327B1
EP0166327B1 EP85107381A EP85107381A EP0166327B1 EP 0166327 B1 EP0166327 B1 EP 0166327B1 EP 85107381 A EP85107381 A EP 85107381A EP 85107381 A EP85107381 A EP 85107381A EP 0166327 B1 EP0166327 B1 EP 0166327B1
Authority
EP
European Patent Office
Prior art keywords
baseboards
activated
cyclohexene
way
solution
Prior art date
Legal status (The legal status 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 status listed.)
Expired
Application number
EP85107381A
Other languages
German (de)
English (en)
Other versions
EP0166327A2 (fr
EP0166327A3 (en
Inventor
Kirkor Dr. Sirinyan
Gerhard Dieter Dr. Wolf
Ulrich Dr. Von Gizycki
Rudolf Dr. Merten
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Priority to AT85107381T priority Critical patent/ATE39367T1/de
Publication of EP0166327A2 publication Critical patent/EP0166327A2/fr
Publication of EP0166327A3 publication Critical patent/EP0166327A3/de
Application granted granted Critical
Publication of EP0166327B1 publication Critical patent/EP0166327B1/fr
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28Sensitising or activating

Definitions

  • the invention relates to a wet chemical process for the production of printed circuit boards.
  • the deposition of adherent metal layers on the usual insulating base materials requires a complex pretreatment.
  • the base plates must first be provided with an adhesion promoter layer and then treated with oxidizing liquid, preferably chromosulfuric acid, before the plates prepared in this way are activated, masked and metallized in commercially available metallization baths with ionic or colloidal noble metal solutions.
  • this technique has the disadvantage that chromium ions which have been introduced poison the baths irreversibly and that the printed circuit boards obtained have unsatisfactory electrical properties.
  • the method according to the invention has the advantage that a metal layer with a thickness of only a maximum of 10 ⁇ m, preferably 0.1-7 , 5 ⁇ m or - particularly preferably 0.1-5.0 ⁇ m - must be etched out, which results in considerable material savings.
  • the palladium complexes are particularly preferred.
  • novel process is advantageously carried out in such a way that base materials with the above. wetted organometallic compounds. This can be done primarily by spraying with a volatile organic solution of the activators mentioned or by dipping into these media.
  • Alcohols such as C 2 H 5 OH and CH 3 0H or their mixtures with one another into consideration.
  • the base materials treated in this way are then, if necessary swollen in a solvent, then sensitized and metallized over the entire area in a reductive metallization bath.
  • the metal coating thus obtained is galvanically reinforced up to a maximum total thickness of 10 ⁇ m.
  • the metallized base material also called “semi-finished product” is partially provided with a mask.
  • resist layers photoresists, photoresists
  • negative resists or “positive resists”
  • positive resists are used to cover the semi-finished products. They are generally known (see, for example, Günther Hermann, “Printed Circuit Boards, Manufacturing and Pretreatment •, pp. 98-103 and 125-127).
  • the unexposed parts are removed with a suitable solvent after the exposure, in the second case the exposed parts.
  • a number of special resist systems can be used to produce reliefs for electronics or for microelectronics.
  • the resist systems curable with the aid of UV radiation, electron radiation and laser radiation should be mentioned (cf. DE-A 2 007 267, DE-A 2 454 879 and DE-A 2 507 874).
  • the relief mask can also be applied by screen printing, coating or stamping.
  • Suitable substrates for the process according to the invention are plates, preferably plates made of glass fiber and glass mat reinforced epoxy resins provided with standard holes (see, for example, Kunststoff Handbuch, Prof. R. Vieweg, XI, pp. 180-246, Carl Hanser Verlag, Kunststoff (1971)) , fluorine-containing polymers (see, for example, reference p. 673-674) such as PTFE (polytetrafluoroethylene), thermosetting plastics such as phenol-formalin and / or melamine resins (see, for example, Prof. R. Vieweg "Plastics Manual" X, p.
  • polypropylene polyethylene
  • ABS acrylonitrile butadiene styrene
  • polycondensates e.g. polycarbonates, aromatic and / or aliphatic polyamides, polyesters, aromatic and / or aliphatic polyamides or Polyamide imides and their mixture or cocondensates.
  • the polymer plates In individual cases, the polymer plates must be swollen with a suitable swelling agent before metallization.
  • solutions of a mixture of halides of elements of the 1st and / or 2nd main group of the periodic table with salts of weak inorganic bases and strong inorganic acids are used.
  • Suitable halides of elements of the 1st and 2nd main group are in particular the chlorides; LiCl, BeCl 2 , MgCl 2 and CaCl 2 are preferred.
  • Suitable salts of weak bases and strong acids are sulfates, nitrates and especially chlorides of metals of the 3rd and 4th main and subgroups as well as base metals of the 6th-8th Subgroup.
  • FeCl 2, FEC1 3, TiCl 3, TiCl 4, BCI 3 and in particular AICI 3 are preferred.
  • Suitable swelling agents and solvents are those as described in conventional manuals on polyamides (see, for example, “Die Polyamide von Hopff. Müller, Wegner, Springer-Verlag (1954), and“ Polymer Handbook ”by Brandrup et al. New York, Volume IV (1975) and «Vieweg / Müller Plastic Handbook; Volume IV (1966)).
  • Examples include: low aliphatic and araliphatic alcohols, such as. B. methanol, ethanol, isopropanol, n-propanol, n-butanol, benzyl alcohol and phenylethyl alcohol. Methanol is particularly preferred.
  • Dimethyl sulfoxide and amide group-containing solvents such as formamide and dimethylformamide are also suitable. Mixtures of these solvents can of course also be used.
  • a particularly preferred swelling agent system is a solution of CaCl 2 / AICI 3 mixture in methanol.
  • conventional polyamide plasticizers 0.2-10% by weight or 0.5-5% by weight, based on the total amount of liquid
  • examples include benzenesulfonic acid monoethylamide, p-toluenesulfonic acid amide, dioxide diphenyl sulfone and dibenzyl alcohol.
  • the “activation” and “acquiring” operations can be combined by dissolving the activator in the swelling agent and using this system.
  • this variant is preferably carried out by immersing these polymers in an organic, preferably anhydrous, solution such as THF (tetrahydrofuran), benzene and toluene, which additionally contains an alkali organic compound with a solitary, contains capable of forming a pair of electrons capable of carbanion or carbcation.
  • an organic, preferably anhydrous, solution such as THF (tetrahydrofuran), benzene and toluene, which additionally contains an alkali organic compound with a solitary, contains capable of forming a pair of electrons capable of carbanion or carbcation.
  • THF tetrahydrofuran
  • benzene and toluene which additionally contains an alkali organic compound with a solitary, contains capable of forming a pair of electrons capable of carbanion or carbcation.
  • naphthalene sodium, naphthalene lithium, benzollite hium, benzene sodium, biphenyl, triphenyl and butyl lithium or sodium are particularly preferred.
  • concentration of the alkali organic compounds should be 0.01 to 250, preferably 2.5-100, particularly preferably 5-75 g per liter of solvent.
  • thermosets based on phenolic, epoxy and melamine resins which can also be used to produce base materials according to the invention, can of course be coated with an adhesion promoter (see, for example, G. Hermann, printed circuit boards, manufacture and preparation. Pp. 164-168, Eugen G. Lenze Verlag , Sauigau / Württ. (1978)), which contains a rubber-elastic component.
  • an adhesion promoter see, for example, G. Hermann, printed circuit boards, manufacture and preparation. Pp. 164-168, Eugen G. Lenze Verlag , Sauigau / Württ. (1978)
  • they can be dissolved in solvents or swelling agents customary for the ABS polymers (see, for example, “Polymer Handbook Brandrup et al. New York, Volume IV (1975)) or in oxidizing media are treated.
  • the pretreated and activated base plates have to be sensitized by reduction.
  • the reducing agents customary in electroplating such as hydrazine hydrate, formaldehyde, hypophosphite or boranes, can preferably be used for this purpose. Of course, other reducing agents are also possible.
  • the reduction is preferably carried out in aqueous solution. However, other solvents such as alcohols, ethers, hydrocarbons can also be used. Of course, suspensions or slurries of the reducing agents can also be used.
  • the surfaces sensitized in this way can be used directly for electroless metallization. However, it may also be necessary to rinse the surface of the reducing agent residues.
  • a very particularly preferred embodiment of the method according to the invention consists in that the reduction in the metallization bath is carried out immediately with the reducing agent of the electroless metallization. This version represents a simplification of the electroless metallization that was previously not possible.
  • This embodiment is very particularly suitable for the nickel baths containing amine borane or copper baths containing formalin, which are preferably used.
  • the first is characterized in that the non-masked areas on the semi-finished product are removed with the etching solution. In this way, printed circuit boards with a relatively thin metal coating, namely a maximum of 10 ⁇ m, are obtained.
  • the preferred procedure consists in galvanically strengthening the non-masked areas up to a maximum of 50 J.l.m and then optionally protecting them with a tin layer before the mask and the underlying thin layer layer are removed with the aid of an etching solution.
  • the metal layers deposited using said method can also be developed in a grid-like manner using the differential etching method.
  • Plastic plate made of polyamide-6 is activated for 5 minutes in a solution of 1 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride palladium (11) chloride in 1 1 CH 2 Cl 2 at room temperature (RT), dried and in a bath which contains, treated for 5 minutes at RT. The plate is then made up in a bath Sensitized for 5 min at RT, rinsed with distilled water and then copper-plated in a commercially available copper plating bath at 30 ° C. up to a metal layer of approx. 1 ⁇ m.
  • the thin-layer plate produced in this way is covered with the aid of a screen printing varnish based on a styrene-butadiene copolymer, which has free comb-shaped webs of about 500 ⁇ m in width, and then in a bath which consists of exists, treated for 10 minutes.
  • a plated-through circuit board with 500 ⁇ m wide and 4.0 ⁇ m thick conductor tracks is obtained.
  • the metal coating adheres so well to the substrate surface that it cannot be removed from the polymer surface despite a 1-minute post-treatment at 265 ° C in a drying cabinet.
  • a 200 x 200 x 1 mm commercial rubber-grafted polyamide 6 plate is provided with 0.2 mm holes in a bath of 1 liter.
  • CH 2 C1 2 and 0.9 g mesityl oxide-palladium chloride activated in the course of 4 minutes at 18 ° C., dried, in a bath
  • Example 2 treated at 20 ° C for 5 minutes, sensitized according to Example 1 and then copper-plated by chemical means in a commercially available copper plating bath.
  • the thin-layer printed circuit board produced in this way is sprayed with a UV-curable lacquer based on oligomeric 1,4-polyisoprene (approx. 5% by weight in xylene) from Agfa Gevaert AG, Leverkusen) and then dried. After a week, the surface of the semi-finished product is covered with a photo mask and partially crosslinked with the help of UV radiation. The non-crosslinked prepolymer part is removed from the test specimen in methanol (very pure) after the mask has been removed. The thin-layer plate is then removed in a bath at 25 ° C developed pictorially.
  • a plated-through circuit board with 40 ⁇ m wide and 7.5 ⁇ m thick conductor tracks is obtained.
  • the peel strength of the metal pad measured according to DIN 53 494 is approx. 60 N / 25 mm and passes the 15 second solder bath test at 255 ° C.
  • a 200 x 200 x 1 mm large commercially available polytetrafluoroethylene film is provided with standard holes and in a solution which consists of is prepared, pretreated for 5 minutes.
  • the plate is then washed neutral with methanol and then in a bath which is made of
  • 1,000 ml CC1 2 CHCI, treated at 30 ° C for 6 minutes and then dried.
  • the plate activated in this way is in a bath which is made of exists at RT for 5 min. sensitized, washed and then nickel-plated in a standard nickel plating bath.
  • test specimen After about two minutes, the test specimen turns silver-gray and after about 20 minutes an electrically highly conductive Ni coating is deposited, which is reinforced to 3.5 ⁇ m with galvanic silver.
  • the thin-layer plate produced in this way is coated with a UV-curable resist lacquer, dried and then covered with a photomask or partially crosslinked with the aid of UV radiation.
  • the non-crosslinked prepolymer portion is removed from the base material in a commercially available developer solution after removal of the mask.
  • the plate is then post-treated in the metal etching solution specified in Example 1.
  • a 200 x 300 mm aromatic polyimide film (Kapton (R) ) is provided with holes according to Example 1, in a solution which consists of 1.0 g of 4-cyclohexene-1,2-dicarboximide palladium chloride and 1 liter. CH 2 C1 2 is activated, sensitized according to Example 1, metallized and then the metal coating developed according to Example 2.
  • a printed circuit board is obtained, the metal coating of which adheres so well to the substrate surface that it cannot be removed from the polymer surface despite a 1-minute aftertreatment in a commercial solder bath at 250 ° C.
  • a 100 x 100 x 1 mm 40% mineral filler-reinforced polymer plate made of polyamide-6 is made in a bath from 0.8 g of 4-cyclohexene-1,2-dicarboxylic acid imide-palladium (II) chloride, 1 500 ml of methanol, 120 g CaC1 2 and 3 g AICI 3 adhesive activated at 30 ° C for 5 minutes.
  • the plate is then sensitized in a bath consisting of 1 200 ml of ethanol, 24 ml of NH 3 solution (25%) and 500 ml of 2N-DMAB (dimethylamine borane) solution, washed for 5 minutes, in a commercially available wet-chemical copper plating bath an approx.
  • the polymer-metal composite in methylene chloride is freed from the polymeric resist coating and 35 minutes in a Cu etching solution consisting of 100 ml HCl (37%), 30 ml H 2 0 2 (40%) and 1,000 ml H 2 0 treated.
  • An electrical circuit board is obtained with continuous conductor tracks 200 ⁇ m wide and approx. 42 ⁇ m thick, consisting of approx. 5 4 m chemical and approx. 35 ⁇ m galvanic copper or approx. 1 ⁇ m galvanic tin.
  • the metal coating adheres so well to the substrate surface that it cannot be removed from the polymer surface despite a two-hour aftertreatment at 160 ° C.
  • a perforated polyamide plate is activated in accordance with Example 5 and a UV-curable resist film (LN ® Nylotron BASF AG) coated. Now the substrate surface is covered with a mask, partially cross-linked with the aid of UV radiation. The non-crosslinked prepolymer part is removed from the plate surface after removal of the mask by treatment with 1,1,1-trichloroethane.
  • the test specimen according to Example 1 is then swollen in a methanolic solution, sensitized, rinsed with distilled water and then partially copper-coated in a commercially available copper plating bath at 60 ° C. up to a metal coating of approximately 17.5 ⁇ m.
  • a finished printed circuit board is obtained, the copper layer of which adheres so well to the surface of the board that it cannot be removed from the board surface despite a one-day post-heating at 140 ° C.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Paper (AREA)
  • Ultra Sonic Daignosis Equipment (AREA)
  • Auxiliary Devices For Music (AREA)
  • Luminescent Compositions (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Control Of Electric Motors In General (AREA)
  • Networks Using Active Elements (AREA)
  • Emergency Protection Circuit Devices (AREA)

Claims (3)

1. Procédé de production de plaquettes de circuits imprimés par métallisation par voie chimique humide de plaquettes de support à l'aide d'activateurs organométalliques, caractérisé en ce que :
a) on active les plaquettes de support sans décapage préalable avec une solution de 0,01 à 10 g/I d'un composé complexe de palladium, d'or, de platine ou d'argent avec un diène conjugué, une cétone à non-saturation α,β, l'anhydride d'acide 4-cyclohexène-1,2-dicarboxylique ou l'imide d'acide 4-cyclohexè- ne-1,2-dicarboxylique,
b) on applique sur les plaquettes ainsi activées par voie chimique humide sans passage de courant ou, de façon combinée par voie chimique humide sans passage de courant et par voie galvanique, une couche de métal électroniquement conductrice d'une épaisseur de couche de 0,05 à 10 µm et ayant une résistance à l'arrachement selon la norme DIN 53 494 d'au moins 25 N/25 mm et
c) on poursuit le traitement des plaquettes de support ainsi métallisées, c'est-à-dire les demi- produits, d'une manière classique jusqu'à l'obtention de plaquettes de circuits imprimés.
2. Procédé suivant la revendication 1, caractérisé en ce que le système activateur contient en outre un agent gonflant pour les plaquettes de support.
3. Procédé suivant la revendication 1 ou 2, caractérisé en ce que l'agent gonflant est une solution méthanolique de CaCI2/AICI3.
EP85107381A 1984-06-26 1985-06-14 Procédé de fabrication de plaques pour circuits imprimés Expired EP0166327B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85107381T ATE39367T1 (de) 1984-06-26 1985-06-14 Verfahren zur herstellung von leiterplatten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3423457 1984-06-26
DE19843423457 DE3423457A1 (de) 1984-06-26 1984-06-26 Verfahren zur herstellung von leiterplatten

Publications (3)

Publication Number Publication Date
EP0166327A2 EP0166327A2 (fr) 1986-01-02
EP0166327A3 EP0166327A3 (en) 1986-10-08
EP0166327B1 true EP0166327B1 (fr) 1988-12-21

Family

ID=6239138

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85107381A Expired EP0166327B1 (fr) 1984-06-26 1985-06-14 Procédé de fabrication de plaques pour circuits imprimés

Country Status (6)

Country Link
EP (1) EP0166327B1 (fr)
JP (1) JPS6118195A (fr)
AT (1) ATE39367T1 (fr)
DE (2) DE3423457A1 (fr)
ES (1) ES8700538A1 (fr)
FI (1) FI852488L (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4576685A (en) * 1985-04-23 1986-03-18 Schering Ag Process and apparatus for plating onto articles

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1696603A1 (de) * 1967-01-03 1972-01-05 Photocircuits Corp Katalytische Materialien und Verfahren zu deren Herstellung

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA956294A (en) * 1973-03-14 1974-10-15 Stanley J. Whittaker Rotary valve
JPS5694690A (en) * 1979-12-27 1981-07-31 Asahi Chemical Ind Method of manufacturing thick film fine pattern
DE3148280A1 (de) * 1981-12-05 1983-06-09 Bayer Ag, 5090 Leverkusen Verfahren zur aktivierung von substratoberflaechen fuer die stromlose metallisierung
DE3324767A1 (de) * 1983-07-08 1985-01-17 Bayer Ag, 5090 Leverkusen Verfahren zur aktivierung von substraten fuer die stromlose metallisierung

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1696603A1 (de) * 1967-01-03 1972-01-05 Photocircuits Corp Katalytische Materialien und Verfahren zu deren Herstellung

Also Published As

Publication number Publication date
JPS6118195A (ja) 1986-01-27
FI852488L (fi) 1985-12-27
EP0166327A2 (fr) 1986-01-02
DE3423457A1 (de) 1986-01-02
ATE39367T1 (de) 1989-01-15
ES544533A0 (es) 1986-10-16
EP0166327A3 (en) 1986-10-08
DE3566905D1 (en) 1989-01-26
FI852488A0 (fi) 1985-06-24
ES8700538A1 (es) 1986-10-16

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