EP0804865A1 - Fabrication de plaquettes de circuits electriques - Google Patents

Fabrication de plaquettes de circuits electriques

Info

Publication number
EP0804865A1
EP0804865A1 EP96900386A EP96900386A EP0804865A1 EP 0804865 A1 EP0804865 A1 EP 0804865A1 EP 96900386 A EP96900386 A EP 96900386A EP 96900386 A EP96900386 A EP 96900386A EP 0804865 A1 EP0804865 A1 EP 0804865A1
Authority
EP
European Patent Office
Prior art keywords
adhesive
track
ink
conductive ink
conductive
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.)
Ceased
Application number
EP96900386A
Other languages
German (de)
English (en)
Inventor
Michael Anthony Cockett
Wrenford John Thatcher
Robert William Courtney
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.)
Coates Brothers and Co Ltd
Original Assignee
Coates Brothers and Co Ltd
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
Priority claimed from GBGB9501069.0A external-priority patent/GB9501069D0/en
Priority claimed from GBGB9504879.9A external-priority patent/GB9504879D0/en
Application filed by Coates Brothers and Co Ltd filed Critical Coates Brothers and Co Ltd
Publication of EP0804865A1 publication Critical patent/EP0804865A1/fr
Ceased legal-status Critical Current

Links

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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/102—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by bonding of conductive powder, i.e. metallic powder
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1258—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by using a substrate provided with a shape pattern, e.g. grooves, banks, resist pattern
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0263—Details about a collection of particles
    • H05K2201/0272—Mixed conductive particles, i.e. using different conductive particles, e.g. differing in shape
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/09—Shape and layout
    • H05K2201/09818—Shape or layout details not covered by a single group of H05K2201/09009 - H05K2201/09809
    • H05K2201/09863—Concave hole or via
    • 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
    • H05K2203/04—Soldering or other types of metallurgic bonding
    • H05K2203/0425—Solder powder or solder coated metal powder
    • 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
    • H05K2203/0568—Resist used for applying paste, ink or powder
    • 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
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
    • H05K3/0023—Etching of the substrate by chemical or physical means by exposure and development of a photosensitive insulating layer
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/107—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by filling grooves in the support with conductive material

Definitions

  • the present invention relates to a process for forming a conductive path during the production of electrical circuit boards, such as printed circuit boards, and conductive ink for use in this process.
  • electrically conductive paths upon printed circuit boards and the like have generally been manufactured by a subtractive method (i.e. by etching away undesired portions of a layer of electrically conductive material - typically copper extending over the surface of a board) or by an additive method (i.e. by building up sequential layers of conductive and dielectric materials upon a substrate).
  • the subtractive method normally begins with a substrate to which a conductive layer of copper or some other metal has been applied.
  • circuit components are produced by masking the areas of copper or metal required to make up the circuit with a protective layer, usually referred to as resist.
  • a protective layer usually referred to as resist.
  • the substrate is sprayed with a corrosive etchant solution the unprotected areas are etched away. Those areas beneath the resist however are protected by it and so remain on the substrate.
  • the resist layer is then stripped away using a suitable solvent or caustic stripping solution to reveal the desired circuit pattern.
  • the resist layer pattern may for example be defined using a silk printing screen.
  • the resist pattern may also be produced by exposing a photosensitive resist layer to UV radiation through a suitable piece of art-work, such that the pattern required to define the circuit is rendered insoluble in dilute alkaline solutions.
  • the areas not required to define the circuit are soluble in the dilute alkaline solution and so may be washed away, leaving or "developing" the resist in the pattern of the circuit required.
  • the resists used in this application are then generally stripped in caustic solutions.
  • One specific type of additive process is commonly known as conductive polymer thick film (PTF). This utilises metal filled (PTF) inks to define conductive circuit tracks.
  • Some other additive processes include the use of metal filled inks.
  • the need to ensure that such metallic inks are firmly bonded to the substrates employed means that a fairly high percentage of adhesive resin needs to be included to affect the said bonding.
  • the high bonding resin content limits the electrical conductivity.
  • WO 90/12482 One proposal for the combination of additive and subtractive type of process is disclosed in WO 90/12482.
  • a non-conductive substrate is coated with a film of vacuum sputtered metal.
  • This is then coated with a photosensitive resin which is selectively exposed and developed to produce the desired circuit pattern etched into the surface of the resist.
  • the areas of sputtered metal bared by this process are then plated up with copper by electrodeposition to produce circuit tracks of the desired thickness.
  • the photosensitive resist is then stripped and the sputtered metal layer flash etched away to yield the desired circuit pattern.
  • further layers of circuitry may be added by sequentially adding further layers of photosensitive material and sputtered metal and repeating the electrodeposition and etching processes.
  • WO 93/06943 A more recent proposal for an additive process is described in WO 93/06943 This is based on the use of a conductive ink including an adhesive resin, as alluded to above.
  • the ink is a mixture of a relatively high melting point metal powder, solder powder, a cross linking flux and a reactive monomer or polymer.
  • the reactive monomer or polymer system acts as an adhesive for bonding the ink to the substrate after curing/drying.
  • the flux may be selected so as only to be activated at a predetermined elevated temperature.
  • a conductive ink comprising a mixture of metals which can be sintered together to form a highly conductive circuit or layer.
  • Such systems do have improved conductivity but generally suffer from problems related to the sintering process. This depends very much on the type of 'flux' or wetting agent used to aid the sintering (or reflow) of the said metal particles.
  • the flux needs to remove the oxides formed enabling the sintering process to take place, especially if the composition includes metals which are readily oxidised such as copper. Furthermore copper oxide is a poor electrical conductor.
  • Typical fluxes are organic and inorganic acids and salts thereof such as stearic acid, hydrochloric acid, amine hydrochlorides and amine resins.
  • Weak fluxing agents for example stearic acid (and other organic acids) do not clean the large surface areas of the finely divided metal powders adequately. Therefore strong fluxing agents are required, amine hydrochlorides are an example, but these strong fluxes often have harmful affects on the final composition such as reduction of adhesion and long term stability
  • WO 93/06943 seeks to overcome this disadvantage by using a flux which is only activated at the solder melt temperature.
  • a flux which is only activated at the solder melt temperature.
  • the method described in the latter document still presents a number of disadvantages.
  • the high level of organic material incorporated in the conductive ink lowers the conductivity of the final circuit.
  • the special temperature sensitive flux yields water during the heating process, leading to bubbling, and hence voids as curing and reflow/sintering progress. The voids lead to even lower conductivity or possibly, total fracture of the inter-component wiring lines formed as a result of the process.
  • This method makes it possible to form an additive conductive path of an electrical circuit board, whereby good adhesion of applied metallic formulations can be achieved without the damaging effects resulting from the inclusion of reactive monomer or polymer in the conductive ink.
  • the method generally involves applying an adhesive to a circuit board substrate and applying a conductive ink over the adhesive in a pattern corresponding to the conductive path.
  • the conductive ink may be held in place by the creation of a track in a surrounding dielectric material.
  • a first aspect of the present invention now provides a method of forming a conductive path of an electrical circuit board, the method comprising applying an adhesive to a circuit board substrate and applying a conductive ink over the adhesive in a pattern corresponding to the conductive path.
  • a second aspect of the present invention provides a method of forming a conductive path of an electrical circuit board, the method comprising applying a photoimageable layer to a circuit board substrate, subjecting the photoimageable layer to a photoimaging and developing process to form a track in the photoimageable layer, the track corresponding to the said conductive path, and introducing a conductive ink into the track to form a conductive ink pattern.
  • the track is formed with an undercut region in side walls thereof. This is especially advantageous in holding the conductive ink in place, by means of a mechanical dovetail arrangement.
  • the system provided by the first aspect of the present invention, as well as other aspects of the present invention which will be defined herein below, enables processing of circuits on any base substrate with adequate thermal stability, for example, coated aluminium, aluminium oxide, ceramic or glass substrates.
  • coated aluminium, aluminium oxide, ceramic or glass substrates offer advantages to the process of circuit manufacture in terms of temperature stability and recycling potential of the completed circuit at the end of its normal life.
  • coated aluminium/aluminium oxide offers significant advantages, especially in chip on board (COB) and similar applications where planarity of the final surface and/or thermal management problems need to be addressed.
  • the present invention in all its aspects is suitable for forming a single conductive path (wiring line) on a substrate or a more complicated wiring pattern comprising a network of wiring lines included at two or more layers known as a "multilayer circuit" .
  • the method of the first aspect of the present invention preferably comprises a subsequent step of heating the conductive ink pattern to effect a bond to the adhesive and simultaneously to improve the bond between the adhesive and the base material: followed by the reflow or sintering of metallic component(s) thereof. A preferred way of effecting this heating step is described in more detail herein below.
  • the conductive ink can be applied in the desired pattern by means of a stencil-type arrangement, which is removed before the heating step.
  • a silk-screen printing process could be used.
  • the pattern by the further step, after application of the adhesive, of applying a photoimageable layer over the adhesive, subjecting the photoimageable layer to a photoimaging and a developing process to form a track in the photoimageable layer, the track corresponding to the required conductive path (i.e. intercompo ⁇ ent wiring), and introducing the conductive ink into the track prior to the heating step.
  • the track formed in the developed photoimageable layer can be formed with side walls which become further apart, the greater the depth from the upper surface of the photoimageable layer.
  • the track is formed with an "undercut”. This provides a dovetail anchor for the solid conductive material formed after sintering of the ink.
  • a second aspect of the present invention provides a method of forming a conductive path of an electrical circuit board, the method comprising applying a photoimageable layer to a circuit board substrate, subjecting the photoimageable layer to a photoimaging and developing process to form a track in the photoimageable layer, the track corresponding to the said conductive path and being formed with an undercut region in side walls thereof, and introducing a conductive ink into the track.
  • the process according to the second aspect of the present invention is preferably followed by a step of heating the conductive ink in the track, to effect bonding of the ink to the adhesive and reflow or sintering of a metallic component thereof.
  • a preferred embodiment of the first and/or second aspect of the present invention provides the following steps:-
  • the substrate Subjecting the substrate to suitable heat treatment to cause the conductive ink to melt and coalesce to form a coherent conductive pattern on the substrate, contained, protected and anchored by the photocurable resist layer. Subsequently, the tracks formed may be soldered or plated to give them protection against oxidative attack.
  • the heating process not only reflows the conductive ink, but also causes the thermal cure of the resist layer and the adhesive bonding layer which is simultaneously cured, attaching the conductive track to the base substrate while remaining insulated from it; and 6. Stripping the surface of extraneous conductive ink either by chemical means, or mechanical abrasion.
  • resists i.e. materials for forming the photoimageable layer
  • those resists which are developable by application of a solution of an alkali or of an organic solvent.
  • soldermasks are typically those used for the preparation of photoimageable solder masks and many materials which are commercially available as soldermasks may be used as the dielectric resist in this invention.
  • Typical of these soldermasks are the liquid products sold as ImagecureTM by Coates, ProbimerTM by Ciba and PSR 4000TM by Taiyo or dry film products sold, for example, by Dupont, Morton Thiokol, Hitachi and others.
  • the liquid products are supplied as two pack systems although single pack systems such as those described in patent GB-1-2 032 939 may also be used.
  • a typical formulation for this type of material comprises from 50 to 60% epoxy novolak acrylate resin solution, from 3 to 5% photoreactive monomers, from 4 to 6%.photoinitiators, from 25 to 30% inorganic fillers, optionally from 2 to 5% pigment and optionally from 0.5 to 2% defoamers and flow aids. Wherever used herein, unless indicated to the contrary, all percentages are percentages by weight.
  • a second cross linking component may be added.
  • a typical cross linking agent is made up of an unreacted epoxy resin and cure catalyst dissolved in a solvent and optionally filled with one or a number of inorganic filler materials.
  • Alkali soluble versions of such resists are typically based on a carboxylated epoxy novolak acrylate resin, produced by reacting an epoxy novolak resin with a mixture of saturated and unsaturated monocarboxylic acids. The hydroxyl groups formed by this reaction are then used to react dicarboxylic acid anhydrides onto the polymer, ring opening them to give free carboxylic acid groups. These confer solubility in mild alkali solutions on the material. This resin is dissolved in an organic solvent in a mixture with radiation sensitive oligomeric materials, photoinitiators, fillers, flow aids, pigments an defoamers.
  • the carboxylated epoxy novolak acrylate resin referred to in the preceding paragraph may be the reaction product of an epoxy phenol or cresol novolak with a mixture of acrylic, methacrylic, hexanoic or benzoic acids, which may have been carboxylated with maieic, succinic, thetrahydro- or hexahydrophthalic anhydrides. Properties may be further enhanced by the incorporation of further organic acids.
  • the resin being dissolved in a suitable solvent such as propylene glycol diacetate, propylene glycol methyl ether acetate, ethyl ethoxy propionate or dipropylene glycol methyl ether acetate.
  • the thermal hardening component of the resist typically comprises from 35 to 50% epoxy resin, from 15 to 30% inorganic filler and from 1 to 7% thermal curing catalyst, the balance being solvent.
  • the epoxy resin may be an epoxy novolak resin or a bis-phenol A type epoxy resin like Epikote 1004 (Shell Chemicals).
  • Inorganic fillers which may be used are barium sulphate, talc and silica.
  • the thermal cure catalyst may be an amine compound such as diamino diphenyimethane or dicyandiamide and the solvent may be a glycol ether or ester such as propylene glycol monomethyl ether acetate.
  • Formulations for suitable photoimagable systems may be as described in GB-A-2 175 908.
  • the photoimageable resist layer may be applied by a variety of means including screen printing, roller coating, dry film lamination, curtain coating or spray.
  • the photoimageable resist material will usually comprise a photoinitiator, especially one of a type which preferentially hardens the surface of the photoimageable layer.
  • a photoinitiator especially one of a type which preferentially hardens the surface of the photoimageable layer.
  • the use of such materials helps to emphasis the definition of the undercut in the track formed in the developed photoimageable material.
  • Another way of forming a relatively hardened "skin" over the upper surface and undercut walls of the developed photoresist layer is to incorporate therein, a pigment or other solid material for limiting penetration of UV radiation into the body of the layer.
  • a pigment or other solid material for limiting penetration of UV radiation into the body of the layer.
  • it is otherwise desirable that no pigmentation be used in the resist formulation It can easily be shown that pigments impede the extent of through cure of the photoreactive layer, which may be applied in thicknesses exceeding 75 microns.
  • solvent(s), from the coating process may remain trapped beneath the surface due to the rapid surface cure of a pigmented system. These solvents can later cause catastrophic blistering and wrinkling of the resist layer during conductive ink reflow.
  • the through cure must be such as to leave deliberately undercut side walls thereby entrapping the inserted conductive ink.
  • any excess metal of the wiring lines, above the plane of the upper surface of the circuit board may be removed by appropriate chemical or physical treatment, at the same time removing an upper layer of the laminated photoimageable resist layer to leave a smooth surface.
  • the adhesive, photocurable resist material and photoimageable material may all be applied by any suitable process such as screen printing, curtain coating, electrostatic or airless spraying or roller coating.
  • the adhesive material used to attach the conductive ink to the substrate in the method according to the first or optionally the second, aspect of the present invention may be of a wide range of chemical types. Especially preferred are those which show good thermal stability and a degree of reactivity to epoxy, phenolic or carboxylic acid group containing materials. Materials which typically may be used in this application are; epoxy resins, epoxy acrylates or carboxylates, high melting point polyamide resins mixed with epoxy resins, together with a suitable cure catalyst. These epoxy resins may be materials such as epoxy novolaks or bisphenol-A epoxy resins. These materials are dissolved in organic solvents to render them coatable. In any event, the adhesive may be a single component adhesive or a two-component adhesive system.
  • Third components are as recited in the preceding paragraph but in any-event, generally speaking epoxy resin, novolak resins, epoxy novolak resins, acrylate resins and polyamide resins are generally preferred, together with a catalyst for effecting curing of said resin at an elevated temperature.
  • carboxylated epoxy acrylate resins such as those used for the preparation of soldermasks.
  • High melting point polyamides are also much preferred, such as Versamid 1 15 (Cray Valley) dissolved in butanol or toluene, also epoxy novolak resins, such as Quatrex 2410 produced by Dow Chemicals.
  • bisphenol-A type epoxy resins such as Epikote 1001 (Shell Chemicals), dissolved in propylene glycol diacetate or other suitable solvent.
  • the adhesive composition is made up of a 60 to 70% solids solution of the adhesive resin in solvent.
  • Suitable thermal cure catalysts for the polyamide- epoxy mixture are dicyandiamide and Epikure 143FF (Shell Chemicals).
  • the thickness of adhesive coating needs to be limited so that it forms a suitable dielectric layer if a conductive base or substrate (such as aluminium) is used but not so thick that it penetrates to an excessive extent into the conductive ink formed thereon and reduces the electrical conductivity of that ink.
  • Preferred adhesive coating thicknesses are in the range of from 4 to 15 most preferably from 8 to 12 microns.
  • the conductive ink is made up of metal powders rendered to a printable consistency by the addition of liquid fluxes, which will later allow the molten ink to melt and coalesce to give a coherent metallic track
  • the condu ⁇ ive ink material typically contains 75% total metal powder (e.g. made up of 25% copper powder with 25% each of silver or tin-lead powder), 17% flux material and 8% of a volatile solvent.
  • the metal powders used typically have a particle size range of 5-15 microns.
  • the flux materials used may be of a proprietary type, such as Alpha flux 850TM (Alpha Metals) or a simple chemical such as glycerol phthalate.
  • the volatile solvent is added to make the ink more mobile and to promote wetting and may be for example acetone, ethanol, methyl ethyl ketone, propylene methyl ether acetate or a high boiling aromatic solvent for example.
  • the ratio of sizes of the metal powders as well as their composition is of particular significance; this relates to the surface area to be wetted out by the flux and consequently influences both the reflow properties and the final conductivity of the reflowed metal paste.
  • the relatively low melting point component of the conductive ink preferably has a melting point in the range of from 100°C to 250°C and the relatively high melting point component has a melting point in the range of from 300°C to 1455°C.
  • the relatively low melting point component comprises at least one metal selected from tin, lead, silver, bismuth, antimony and indium or an alloy of at least any two or more of such metals.
  • the relatively high melting point component comprises at least one metal selected from tin, silver, copper, zinc, iron, manganese, nickel and cobolt or an alloy of at least any two or more of such metals.
  • the resulting wiring line After elevating the ink to the second temperature, greater than the melting point of the relatively lower melting point component, the resulting wiring line has a higher melting point than that of the aforementioned relatively lower melting point component.
  • Such a line is capable of being conventionally soldered, either with or without prior electroless or other metallic plating.
  • the heating step is preferably effected by progressively raising the temperature of the conductive ink such that the ink dries at a first temperature and then the metallic component sinters or melts at a second temperature, higher than the first temperature.
  • the advantages of this progressive heating process can be realised if the ink has a metallic component supported in a flux component and comprises a mixture of metals or alloys, having a relatively low melting point component and a relatively high melting point component.
  • the adhesive is applied to a thickness of 8 - 12 microns by screen printing, using a fine mesh typically 150T/cm.
  • the coating may also be applied by other means such as roller coating, dip coating or spray. It is unlikely that under most conditions, curtain coating could render a sufficiently thin film reliably, although this is not excluded from the ambit of the present invention.
  • any flux component of the conductive ink comprises a wetting agent and a reactive agent capable of reacting with copper.
  • the flux it is better for the flux to be made incorporating the wetting agent but excluding the reactive agent, which is then added immediately prior to application.
  • the conductive ink for use in the method according to the first or the second aspect of the present invention differs from that utilised in the method described in WO 93/06943.
  • a third aspect of the present invention provides an electrically conductive composition comprising a metallic component and a flux, the composition being substantially free of any resin or reactive monomer or polymer.
  • the composition according to the third aspect of the present invention is completely free of any resin or reactive monomer or polymer.
  • the metallic component is preferably a metal powder having a composition as hereinbefore described in respect of the first and second aspects of the present invention and the flux is preferably also as hereinbefore described in that context.
  • the term "substantially free of an reactive monomer or polymer” preferably means that the amount of (i) resin; or (ii) reactive monomer or polymer; or (i) + (ii) may be independently selected from within a range up to a maximum of any of 25%, 20%, 15%, 10%, 7.5%, 5%, 2.5%, 2%. 1%, 0.75%, 0.5%, 0.25%, 0.2%, 0.1%, 0.05%, and 0.01% by weight of the total composition.
  • Figure 1 shows a cross-section through a conductive track on a circuit board substrate, the conductive track being formed by a method according to the present invention.
  • a circuit board 1 comprises a board substrate 3, e.g. formed of aluminium or aluminium oxide. Upon an upper surface 5 of this substrate 3 is formed a base adhesive/dielectric layer 7.
  • a layer of photoimageable resist 9 is then formed on the adhesive layer 7 and photoimaged to define a pattern for the paths 11 of the circuit board wiring.
  • the developing/processing of the imaged resist layer 9 leaves etched-away tracks 13 therein.
  • the side walls 15, 17 of each such track 13 become further apart, the deeper the distance from the upper surface 19 of the resist layer 9, towards the adhesive layer 7 In other words, undercuts 21, 23 are defined by these side walls 15, 17
  • Conductive ink 25 is then introduced into each such track 11 and subjected to a progressively increasing temperature to cure the ink to the adhesive layer and/or sinter the metal particles 27 therein.
  • the resist layer 9 is preferred to form the resist layer 9 as a plurality of discrete layers so that as a final step after cooling, the upper layer (having the surface layer 19 thereon) can be removed together with any excess metal proud of the upper surface 29 of the solid wiring line.
  • the resultant circuit pattern had an electrical resistivity of 500 10" ⁇ ohmscms. This was then exposed to a temperature of 215°C for 3 minutes and dipped into molten solder at 265°C for 2-3 seconds to give a continuous circuit track with very low electrical resistivity ( ⁇ 10"5 ohms cm).
  • XV501TSM (Imagecure - Registered Trade Mark) was silk screen printed through a 90T mesh, onto a piece of glass epoxy circuit base, and dried for 20 minutes at 90°C to give a thickness of about 8 microns.
  • the resultant circuit pattern had an electrical resistivity of 500 x 10" ⁇ ohmscms. This was then immersed for 10 minutes in commercial immersion tin electroless plating solution and then exposed to a temperature of 215°C for 3 minutes, and dipped into molten solder at
  • AlphaTM Flux 850 7.15% Use of fast drying solvent to reduce drying time and hence oxidation of copper.
  • the substrate used was anodised aluminium sheet.
  • a coating of ImagecureTM XV501 TSM was applied to the surface of the sheet to a dry thickness of approximately 75 ' microns. This photo sensitive surface was imaged to produce slots of various widths. These slots were coated with a thermoplastic resin to about 8 microns dry thickness.
  • the resultant photo imaged track pattern had a resistivity >10"-> ohm cms.
  • An adhesive formulation made up of 2 parts Epikote 828 (Shell Chemicals), 3 parts Versamid 115 (Cray Valley Products) and 5 parts propylene glycol methyl ether acetate was screen printed through a 100T mesh silk screen on to bare FR4 epoxy glass laminate. The adhesive was dried to give a dry film weight of 5-8 microns.
  • a photocurable resin was prepared by dissolving an epoxy resin (40 parts) in trimethylol propane triacrylate (30 parts), then rearting with acrylic acid (12 parts), benzoic acid (4 parts) in the presence of trace proportions of a UV inhibitor and a catalyst .
  • the resulting acrylated resin was then carboxylated using tetrahydrophthalic anhydride to give an acid value of 57mg KOH/gm. This was mixed in the following formulation (Coating A): Coating A:
  • Antifoam 0.5 SAG100, OSI
  • Coating A was screen printed through a 32T mesh silk screen and cured under a UV cure unit at an exposure level of LOOOmj/cm* ⁇ .
  • the resulting cured film was 80 microns thick.
  • a photoimageable resin was produced by reacting an epoxy resin (40 parts) dissolved in propylene glycol diacetate (30.7 parts), with acrylic acid and benzoic acid (12 parts and 3 parts respectively) in the presence of trace proportions of a UV inhibitor and a catalyst. The resulting acrylated resin was then carboxylated with tetrahydrophthalic anhydride (14 parts). This photoreactive resin was then incorporated into the following photoimagable ink formula: Material Parts
  • This formulation was printed on to the photocured layer of Coating A using a 100T mesh silk screen and dried to give a tack free finish.
  • the resultant film was 12 microns thick.
  • the resist layer was then photoimaged through suitable art work and the desired pattern developed using 0.6% w/w sodium carbonate solution at 40°C.
  • Ethanol 8 was screen printed through a 32T mesh silk screen with a soft squeegee, ensuring that the grooves in the resist surface were filled with conductive material.
  • the solvent was then driven from the ink by heating the board to 80°C for 15 minutes.
  • the completed board was then treated with a 10% w/w solution of sodium hydroxide to strip away the thin layer of photoimageable resist and any extraneous conductive ink from the board surface.
  • the completed board was then subjected to vapour phase reflow at 215°C to produce a coherent metal track system defined by the image in the resist layer, which could then be soldered.
  • the circuit produced showed good conductance and resistance to stripping of the tracks by tape testing.
  • An adhesive was prepared by dissolving 50 parts Epikote 1001 (Shell Chemicals) in propylene glycol (50 parts). This adhesive was applied by airless spraying to a piece of plain FR2 paper-phenolic laminate and dried to yield an adhesive coating of 10-12 microns thickness.
  • a photocurable resin was prepared by mixing the following constituents:
  • a photoimageable resist (ImagecureTM) was applied to the surface of the photocurable resist layer by curtain coating.
  • the ink was dried to a tack free finish by heating to 90°C for 15 minutes and then photoimaged through suitable art work.
  • the image was developed using 0.6% w/w sodium carbonate to yield a board with the desired track design etched into its surface.
  • a conductive ink of the following formulation was then forced into the tracks by drawing a soft rubber squeegee loaded with the ink across the boards surface.
  • the photoimageable layer was then stripped from the board surface by wiping with propylene glycol methyl ether acetate, taking any conductive ink overprinted on its surface with it
  • the conductive ink was then reflowed and soldered by passing the board over a solder wave at 238°C to yield a conductive, coherent track pattern showing good reproducibility of the artwork used.
  • XV501TSM (ImagecureTM) was silk screen printed through a 90T mesh onto a piece of glass epoxy laminate and dried at 90°C for 20 minutes to form an adhesive layer.
  • a conductive ink comprising
  • Isopropyl ether acetate 5 was manufactured by using a silverson H.S.S. then triple roll milled to give good wetting out of the metal and removal of air.
  • This ink was screen printed through a stainless steel mesh to give an electrical test pattern and dried for 30 minutes at 90°C.
  • the resultant circuit had a resistivity of 500 x 10"- 5 ohms cm at this stage.
  • the pattern was then reflowed at 215°C for 2-3 seconds, to give a continuous track with an electrical resistivity of less than 10"- 5 ohms cm.
  • Example 12 As for Example 12 except that the conductive ink formulation was
  • This ink could only be soldered after electroless nickel gold plating.
  • the tin lead coating on the copper reduces the tendency to oxidation, improves both the reflow and conductivity, with an improvement in solderability over Example 13

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

Un procédé, qui permet de former un chemin conducteur (11) sur un plaquette de circuit électrique (1), consiste à appliquer un adhésif (7) sur un substrat (3) puis une encre conductrice (25) sur cet adhésif (7), selon un motif correspondant au chemin conducteur souhaité (11). On peut appliquer sur cet adhésif (7) ou ce substrat une couche photosensible de formation d'image (9) et la soumettre à un processus de formation d'image et de développement. Ceci permet de former dans cette couche photosensible (9) une piste (13) correspondant au chemin conducteur souhaité (11). On introduit l'encre conductrice (25) dans cette piste (13) puis on procède à un chauffage qui polymérise l'adhésif (7) et colle l'encre conductrice (25) à la couche adhésive (7) tout en donnant une refusion ou un frittage d'un constituant métallique (27) de cette encre (25), laquelle comprend aussi un flux mais est pratiquement dépourvue de résine ou de tout monomère ou polymère réactif.
EP96900386A 1995-01-18 1996-01-18 Fabrication de plaquettes de circuits electriques Ceased EP0804865A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GBGB9501069.0A GB9501069D0 (en) 1995-01-18 1995-01-18 Electrical circuit boards
GB9501069 1995-01-18
GB9504879 1995-03-10
GBGB9504879.9A GB9504879D0 (en) 1995-03-10 1995-03-10 Circuit forming process
PCT/GB1996/000105 WO1996022670A1 (fr) 1995-01-18 1996-01-18 Fabrication de plaquettes de circuits electriques

Publications (1)

Publication Number Publication Date
EP0804865A1 true EP0804865A1 (fr) 1997-11-05

Family

ID=26306345

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96900386A Ceased EP0804865A1 (fr) 1995-01-18 1996-01-18 Fabrication de plaquettes de circuits electriques

Country Status (3)

Country Link
EP (1) EP0804865A1 (fr)
AU (1) AU4397696A (fr)
WO (1) WO1996022670A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0933010B1 (fr) * 1996-08-16 2002-01-23 Hugh P. Craig Compositions d'impression et leur application sur des surfaces dielectriques utilisees dans la fabrication de cartes de circuits imprimes
US7022266B1 (en) 1996-08-16 2006-04-04 Dow Corning Corporation Printable compositions, and their application to dielectric surfaces used in the manufacture of printed circuit boards
CN104023478A (zh) * 2014-06-27 2014-09-03 厦门大学 一种基于气流喷印的柔性电路制备方法
CN115806754A (zh) * 2022-12-07 2023-03-17 连州市祥丰化工有限公司 一种感光成像显影成型的导电油墨及其制备方法和线路板

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2959498A (en) * 1957-10-02 1960-11-08 Du Pont Conductive circuit bonded to a resinous dielectric and method for producing same
DE1128493B (de) * 1959-09-11 1962-04-26 Siemens Elektrogeraete Gmbh Verfahren zur Herstellung von gedruckten Schaltungen nach dem Pulververfahren
US3800020A (en) * 1972-03-23 1974-03-26 Cramer P Co Method of making a circuit board
DE2231614C3 (de) * 1972-06-28 1981-02-12 Du Pont De Nemours (Deutschland) Gmbh, 4000 Duesseldorf Verfahren zur Herstellung gedruckter Schaltungen unter Verwendung eines Photopolymers als Maske sowie einer leitfähigen Paste als Stromleiter und Vorrichtungen zur Durchführung des Verfahrens
DE2411988A1 (de) * 1973-03-14 1974-09-19 Du Pont Metallisierungspaste und ihre verwendung fuer die herstellung von nicht unterbrochenen mustern auf unterlagen
DE2856888A1 (de) * 1978-12-30 1980-07-17 Licentia Gmbh Verfahren zur herstellung von leiterplatten
JPS63309390A (ja) * 1987-01-12 1988-12-16 Asahi Chem Ind Co Ltd はんだペ−スト
JPH02231788A (ja) * 1989-03-03 1990-09-13 Sharp Corp 印刷配線基板の製造方法
US5376403A (en) * 1990-02-09 1994-12-27 Capote; Miguel A. Electrically conductive compositions and methods for the preparation and use thereof
JPH0417994A (ja) * 1990-05-10 1992-01-22 Asahi Chem Ind Co Ltd はんだ組成物
DE4237766A1 (de) * 1992-11-09 1994-05-11 Siemens Ag Diskretverdrahtungsverfahren für Leiterplatten und/oder elektronische Baugruppen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9622670A1 *

Also Published As

Publication number Publication date
AU4397696A (en) 1996-08-07
WO1996022670A1 (fr) 1996-07-25

Similar Documents

Publication Publication Date Title
US20060060558A1 (en) Method of fabricating package substrate using electroless nickel plating
KR100417544B1 (ko) 인쇄 회로 보드, 인쇄 회로 보드 제조 방법, 및 유전 중합체 합성물
US7910156B2 (en) Method of making circuitized substrate with selected conductors having solder thereon
JP2778323B2 (ja) プリント配線基板およびその製造方法
WO1996022670A1 (fr) Fabrication de plaquettes de circuits electriques
KR950003244B1 (ko) 다층 회로판 제조공정
US6527963B1 (en) Method of manufacturing multilayer wiring boards
EP0003363B1 (fr) Réalisation de circuits imprimés par renforcement par soudure d'images de poudres métalliques
JP2877993B2 (ja) 配線板用接着剤とこの接着剤を用いたプリント配線板の製造方法およびプリント配線板
KR100199539B1 (ko) 다층인쇄회로판을제조하는방법_
JP3138520B2 (ja) 多層プリント配線板およびその製造方法
JP2004240233A (ja) ソルダーレジスト組成物、回路基板及びその製造方法
JP2001024328A (ja) 多層配線板
WO1997036464A1 (fr) Production de plaquettes a circuits electriques
JPH06260763A (ja) 多層配線基板の製造方法
JP3298957B2 (ja) 無電解めっき用接着剤シートとこの接着剤シートを用いたプリント配線板の製造方法およびプリント配線板
JP3007648B2 (ja) 無電解めっき用接着剤プリント配線板の製造方法およびプリント配線板
GB2320728A (en) Depositing a metallic film involving pretreatment
EP0261301A2 (fr) Procédé de fabrication d'une plaque de circuit imprimé comportant des trous métallisés en travers
JP2713037B2 (ja) プリント配線板及びその製造方法
JP4301152B2 (ja) バイアホール形成金属張積層板及びスルーホール形成アンクラッド板
JPH04151895A (ja) プリント配線板への実装方法
EP0917413A2 (fr) Procédé pour favoriser l'adhésion d'encres de légende en utilisant de la lumière ultraviolette
JP3002591B2 (ja) 接着剤シートとこの接着剤シートを用いたプリント配線板の製造方法およびプリント配線板
JPH05218638A (ja) 配線板用接着剤とこの接着剤を用いたプリント配線板の製造方法およびプリント配線板

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19970724

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT

17Q First examination report despatched

Effective date: 19980209

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 19991101