WO2002083328A1 - Procede d'amelioration de l'agglomeration de compositions rigides et thermodurcissables sur du metal, et articles ainsi obtenus - Google Patents

Procede d'amelioration de l'agglomeration de compositions rigides et thermodurcissables sur du metal, et articles ainsi obtenus Download PDF

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Publication number
WO2002083328A1
WO2002083328A1 PCT/US2002/011665 US0211665W WO02083328A1 WO 2002083328 A1 WO2002083328 A1 WO 2002083328A1 US 0211665 W US0211665 W US 0211665W WO 02083328 A1 WO02083328 A1 WO 02083328A1
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WIPO (PCT)
Prior art keywords
adhesion promoting
thermosetting composition
polymer
coating
layer
Prior art date
Application number
PCT/US2002/011665
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English (en)
Inventor
Vincent R. Landi
John T. Neill
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World Properties Inc.
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Publication date
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Publication of WO2002083328A1 publication Critical patent/WO2002083328A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second 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
    • H05K3/38—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/40—Metallic substrate based on other transition elements
    • B05D2202/45—Metallic substrate based on other transition elements based on Cu
    • 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
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0133—Elastomeric or compliant polymer
    • 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
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0358—Resin coated copper [RCC]
    • 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
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
    • H05K2203/0759—Forming a polymer layer by liquid coating, e.g. a non-metallic protective coating or an organic bonding 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
    • H05K3/4655—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern by using a laminate characterized by the insulating layer

Definitions

  • This disclosure relates to printed circuit boards comprising conductive metals adhered to thermosetting substrates.
  • this disclosure relates to methods for improving the bond strength between the surface of a conductive metal and a thermosetting substrate.
  • Circuit board materials are well known in the art, generally comprising a thermosetting substrate adhered to a conductive metal surface.
  • thermosetting substrate adhered to a conductive metal surface.
  • circuit board substrates with a low dielectric constant and a high glass transition temperature.
  • the resulting circuit board material may have low peel strength between the metal layer and the substrate. Peel strength may be even more severely reduced when low or very low profile copper foils are employed, such foils also being critical to very dense circuit designs.
  • U.S. Patent No. 5,904,797 to Kwei discloses using chromium (III) methacrylate/polyvinyl alcohol solutions to improve bonding between thermoset resins and hydrophilic surfaces.
  • the chromium methacrylate chemically bonds the thermoset resin to the hydrophilic surface. While chromium methacrylate is useful for some thermoset resins, it is not useful for all, notably polybutadiene and polyisoprene resins.
  • PCT Application No. 96/19067 to McGrath discloses contacting the metal surface with an adhesion promoting composition comprising hydrogen peroxide, an inorganic acid, a corrosion inhibitor, and a quaternary ammonium surfactant.
  • PCT Application No. 99/57949 to Holman discloses using an intermediate layer comprising an organic resin, preferably an epoxy or phenoxy resin, to improve the peel strength of a laminate.
  • the intermediate layer is formed by applying a solution of the organic resin in an organic solvent and then removing the solvent.
  • Use of organic solvents requires costly air handling equipment and can have negative environmental impact.
  • a method for enhancing the adhesion between a metal surface and the surface of a curable thermosetting composition comprises contacting the metal surface with an aqueous emulsion or dispersion comprising an elastomeric polymer, drying the aqueous emulsion or dispersion to form an adhesion promoting polymer layer, contacting the adhesion promoting polymer layer with a curable thermosetting composition, and curing the thermosetting composition.
  • the emulsion or dispersion can further comprise ionic or non-ionic surfactants, viscosity modifiers, coupling agents, wetting agents, fillers, reactive monomers, anti-oxidants and cross-linking agents.
  • the adhesion promoting polymer layer may be at least partially cured before contacting with the curable thermosetting composition.
  • the aqueous emulsion or dispersion contains about 10 to about 70% solids.
  • the elastomeric polymer is a butadiene or isoprene polymer and even more preferably the butadiene or isoprene polymer is a styrene-butadiene rubber.
  • the weight of the adhesion promoting polymer layer on the metal surface after drying is about 2 to about 20 grams per square meter (g/m 2 ).
  • a circuit material comprises an adhesion promoting layer disposed between a metal layer and a thermosetting composition wherein the adhesion promoting layer comprises an elastomeric polymer.
  • the circuit material has superior bond strength when compared to circuit materials that do not employ an adhesion promoting layer comprising an elastomeric polymer.
  • Figure 1 shows an exemplary coated metal foil.
  • Figure 2 shows an exemplary coated curable thennosetting dielectric prepreg.
  • Figure 3 shows an exemplary circuit material.
  • Figure 4 shows an exemplary multilayer circuit material.
  • a method for enhancing the adhesion between a metal surface and the surface of a curable thermosetting composition comprises contacting a metal surface with an aqueous emulsion or dispersion comprising an elastomeric polymer, preferably a butadiene or isoprene polymer, drying the aqueous emulsion or dispersion to form an adhesion promoting polymer layer, contacting the adhesion promoting polymer layer with a curable thermosetting composition, and curing the thermosetting composition.
  • the emulsion or dispersion can further comprise fillers, cross-linking agents, wetting agents, coupling agents, reactive monomers, ionic or non-ionic surfactants, viscosity modifiers, anti-oxidants and combinations comprising one of the foregoing additives.
  • the adhesion promoting polymer layer may be at least partially cured before contacting with the curable thermosetting composition.
  • an "emulsion" and "dispersion” differ from a solution and describe a stable multi-phase mixture resulting from emulsion polymerization or from emulsification of a polymer solution.
  • thermosetting composition Use of an aqueous emulsion or dispersion comprising an elastomeric polymer causes a significant increase in the bond strength between the metal surface and the thermosetting composition, is environmentally friendly, and provides an adhesion promoting layer which has dielectric properties similar to the thermosetting composition.
  • the aqueous emulsion or dispersion may comprise a wide variety of elastomeric polymers.
  • Useful elastomeric polymers include polybutadiene; polyisoprene; random and block copolymers of butadiene and/or isoprene with styrene, os-methyl styrene, vinyl pyridine, acrylonitrile; acrylic-, methacrylic-, itaconic-acid and their esters such as methyl, ethyl, butyl, and glycidyl; chloroprene rubber; natural rubber; ethylene-propylene-diene monomer (EPDM); ethylene- propylene rubber (EPR); butyl rubber; styrene-isoprene-styrene triblock (SIS); styrene-(ethylene-butylene)-styrene triblock (SEBS); styrene-(ethylene-propylene)- s
  • the elastomeric polymer has a glass transition temperature at or below room temperature. While it is preferable that these elastomeric polymers and copolymers be polymerized by an emulsion method it is also within the scope of the invention to employ polymers formed in solution and later formed into a dispersion.
  • a preferred elastomeric polymer is emulsion polymerized styrene-butadiene rubber.
  • the styrene-butadiene rubber may be functionalized with any functional group capable of facilitating cross-linking.
  • the styrene-butadiene rubber is carboxylated.
  • Emulsions of styrene-butadiene rubber are available commercially such as the GOOD-RITE ® products available from oveon, Inc.
  • the commercially available emulsion may be diluted to obtain the desired solids content.
  • the emulsion preferably has a solids content of about 10 to about 70%, with about 20 to about 54% preferred, and about 25 to about 40% especially preferred.
  • the styrene-butadiene rubber may contain up to about 70% bound styrene.
  • Examples of preferred fillers for use in the emulsion or dispersion include titanium dioxide (rutile and anatase), barium titanate, strontium titanate, silica (particles and hollow spheres) including fused amorphous silica, corundum, wollastonite, aramide fibers (e.g., Kevlar), fiberglass, Ba 2 Ti 9 O 20 , glass spheres, quartz, boron nitride, aluminum nitride, silicon carbide, beryllia, alumina or magnesia, used alone or in combination.
  • Particularly preferred fillers are rutile titanium dioxide and amorphous silica. Fillers may be used in amounts of about 1 to about 30 parts per hundred parts of resin (plu).
  • the filler may be treated with one or more coupling agents, such as silanes, zirconates or titanates.
  • Suitable cross-linking agents include all types useful in cross-linking elastomeric polymers and copolymers, especially those useful in cross-linking polybutadiene or polyisoprene. Examples include phenolic resins, melamine resins, azides, peroxides, sulfur and sulfur derivatives. Free radical initiators are preferred as crosslinking agents. Examples of free radical initiators include peroxides, hydroperoxides and non-peroxide initiators such as 2,3-dimethyl-2,3-diphenyl butane. Peroxide cross-linking agents are especially preferred.
  • the cross-linking agent when used, is typically present in an amount of about 0.25 to about 10 phr.
  • Useful wetting agents include those materials that improve wetting, promote adhesion or both improve wetting and promote adhesion. Examples of these materials include, but are not limited to, polyether polysiloxane blends such as CoatOSil 1211 available from Witco and BYK 333 available from BYK Chemie. Wetting agents may be used in amounts of about 0 to about 5 weight percent (wt %), based on the total weight of the composition.
  • Coupling agents useful in the emulsion or dispersion are known materials that may promote the formation of or participate in a covalent bond or series of covalent bonds connecting a metal surface and a polymer coating on a metal surface.
  • a coupling agent is 3-mercaptopropylmethyldimethoxy silane.
  • Useful amounts of coupling agents typically are about 0 to about 1 wt %, based on the total weight of the composition.
  • Reactive monomers are monomers with unsaturation which may be included in the emulsion or dispersion for a specific property or for specific processing conditions. Inclusion of one or more reactive monomers with unsaturation has the benefit of increasing cross link density upon cure. Suitable monomers must be capable of co-reacting with the elastomeric polymer and/or the thermosetting composition. Examples of suitable monomers include styrene, vinyl toluene, divinyl benzene, triallylcyanurate, diallylphthalate, and multifunctional acrylate monomers (such as Sartomer compounds available from Sartomer Co.), among others, all of which are commercially available.
  • the useful amount of monomers with vinyl unsaturation is about 0 to about 50% by weight of the emulsion or dispersion.
  • Metal surfaces suitable for use herein include surfaces provided by metals useful in the formation of circuit boards such as: copper, aluminum, zinc, and their alloys. There are no limitations regarding the thickness of the metal nor are there any limitations as to the shape, size or texture of the surface.
  • the surface may be coated by one or more coatings known in the art such as a passivation coating, chromate coating, titanate coating, zirconate coating and silane coating. Silane coatings may comprise a single silane or a mixture of silanes, as is known in the art.
  • the metal surface may be used as obtained from the supplier or subsequent to a cleaning procedure.
  • thermosetting compositions for use as substrates in electrical circuits employ resins that cure by a free radical process.
  • resins include rubber, polyester, vinyl, acrylic, polybutadiene, polyisoprene, polybutadiene and polyisoprene copolymers, acrylate ester, allylated polyphenylene ether resins BT resins, epoxy resin, cyanate ester resin, and combinations comprising one of the foregoing resins.
  • Thermosetting mixtures of thermosetting resins and thermoplastics may also be used, non-limiting examples including epoxy-PTFE, epoxy-polyphenylene ether, epoxy- PEI, cyanate ester-PPE, and 1,2-polybutadiene-polyethylene.
  • thermosetting compositions containing polybutadiene, polyisoprene, and/or polybutadiene and polyisoprene copolymers are especially preferred.
  • the thermosetting compositions may also include particulate fillers, fabric, elastomers, flame retardants, and other components known in the art.
  • Particularly preferred thermosetting compositions are RO4350B and RO4003, both available from Rogers Corporation, Rogers, CT.
  • thermosetting compositions are processed as described in U.S. Patent No. 5,571,609 to St. Lawrence et al., which is incorporated by reference herein.
  • the thermosetting composition generally comprises: (1) a polybutadiene or polyisoprene resin or mixture thereof; (2) an optional unsaturated butadiene- or isoprene-containing polymer capable of participating in crosslinking with the polybutadiene or polyisoprene resin during cure; and (3) an optional low molecular weight polymer resin.
  • the polybutadiene or polyisoprene resins may be liquid or solid at room temperature.
  • Liquid resins may have a molecular weight greater than 5,000, but preferably have a molecular weight of less than 5,000 (most preferably between 1,000 or 3,000).
  • the preferably liquid (at room temperature) resin portion maintains the viscosity of the composition at a manageable level during processing to facilitate handling, and it also crosslinks during cure.
  • Polybutadiene and polyisoprene resins having at least 90% 1,2-addition by weight are preferred because they exhibit the greatest crosslink density upon cure owing to the large number of pendant vinyl groups available for crosslinking. High crosslink densities are desirable because the products exhibit superior performance in an electrochemical cell environment at elevated temperatures.
  • a preferred resin is B3000 resin, a low molecular weight polybutadiene liquid resin having greater than 90 weight percent (wt.%) 1,2-addition.
  • B3000 resin is commercially available from Nippon Soda Co., Ltd.
  • the thermosetting composition optionally comprises functionalized liquid polybutadiene or polyisoprene resins.
  • suitable functionalities for butadiene liquid resins include but are not limited to epoxy, maleate, hydroxy, carboxyl and methacrylate.
  • useful liquid butadiene copolymers are butadiene-co-styrene and butadiene-co-acrylonitrile.
  • Possible functionalized liquid polybutadiene resins include Nisso G-1000, G-2000, G-3000; Nisso C-1000; Nisso BN-1010, BN-2010, BN-3010, CN-1010; Nisso TE-2000; and Nisso BF-1000 commercially available from Nippon Soda Co., Ltd.
  • the optional, butadiene- or isoprene-containing polymer may be unsaturated and can be liquid or solid. It is preferably a solid, thermoplastic elastomer comprising a linear or graft-type block copolymer having a polybutadiene or polyisoprene block, and a thermoplastic block that preferably is styrene or ⁇ -methyl styrene.
  • Possible block copolymers e.g., styrene-butadiene-styrene tri-block copolymers, include Vector 8508M (commercially available from Dexco Polymers, Houston, TX), Sol-T- 6302 (commercially available from Enichem Elastomers American, Houston, TX), and Finaprene 401 (commercially available from Fina Oil and Chemical Company, Dallas, TX).
  • the copolymer is a styrene-butadiene di-block copolymer, such as Kraton Dl 118X (commercially available from Shell Chemical Corporation).
  • Kraton Dl 118X is a di-block styrene-butadiene copolymer containing 30 vol% styrene.
  • the unsaturated butadiene- or isoprene-containing polymer may also contain a second block copolymer similar to the first except that the polybutadiene or polyisoprene block is hydrogenated, thereby forming a polyethylene block (in the case of polybutadiene) or an ethylene-propylene copolymer (in the case of polyisoprene).
  • materials with enhanced toughness can be produced.
  • the unsaturated butadiene- or isoprene- containing polymer comprises a solid thermoplastic elastomer block copolymer
  • composition having the formula X m (Y-X) n (linear copolymer) or x ' n (graft copolymer), where Y is a polybutadiene or polyisoprene block, X is a thermoplastic block, and m and n represent the average block numbers in the copolymer, m is 0 or 1 and n is at least 1.
  • the composition may further include a second thermoplastic elastomer block
  • copolymer having the formula W p -(Z-W) q (linear copolymer) or (graft copolymer) where Z is a polyethylene or ethylene-propylene copolymer block, W is a thermoplastic block, and p and q represent the average block numbers in the copolymer, p being 0 and 1 and q being at least 1.
  • the volume to volume ratio of the polybutadiene or polyisoprene resin to butadiene- or isoprene-containing polymer preferably is between 1 :9 and 9:1, inclusive.
  • the selection of the butadiene- or isoprene-containing polymer depends on chemical and hydrolysis resistance as well as the toughness conferred upon the molded material.
  • the optional low molecular weight polymer resin is generally employed to enhance toughness and other desired characteristics of composition.
  • suitable low molecular weight polymer resins include, but are not limited to, telechelic polymers such as polystyrene, multifunctional acrylate monomers, EPR or EPDM containing varying amounts of pendant norbornene groups and/or unsaturated functional groups.
  • the optional low molecular weight polymer resin can be present in amounts of about 0 to about 30 wt% of the resin composition.
  • Monomers with vinyl unsaturation may also be included in the resin system for specific property or processing conditions, such as to decrease the viscosity of the conductive moldable composite material, especially with high filler loading.
  • Viscosity is a key factor in obtaining acceptable molding rheologies. Inclusion of one or more monomers with vinyl unsaturation has the added benefit of increasing crosslink density upon cure. Suitable monomers must be capable of co-reacting with one of the other resin system components. Examples of suitable monomers include styrene, vinyl toluene, divinyl benzene, triallylcyanurate, diallylphthalate, and multifunctional acrylate monomers (such as Sartomer compounds available from Arco Specialty Chemicals Co.), among others, all of which are commercially available.
  • the useful amount of monomers with vinyl unsaturation is 0 to about 80% by weight of the resin composition and preferably about 3% to about 50% by weight of the resin composition.
  • a curing agent is preferably added to the resin system to accelerate the curing reaction.
  • the curing agent decomposes to form free radicals, which then initiate cross linking of the polymeric chains.
  • Preferred curing agents are organic peroxides such as Luperox, dicumyl peroxide, t-butyl perbenzoate, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane, a. ⁇ '-bis(t-butyl peroxy)diisopropylbenzene, and 2,5-dimethyl-2,5-di(t-butyl peroxy) hexyne-3, all of which are commercially available. They may be used alone or in combination.
  • Typical amounts of curing agent are from about 1.5 to about 6 parts per hundred parts of the total resin composition.
  • the aqueous emulsion or dispersion may be applied to the metal surface by dip-, spray-, wash-, die- or other coating technique to provide a weight of elastomeric polymer or copolymer on the metal surface of about 2 to about 20 grams per square meter, (g/m 2 ), preferably about 4 to about 10 g/m 2 , when dry.
  • the coating thickness is chosen to optimize bond strength and other characteristics such as electrical properties and resistance to attack by organic solvents.
  • the emulsion or dispersion is allowed to dry under ambient conditions or by forced or heated air to form a polymer layer.
  • the polymer layer may be at least partially cured in the drying process or the polymer layer may be at least partially cured, if desired, by other methods known in the art.
  • the thermosetting composition is applied to the polymer layer.
  • the thermosetting composition is cured and the laminated material is formed by an effective quantity of heat and pressure, which will depend upon the particular thermosetting composition.
  • the thermosetting composition can be cured by other methods well known to those skilled in the art such as microwave, electron beam, and catalytic methods and then laminated with the metal surface using heat and optionally pressure.
  • the circuit board material comprises an adhesion promoting polymer layer disposed between a metal layer and a thermosetting composition, wherein the adhesion promoting polymer layer comprises an elastomeric polymer.
  • the adhesion promoting polymer layer comprises an elastomeric polymer.
  • Figure 1 shows an exemplary coated metal foil 6 comprising metal layer 2 disposed adjacent to adhesion promoting polymer layer 4.
  • Figure 2 shows an exemplary coated curable thermosetting dielectric prepreg 8 comprising curable thermosetting composition 10 disposed adjacent to an adhesion promoting polymer layer 4.
  • Figure 3 shows a circuit material 14 comprising metal layer 2 disposed adjacent to adhesion promoting polymer layer 4, which is disposed adjacent to thermosetting composition 12.
  • Figure 4 shows an exemplary multilayer circuit material 22 comprising a first thermosetting composition 12 disposed adjacent to a first adhesion promoting polymer layer 4.
  • First adhesion promoting polymer layer 4 is also disposed adjacent to first metal layer 2 that, in turn, is disposed adjacent to a second thermosetting composition 16.
  • Second thermosetting composition 16 is disposed adjacent to second adhesion promoting polymer layer 18, which is disposed adjacent to second metal layer 20.
  • the circuit material may comprise an additional adhesion promoting layer (not shown) between first metal layer 2 and second thermosetting composition 16.
  • the first and second thermosetting compositions may be the same or different.
  • the first and second adhesion promoting polymer layers may be the same or different and first and second metal layers may be the same or different. Additional layers may also be present.
  • the invention is further illustrated by the following non-limiting Examples.
  • Example 1 is a control and Examples 2-4 are according to the invention.
  • Example 1 uses no aqueous emulsion of a butadiene or isoprene polymer while Examples 2-4 uses GOOD-RITE® 1800x73, an aqueous emulsion of a random styrene butadiene rubber diluted to a solids content of approximately 40%.
  • the solutions were all applied to 1/2 oz. copper foil (TWX available from Yates Foil).
  • TWX available from Yates Foil
  • the coated copper foil was dried under ambient conditions, and then an RO4350B prepreg (a polybutadiene-based thermosetting composition available from Rogers Corporation, Rogers CT) was applied and heated under pressure to effect lamination.
  • Table 1 shows the weight of the butadiene or isoprene polymer on the foil after drying and the peel strength. Peel strength was tested in accordance with IPC-TM-6507.48.
  • Table 1 shows that peel strength is increased to 4.82-5.10 pli from 3.93 pli by treating the copper foil with an aqueous emulsion of a butadiene or isoprene polymer. Examples 5-7
  • Examples 5-7 were made according to the same method as used in Examples 1-4 except GOOD-RITE ® SB 0738 was used.
  • GOOD-RITE ® SB 0738 is an aqueous emulsion of carboxylated random styrene butadiene rubber.
  • Example 5 is a control and does not employ an aqueous emulsion. Results are shown in Table 2 TABLE 2
  • Table 2 shows an increase in bond strength of 1.2 to 2.2 pli over the control, a 30-55%) increase.
  • Examples 8-10 were prepared in a similar fashion to Examples 5-7 except that a wetting agent, either CoatOSil 1211 available from Witco or BYK333 available from BYK Chemie was added to the GOOD-RITE ® SB 0738 aqueous emulsion. CoatOSil was added in an amount of 1 part by weight per 100 parts by weight of GOOD-RITE ® SB 0738. BYK 333 was added in an amount of 0.3 parts by weight per 100 parts by weight of GOOD-RITE ® SB 0738.
  • Example 8 is a control and does not employ either an aqueous emulsion or a wetting agent. Results are shown in Table 3.
  • Table 3 shows an increase in bond strength of 2.2 to 2.7 pli over the control, a 56-69% increase.

Abstract

L'invention porte sur un procédé d'amélioration de l'adhésion entre une surface métallique et la surface d'une composition thermodurcissable consistant à mettre la surface métallique en contact avec une émulsion aqueuse renfermant un polymère élastomère, à sécher l'émulsion aqueuse ou la dispersion afin d'obtenir une couche polymère favorisant l'adhésion, à mettre la couche polymère favorisant l'adhésion en contact avec une composition thermodurcissable et à durcir la composition thermodurcissable. L'émulsion ou la dispersion peut renfermer, en outre, des tensions actifs ioniques ou non inoniques, des modificateurs de viscosité, des agents de couplage, des agents mouillants, des charges, des monomères réactifs, des antioxydants et des agents de réticulation. Le procédé permet d'obtenir une matière de circuit comprenant une couche polymère favorisant l'adhésion venant entre une couche métallique et une composition thermodurcissable. La matière de circuit fait preuve d'une meilleure résistance d'agglomération par rapport aux matières de circuit n'utilisant pas de couche favorisant l'adhésion comprenant un polymère élastomère.
PCT/US2002/011665 2001-04-11 2002-04-11 Procede d'amelioration de l'agglomeration de compositions rigides et thermodurcissables sur du metal, et articles ainsi obtenus WO2002083328A1 (fr)

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US60/283,236 2001-04-11

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WO (1) WO2002083328A1 (fr)

Cited By (4)

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WO2007107605A2 (fr) * 2006-03-23 2007-09-27 Rhodia Operations Procede destine au traitement d'une surface hydrophobe par une phase aqueuse
WO2008020984A2 (fr) * 2006-08-08 2008-02-21 World Properties, Inc. Matériaux de circuit avec liaison améliorée, leur procédé de fabrication et articles formés à partir de ceux-ci
WO2010144792A1 (fr) * 2009-06-11 2010-12-16 Rogers Corporation Matériaux diélectriques, procédés de fabrication de sous-ensembles à partir de ceux-ci et sous-ensembles formés à partir de ceux-ci
US8257820B2 (en) 2006-08-08 2012-09-04 World Properties, Inc. Circuit materials with improved bond, method of manufacture thereof, and articles formed therefrom

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DE2310783A1 (de) * 1973-03-03 1974-09-12 Richardson Co Isolierstoffplatte fuer gedruckte schaltungen
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007107605A2 (fr) * 2006-03-23 2007-09-27 Rhodia Operations Procede destine au traitement d'une surface hydrophobe par une phase aqueuse
WO2007107605A3 (fr) * 2006-03-23 2008-01-03 Rhodia Recherches & Tech Procede destine au traitement d'une surface hydrophobe par une phase aqueuse
US8946306B2 (en) 2006-03-23 2015-02-03 Rhodia Operations Process for the treatment of a hydrophobic surface by an aqueous phase
US8222304B2 (en) 2006-03-23 2012-07-17 Rhodia Operations Process for the treatment of a hydrophobic surface by an aqueous phase
GB2455917B (en) * 2006-08-08 2011-08-17 World Properties Inc Circuit materials with improved bond, method of manufacture thereof, and articles formed therefrom
GB2455917A (en) * 2006-08-08 2009-07-01 World Properties Inc Circuit materials with improved bond, method of manufacture thereof, and articles formed therefrom
WO2008020984A3 (fr) * 2006-08-08 2008-04-10 World Properties Inc Matériaux de circuit avec liaison améliorée, leur procédé de fabrication et articles formés à partir de ceux-ci
US8257820B2 (en) 2006-08-08 2012-09-04 World Properties, Inc. Circuit materials with improved bond, method of manufacture thereof, and articles formed therefrom
US8431222B2 (en) 2006-08-08 2013-04-30 World Properties, Inc. Circuit materials with improved bond, method of manufacture thereof, and articles formed therefrom
US8632874B2 (en) 2006-08-08 2014-01-21 Rogers Corporation Dielectric materials, methods of forming subassemblies therefrom, and the subassemblies formed therewith
US8722192B2 (en) 2006-08-08 2014-05-13 World Properties, Inc. Circuit materials with improved bond, method of manufacture thereof, and articles formed therefrom
WO2008020984A2 (fr) * 2006-08-08 2008-02-21 World Properties, Inc. Matériaux de circuit avec liaison améliorée, leur procédé de fabrication et articles formés à partir de ceux-ci
US8519273B2 (en) 2008-04-10 2013-08-27 Sankar Paul Circuit materials with improved bond, method of manufacture thereof, and articles formed therefrom
WO2010144792A1 (fr) * 2009-06-11 2010-12-16 Rogers Corporation Matériaux diélectriques, procédés de fabrication de sous-ensembles à partir de ceux-ci et sous-ensembles formés à partir de ceux-ci

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