WO2001023466A1 - Adhesif electroconducteur contenant du polyurethanne modifie en epoxy - Google Patents

Adhesif electroconducteur contenant du polyurethanne modifie en epoxy Download PDF

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Publication number
WO2001023466A1
WO2001023466A1 PCT/US2000/026549 US0026549W WO0123466A1 WO 2001023466 A1 WO2001023466 A1 WO 2001023466A1 US 0026549 W US0026549 W US 0026549W WO 0123466 A1 WO0123466 A1 WO 0123466A1
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Prior art keywords
electrically conductive
hydrocarbon radical
conductive adhesive
group
epoxide
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PCT/US2000/026549
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English (en)
Inventor
Daoqiang Lu
Ching-Ping Wong
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Georgia Tech Research Corp.
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Publication date
Application filed by Georgia Tech Research Corp. filed Critical Georgia Tech Research Corp.
Priority to AU77223/00A priority Critical patent/AU7722300A/en
Publication of WO2001023466A1 publication Critical patent/WO2001023466A1/fr

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    • 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
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3227—Compounds containing acyclic nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/28—Non-macromolecular organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/54—Inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • 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
    • H05K2201/0206—Materials
    • H05K2201/0239—Coupling agent for particles

Definitions

  • This invention relates to novel electrically conductive adhesives for solder replacement in electronics packaging applications. More specifically, the present invention relates to novel electrically conductive adhesives which are fabricated using epoxide- modified polyurethane (EPU) resins and show superior impact performance and very stable contact resistance with non-noble metal finished components.
  • EPU epoxide- modified polyurethane
  • Soldering processes with tin lead solders are standard interconnection technologies of electronic components on printed circuit boards (PCBs).
  • the most common reflow soldering process for the surface mount technology (SMT) uses tin/lead solder pastes.
  • SMT surface mount technology
  • Lead is well-known hazard to human health. Even small quantities can damage the brain, nervous system, liver, and kidneys when ingested.
  • Sn/Pb solders are disposed in landfills, lead can leach into soils and pollute ground water. Accordingly, pressure to remove or minimize the use of lead is steadily building.
  • electrically conductive adhesives to replace conventional tin/lead solders in both rigid and flexible substrate applications in order to reduce the adverse effects of lead and the organic solvents which are used to clean the flux.
  • electrically conductive adhesives offer many advantages: low processing temperature, fine pitch capability, lower sensitivity to thermomechanical stresses, environmentally friendly, and simple processing. Even though electrically conductive adhesives do not have the conductivity of metals and solders, their conductivity is adequate for many electrical circuits. However, limitations and concerns do exist.
  • NCMS National Center of Manufacturing and Science
  • Polyurethane materials exhibit high toughness and good adhesion, but difficulties in working with polyurethane resins has rendered their use impractical. Therefore, there exists a need in the art for a polymeric material having high toughness and good adhesion, while still being practical for use in polyurethane adhesives.
  • U.S. Patent No. 3,624,178 to Allscheil, et al. discloses epoxide-modified polyurethanes for use as coating agents, laminates, paints, adhesives and as insulating compounds for the electrical industry. The reference does not suggest using the polyurethanes in electrically conductive adhesives.
  • the present invention relates to novel electrically conductive adhesives made with epoxide-modified polyurethane resins.
  • the novel adhesives comprise (a) a novel epoxide- modified polyurethane resin; (b) a cross-linking agent; (c) an adhesion promoter; and (d) a conductive filler.
  • the epoxide-modified polyurethanes useful in the electrically conductive adhesives of the present invention have a structure selected from: or
  • R is a substituted or unsubstituted aliphatic hydrocarbon radical, a substituted or unsubstituted cycloaliphatic hydrocarbon radical, a substituted or unsubstituted aromatic hydrocarbon radical, or a substituted or unsubstituted araliphatic hydrocarbon radical;
  • R 2 is a substituted or unsubstituted aliphatic hydrocarbon radical, a substituted or unsubstituted cycloaliphatic hydrocarbon radical, a substituted or unsubstituted alkoxy radical, a substituted or unsubstituted polyester; or a substituted or unsubstituted polyether;
  • R 4 is either:
  • R 3 is a substituted or unsubstituted aliphatic hydrocarbon radical, a substituted or unsubstituted cycloaliphatic hydrocarbon radical, a substituted or unsubstituted alkoxy radical, a substituted or unsubstituted polyester, or a substituted or unsubstituted polyether; and X, and X 2 are either a single bond, -O-; -COO-; -NH-; or -S-.
  • the cross-linking agent is any compound suitable for hardening the composition, but is preferably a carboxylic acid anhydride cross-linker.
  • the adhesion promoter is a material which promotes the adhesion between the substrate and the adhesive.
  • exemplary adhesion promoters include organofunctional silane adhesion promoters.
  • the adhesion promoter material is present in the electrically conductive adhesive composition in an amount between 0.02 to 10 weight percent. Preferably the composition contains between 0.1 to 2 weight percent.
  • the conductive filler is any solid powder which has a high electrical conductivity.
  • the fillers include, but are not limited to silver, nickel, copper, aluminum, palladium, platinum, gold and other alloys, or carbon black, carbon fiber and graphite.
  • the filler can be in any form capable of being incorporated into the adhesive, including powder or flake form.
  • the preferred powder is silver flakes.
  • the conductive adhesive composition of the present invention comprises 5 to 95 weight percent of a conductive filler.
  • the composition comprises 50 to 80 percent of metal fillers.
  • the adhesive of the present invention may optionally include one or more of (e) an epoxy resin; (f) a catalyst; and (g) a diluent.
  • Epoxy resins include, but are not limited to, bisphenol A, bisphenol F, cycloaliphatic, biphenyl, naphthalene and novolac type epoxies.
  • a preferable epoxy resin is bisphenol F.
  • the epoxy resin is preferably present in the adhesive composition from about 0 to 80 weight percent.
  • Exemplary catalysts include, but are not limited to, imidazoles, tertiary amines and ureas.
  • the formulation of the present invention further may contain from 0 to 10 weight percent, preferably 0 to 2 weight percent of a catalyst.
  • a reactive or nonreactive diluent may be used for some formulations with high viscosity.
  • reactive diluents include, but are not limited to, glycidyl ethers.
  • the composition of the present invention may contain between 0 to 50 weight percent of a diluent.
  • urethane is used herein in its conventional sense to denote organic compounds containing a recurring — O — (CO) — NH — linkage.
  • polyurethane is intended to mean a polymer, either a homopolymer or copolymer, containing a plurality of urethane units as just defined.
  • active hydrogen refers to hydrogen atoms which react positively in the well-known Zerevitinov test.
  • the Zerevitinov test is the reaction of an organic compound containing active hydrogen atoms with methylmagnesium halide to give methane, which is collected and determined volumetrically.
  • groups containing active hydrogen atoms are -OH, -COOH, -SH and -NHR where R can be hydrogen, alkyl, cycloalkyl, aryl aromatic and the like.
  • alkyl refers to a branched, unbranched or cyclic saturated hydrocarbon group of 1 to 26 carbon atoms, such as methyl, ethyl, «-propyl, isopropyl, n- butyl, isobutyl, t-butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like.
  • Preferred alkyl groups herein contain 1 to 10, more typically 1 to 8, carbon atoms.
  • lower alkyl intends an alkyl group of one to six carbon atoms, preferably one to four carbon atoms.
  • the alkyl groups present on the polymers described herein may be unsubstituted or they may be substituted with one or more functional groups, e.g., amine, hydroxyl, an olefinic group such as a vinyl or an allyl group, or the like.
  • alkylene refers to a difunctional saturated branched or unbranched hydrocarbon chain containing from 1 to 26 carbon atoms.
  • “Lower alkylene” refers to alkylene linkages containing from 1 to 6 carbon atoms, and includes, for example, methylene (— CH — ), ethylene (— CH 2 CH 2 — ), propylene (— CH 2 CH 2 CH 2 — ), 2- methylpropylene (— CH 2 — CH(CH 3 )— CH — ), hexylene (— (CH 2 ) 6 — ), and the like.
  • alkoxy refers to an alkyl group as defined above bound through an ether linkage, typically to a carbon atom. "Lower alkoxy” intends an alkoxy group containing one to six, more preferably one to four, carbon atoms.
  • cycloalkyl refers to a saturated hydrocarbon ring group having from 3 to 8 carbon atoms, and includes, for example, cyclopropyl, cyclobutyl, cyclohexyl, methylcyclohexyl, cyclooctyl, and the like. Typically, however, cycloalkyl species will contain 5 or 6 carbon atoms.
  • amino intends an amino group — NH 2 .
  • amino is thus intended to include primary amino — NH 2 , "alkylamino” (i.e., a secondary amino group containing a single alkyl substituent), and “dialkylamino” (i.e., a tertiary amino group containing two alkyl substituents).
  • Halo or "halogen” refers to fluoro, chloro, bromo or iodo, and usually relates to halo substitution for a hydrogen atom in an organic compound. Of the halos, chloro and fluoro are generally preferred.
  • Branched refers to those carbon chains having at least one tertiary or quaternary aliphatic carbon atom.
  • Unbranched refers to a structure where the carbon chain does not have any tertiary or quaternary aliphatic carbon atoms.
  • Optional or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
  • the phrase “optionally substituted alkyl group” means that the alkyl group may or may not be substituted and that the description includes both unsubstituted alkyl and alkyl where there is substitution.
  • a process which is “optionally” carried out in the presence of a particular chemical agent means that such an agent may or may not be present.
  • the preferred epoxide modified polyurethanes of the present invention are of the general structure:
  • n can be any integer equal to or greater than one, and is preferably equal to 1.
  • R can be a substituted or unsubstituted aliphatic hydrocarbon radical having 2 or more carbon atoms; a substituted or unsubstituted cycloaliphatic hydrocarbon radical having 4 or more carbon atoms; a substituted or unsubstituted aromatic hydrocarbon radical having 6 or more carbon atoms; or a substituted or unsubstituted araliphatic hydrocarbon radical having 7 or more carbon atoms.
  • R is preferably selected from the group consisting of the following hydrocarbon radicals:
  • R 2 can be a substituted or unsubstituted aliphatic hydrocarbon radical having 2 or more carbon atoms; a substituted or unsubstituted cycloaliphatic hydrocarbon radical having 4 or more carbon atoms; a substituted or unsubstituted alkoxy, a substituted or unsubstituted polyester; or a substituted or unsubstituted polyether.
  • R 2 is preferably a polyester or polyether radical. Most preferably, R 2 is a polyether and the most preferred polyether radical is:
  • R 3 can be a substituted or unsubstituted aliphatic hydrocarbon radical having 2 or more carbon atoms; a substituted or unsubstituted cycloaliphatic hydrocarbon radical having 4 or more carbon atoms; a substituted or unsubstituted alkoxy, a substituted or unsubstituted polyester; or a substituted or unsubstituted polyether.
  • R 3 is a polyether or a C,. 6 alkyl. Most preferably, R 3 is selected from the group consisting of methyl and — CH 2 — O— CH 2 CHCH 2 — O— CH 2 — .
  • X Culture X'êt and X 2 are selected independently from the group consisting of a single bond, -O-; -COO-; -NH-; and -S-.
  • X tract X'êt and X 2 are -O-.
  • R 2 is a -O- terminated moiety (such as a polyether) then X', attached to that terminus is a single bond and X, attached to the opposite terminus is -O-. 3.
  • the epoxide-modified polyurethanes according to the present invention are prepared by reacting (a) a polyisocyante, preferably a diisocyanate, with (b) a compound containing at least two active-hydrogen groups, preferably a difunctional or trifunctional polyhydroxyl compound, most preferably the corresponding polyhydroxypolyester or polyhydroxypolyether.
  • a polyisocyante preferably a diisocyanate
  • a compound containing at least two active-hydrogen groups preferably a difunctional or trifunctional polyhydroxyl compound, most preferably the corresponding polyhydroxypolyester or polyhydroxypolyether.
  • the product of reacting (a) and (b) is then reacted with (c) a compound having one or more epoxide groups and an active hydrogen; and, optionally, (d) other auxiliaries and additives known to those skilled in the chemistry of polyurethane elastomers.
  • R,-(NCO) p where p is greater than 1, and where R, is as defined above, can be used in the process according to the invention.
  • the polyisocyanate (a), is preferably a diisocyanate corresponding to the formula:
  • Suitable aliphatic or cycloaliphatic diisocyanates are, for example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,2-cyclohexylene diisocyanate, hexahydroxylylene diisocyanate, 4,4'-dicyclohexyl diisocyanate, l,2-di-(isocyanatomethyl)- cyclobutane, l,3-bis-(isocyanatopropyl)-2-methyl-2-propyl propane, l-methyl-2,4- diisocyanatocyclohexane, l-methyl-2,6-diisocyanatocyclohexane, bis-(4- isocyanatocyclohexyl)-methane,
  • R 5 is selected from the group consisting of cyclohexyl, cyclohexyl mono- substituted with X 5 , cyclohexyl di-substituted with X 5 , and cyclohexyl tri-substituted with X 5 ;
  • R 6 is selected from the group consisting of a single bond and lower alkylenes; preferably methylene;
  • R 7 is selected from the group consisting of single bond, cyclohexyl, cyclohexyl mono- substituted with X 5 , cyclohexyl di-substituted with X 5 , and cyclohexyl tri-substituted with X 5 ; and X 5 is selected from the group consisting of lower alkyls, with methyl being the most preferred. If R 7 is a single bond, then it is preferred that R 6 also be a single bond.
  • diisocyanate compounds include hexamethylene diisocyanate, 4,4'-dicyclohexyl diisocyanate, 1,4-diisocyanatocyclohexane, and 3,3,5- trimethyl-5-isocyanatomethyl cyclohexyl isocyanate ("isophorone diisocyanate").
  • the polyisocyanate is reacted with an active hydrogen-containing compound containing m active hydrogen groups (compound (b)) of the formula:
  • M is preferably equal to 2.
  • the active hydrogen- containing compound corresponds to the formula:
  • X — R 2 — X' 3 (IX) where R 2 and X 3 are as defined above; and X' 3 is an active hydrogen-containing group corresponding to the formula HX',; where the H is an active hydrogen and X', is as defined above.
  • R 2 is a -O- terminated moiety (such as a polyether) and X', attached to that terminus in formula (II) is a single bond, then X 3 is -OH and X' 3 is H, rather than HX',.
  • Suitable active hydrogen-containing compounds are well known in polyurethane chemistry and must contain at least two hydrogen atoms capable of reacting with isocyanates. Active hydrogen-containing groups include amino groups, thiol groups, carboxyl groups, and hydroxyl groups.
  • the preferred active hydrogen-containing compounds (b) are polyhydroxyl compounds and in particular compounds which contain 2 to 3 hydroxyl groups. Specific examples include polyhydric alcohols, polyesters, polyethers, polythioethers, polyacetals, polycarbonates or polyester amides containing at least two, preferably from 2 to 3 hydroxyl groups, of the type commonly used in the production of homogeneous and cellular polyurethanes.
  • polyesters containing hydroxyl groups include reaction products of polyhydric, preferably dihydric and optionally trihydric alcohols, with polyvalent, preferable divalent, carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or esters of lower alcohols or mixtures thereof can also be used for the production of the polyesters.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and/or heterocyclic, and can optionally be substituted, for example, by halogen atoms, and/or they can be unsaturated.
  • these polycarboxylic acids are succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, tetrachlorphthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride, maleic acid, maleic acid anhydride, fumaric acid, dimeric and trimeric fatty acids, such as oleic acid, optionally in admixture with monomeric fatty acids, terephthalic acid dimethyl ester, terephthalic acid-bis-glycol
  • suitable polyhydric alcohols include ethylene glycol 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1,6-hexane diol, 1,8- octane diol, neopentyl glycol, cyclohexane dimethanol (1,4-bis-hydroxymethyl-cyclohexane), 2-methyl-l,3-propane diol, glycerol, trimethylol-propane, 1,2,6-hexane triol, 1,2,4-butane triol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside, diethylene glycol, triethylene gylcol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, polytetramethylene glycol, polyoxypropylene glycols, dibutylene glycol and poly
  • the polyesters may contain terminal carboxyl groups.
  • Polyesters for lactones, for example, ⁇ -caprolactone, or hydroxycarboxylic acids, for example, ⁇ -hydroxycaproic acid can be used.
  • the polyethers suitable for use in accordance with the invention are also those of the type known and may be obtained, for example, by the polymerization of epoxides, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorhydrin for example, in the presence of BF3, or by the chemical addition of these epoxides, optionally in admixture with starter components with reactive hydrogen atoms such as water, ethylene glycol, 1,3- or 1,2-propylene glycol, trimethylolpropane, 4,4'- dihydroxydiphenylpropane, aniline, ammonia, ethanolamine and ethylene diamine.
  • epoxides such as ethylene oxide, propylene oxide,
  • polythio-ethers suitable for use include the condensation products of thiodiglycol with itself and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or aminoalcohols. Depending on the co-components, these products are polythio-mixed-ethers, polythio-ether-esters or polythio-ether-ester-amides.
  • Suitable polyacetals include those compounds which can be obtained from glycols, such as di ethylene glycol, tri ethylene glycol, 4,4'-dioxethoxy diphenyl-dimethylmethane and hexane diol, and formaldehyde. Polyacetals suitable for the purpose of the invention can also be obtained by polymerizing cyclic acetals.
  • Suitable polycarbonates containing hydroxyl groups are known and include those obtained by reacting diols, such as 1,3-propane diol, 1,4-butane diol and/or 1,6-hexane diol, diethylene glycol, triethylene glycol and tetraethylene glycol, with diarylcarbonates, such as diphenylcarbonate, or phosgene.
  • diols such as 1,3-propane diol, 1,4-butane diol and/or 1,6-hexane diol
  • diethylene glycol triethylene glycol and tetraethylene glycol
  • diarylcarbonates such as diphenylcarbonate, or phosgene.
  • polyester amides and polyamides include the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyhydric saturated and unsaturated amino alcohols, diamines, polyamines and mixtures thereof.
  • Polyhydroxyl compounds already containing urethane or urea groups, and modified natural polyols, such as caster oil, carbohydrates and starch, can also be used.
  • modified natural polyols such as caster oil, carbohydrates and starch.
  • the addition products of alkylene oxides with phenol-formaldehyde resins or even with urea- formaldehyde resins can also be used in accordance with the invention.
  • the most preferred active hydrogen-containing compounds are represented by the formula:
  • the most preferred active hydrogen-containing compound containing at least two active hydrogen groups is known as PolyTHF (m in formula (VIII) is 4), and is represented by the formula:
  • the polyurethane addition reaction described above is preferably carried out by the known prepolymer process in which (a) the diisocyanate is reacted with a polyhydroxyl compound (b) at an equivalent ratio of isocyanate groups to isocyanate-reactive groups (i.e., active hydrogens) greater than 1.3:1.
  • the resulting NCO prepolymer thus obtained is then reacted with (c) a compound having one or more epoxide groups and an active hydrogen.
  • the temperatures at which the reactions are carried out are generally in the range from 25°C to 100°C, preferably at room temperature. The reactions can be carried out in the presence or even in the absence of suitable inert solvents.
  • the NCO prepolymer has the structural formula:
  • the resulting NCO prepolymer is then reacted with two equivalents of an epoxide- containing compound, which also contains at least one active hydrogen, preferably corresponding to the formula:
  • X 4 is an active hydrogen-containing group corresponding to the formula HX 2 — ; where the H is an active hydrogen; and R 4 and X 2 are as defined above.
  • the epoxide compound (c) is any compound having one or more epoxide groups and at least one active hydrogen atom which can react with isocyanates.
  • Preferred for component (c) are epoxide compounds where the active hydrogen-containing group is -COOH, or -NHR where R is a lower alkyl or hydrogen, and especially preferred where the active hydrogen- containing group is -OH.
  • Most preferred epoxide compounds include glycidol and glycerol diglycidyl ether.
  • Other suitable epoxide and active hydrogen containing compounds (component c) include, but are in no way limited to, those compounds having the structures:
  • auxiliaries and/or additives can optionally be added to the formative components in the preparation of the EPUs of the present invention.
  • auxiliaries and/or additives include blowing agents, lubricants, inhibitors, stabilizers against hydrolysis or discoloration, dyes, pigments, inorganic and/or organic fillers and reinforcers.
  • auxiliaries and/or additives can be introduced into the formative components or into the reaction mixture for preparing the EPUs.
  • the auxiliaries and/or additives which can be used may be found in the specialist literature, for example the monograph by J. H. Saunders and K. C. Frisch "High Polymers,” Volume XVI, Polyurethane, Parts 1 and 2 (Interscience Publishers 1962 and 1964), the Kunststoff-Handbuch, Volume 7, Polyurethane 1st, 2nd and 3rd Editions (Carl Hanser Verlag, 1966, 1983 and 1993) or DE-A-29 01 774. 4.
  • the Cross-Linking Agent can be aliphatic amines, aromatic amines, carboxylic acid anhydrides, thiols, alcohols, phenols, isocyanates, tertiary amines, boron complexes, inorganic acids, hydrazides, imidazoles and their derivatives, and modified products thereof.
  • Preferred hardeners are liquid imidazole or anhydrides because they provide the formulations with lower viscosity.
  • the cross-linking or hardening agent is preferably in liquid form. If a solid hardening agent is employed, such should be melted when added to the composition.
  • anhydride hardeners examples include methyl-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydro-4-methylphthalic anhydride maleic anhydride, trimellitic anhydride, pyromellitic cianhydride, tetrahydrophthalic anhydride, phthalic anhydride, norbomenedicarboxylic anhydride, nadic methyl anhydride, and methylcyclohexane-1, 2 dicarboxylic anhydride.
  • Additional suitable anhydrides which are known in the art can be found, for instance, in H. Lee and K.
  • organic carboxylic acid anhydride hardeners include hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, and mixtures thereof.
  • the cross-linking agent is present at about 1 to 50 weight % of the adhesive composition.
  • the composition further contains an adhesion promoter, most preferably an organofunctional silane adhesion promoter.
  • the adhesion promoter promotes adhesion between the substrate and the adhesive composition.
  • the silane material preferably, but not necessarily, contains the amine, epoxy, or vinyl functionality to increase its compatibility with the composition, but most any organofunctional silane may be used.
  • Suitable classes of silanes include alkylchlorosilanes, dialkyldichlorosilanes, alkyltrichlorosilanes; organosilane esters; vinylsilanes; aminoalkylsilanes; diaminoalkylsilanes; styrylaminosilanes; ureidoalkylsilane esters; epoxyalkylsilane esters; alkoxysilanes; acryloxyalkylsilane esters; methacryloxyalkylsilane esters; and mercaptoalkylsilane esters, and combinations thereof.
  • silanes include, but are not limited to, vinyltrichlorosilane; methyltrichlorosilane; ethyltrichlorosilane; methyldichlorosilane; dimethyldichlorosilane; methylvinyldichlorosilane; methyltriethoxy silane; methyltrimethoxysilane; vinyltriethoxysilane; vinyltrimethoxysilane; vinyl-tris-(2- methoxyethoxy silane); vinyltriacetoxysilane; gamma-methacryloxylpropyltrimethoxysilane; gamma-methacryloxypropyl-tris-(2-methoxyethoxy)silane; beta-(3,4- epoxycyclohexyl)ethyltrimethoxysilane; gamma-glycidoxypropyl-trimethoxysilane; gamma- mercaptopropyltriethoxy
  • silanes include A- 1100, gamma- aminopropyltriethoxysilane, from Union Carbide, Danbury, Conn.; A- 174, gamma- methacryloxypropyltrimethoxysilane, also from Union Carbide; and Z-6040 glycidoxypropyltrimethoxysilane, from Dow Coming Corporation, Midland, MI. It is believed that any organofunctional silane may be used, so long as it is soluble in the reaction mixture and does not interfere with the curing of the composition.
  • the silane component comprises from a small but effective amount, i.e., about 0.02 % by weight of the basic composition, up to about 10.0 % by weight of the composition. Optimally, about 0.1 % to about 2.0 % of silane are used.
  • the conductive filler may be (1) any kind of solid metal or metal oxide particles such as nickel, copper, aluminum, palladium, silver, gold, platinum and other alloys and (2) carbon black, carbon fiber, and graphite.
  • the preferred metallic fillers are silver flakes because they are highly electrically conductive, relatively cheaper compared to gold, and silver oxide is highly electrically conductive.
  • the conductive adhesive composition of present invention comprises 5 to 95 weight %, preferably 50 to 80 % for metal fillers and 10 to 50 % for carbon black, carbon fiber and graphite fillers.
  • Suitable epoxy resins include cycloaliphatic epoxys, bisphenol A, bisphenol F, biphenyl, naphthalene, novolac resins, and compounds of the general formula:
  • the preferred epoxy resins are cycloaliphatic epoxy resins.
  • the cycloaliphatic type epoxides employed as the preferred epoxy resin ingredient in the invention are selected from non-glycidyl ether epoxides containing more than one 1,2 epoxy group per molecule. These generally are prepared by epoxidizing unsaturated cyclic hydrocarbon compounds, such as cyclo-olefms, using hydrogen peroxide or peracids such as peracetic acid and perbenzoic acid.
  • the organic peracids generally are prepared by reacting hydrogen peroxide with either carboxylic acids, acid chlorides or ketones to give the compound R— COOOH.
  • Such non-glycidyl ether cycloaliphatic epoxides are characterized by having a ring structure wherein the epoxide group may be part of the ring or may be attached to the ring structure. These epoxides also may contain ester linkages. The ester linkages generally are not near the epoxide group and are relatively inert to reactions.
  • non-glycidyl ether cycloaliphatic epoxides examples include 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate (containing two epoxide groups which are part of the ring structures, and an ester linkage); vinylcyclohexene dioxide (containing two epoxide groups, one of which is part of a ring structure); 3,4-epoxy-6-methyl cyclohexyl methyl-3, 4-epoxycyclohexane carboxylate and dicyclopentadiene dioxide, having the following respective structures:
  • cycloaliphatic epoxides are characterized by the location of the epoxy group(s) on a ring structure rather than on an aliphatic side chain.
  • the cycloaliphatic epoxide particularly useful in this invention will have the formula selected from the group consisting of:
  • R' is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, and benzyl radicals; and
  • R" is selected from the group consisting of O, CH 2 OOC, and CH 2 OOC(CH 2 ) 4 COO radicals.
  • cycloaliphatic epoxy resins may be characterized by reference to their epoxy equivalent weight, which is defined as the weight of epoxide in grams which contains one equivalent of epoxy.
  • Suitable cycloaliphatic epoxy resins have a preferred epoxy equivalent weight from about 50 to about 250. They generally will have a viscosity between about 5 to about 900 cps at 25 degrees C.
  • Suitable cycloaliphatic epoxides which are known in the art are suggested in U.S. Patent Nos. 5,194,930; 3,207,357; 2,890,194; 2,890,197; and 4,294,746, disclosures of which are incorporated herein by this reference and made a part hereof.
  • suitable cycloaliphatic epoxides are: 3, 4-epoxycyclohexylmethyl-3, 4- epoxycyclohexane carboxylate available from the Union Carbide under the trade designation
  • cycloaliphatic epoxides can be employed when desired.
  • the most preferred epoxide is 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate.
  • the bisphenol A type epoxides employed as the preferred resin ingredient in the invention are selected from glycidyl ether epoxides containing more than one 1,2 epoxy group per molecule. They are prepared according to methods known in the art by the reaction of 1 mole bisphenol and 2 mole epichlorohydrin in basic media. Generally, the bisphenol A type epoxide particularly useful in this invention will have the formula represented by:
  • the epoxy novolac resin employed as the preferred resin ingredient in the invention is selected from glycidyl ether epoxides containing more than one 1,2 epoxy group per molecule. They are prepared according to methods known in the art by the reaction of phenolic resin and epichlorohydrin in basic media. Generally, the epoxy novolac resin particularly useful in this invention will have the formula represented by:
  • the preferred epoxy novolac resin in this invention is poly(phenyl glycidyl ether)-co- formaldehyde.
  • the epoxy equivalent weight for this epoxy novolac resin ranges from about 200 to about 500.
  • a catalyst, or curing accelerator is a substance that increases, catalytically, the hardening rate of a synthetic resin.
  • the catalyst is selected to make the curing reaction occur at the desired temperature range. It has been found that the selection of the catalyst can influence the latency of the underfill formulation.
  • Imidazolium salts, imidazoles, onium- borate compounds, tertiary amines, ureas, and metal acetylacetonates are suitable catalysts in the present invention to obtain a successful adhesive material.
  • imidazolium salts suitable for use in this invention are characterized by the general formula:
  • R,, R 2 , R 3 , R 4 , and R 5 can be the same or different and are selected from the group consisting of H, C,_ 6 alkyls, and phenyl.
  • the anionic counter ion AC " can be any suitable anionic moiety.
  • AC " is selected from the group consisting of OAC " , AcAc " , C,_ 6 alkyl substituted OAc " , C,. 5 alkyl substituted I “ , BF 4 " , PF 6 “ , AsF 6 “ , SbF 6 “ , and CF 3 SO 3 " .
  • Y is the number of positive charge of M and is 1 to 6, and will be equal to X.
  • suitable metal acetylacetonates include cobaltous (Co 2+ ) acetylacetonate, cobaltic (Co 3+ ) acetylacetonate, coppric, copprous and ferric (Fe 3+ ) acetylacetonate.
  • R,, R 2 , R 3 , R 4 can be the same or different, and are selected from the group consisting of C,., 0 alkyls and phenyl.
  • Suitable tertiary amines include, for example, tri ethyl amine, diaza-bicyclo-(2,2,2)- octane, l,5-diaza-bicyclo-(4,3,0)-non-5-ene, l,8-diaza-bicyclo-(5,4,0)-undec-7-ene, dimethyl aniline, dimethyl benzyl amine, pyridine, 2-, 3-, 4-picoline, N,N-diethyl aniline, quinoline, N- methyl piperidine, N-methyl dicyclohexyl amine, N,N-dimethyl cyclohexyl amine, N- cyclohexyl piperidine, N-cyclohexyl morpholine and 2,6-, 2,4-lutidine.
  • the composition of the present invention can contain about 0 to 10 weight % catalyst; more preferably, 0 to 2 weight %. 9.
  • the composition may be prepared either in the absence of or in the presence reactive or nonreactive diluent.
  • a diluent is preferred in formulations with high viscosity.
  • Suitable nonrective diluents include, for example, aliphatic and cycloaliphatic hydrocarbons, halogen containing hydrocarbons such as methylene chloride, chloroform, di- and tri- chlorethylene, aromatic hydrocarbons, such as benzene, toluene, xylene, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene, dioxane, ethyl acetate, ethyl glycol acetate, acetone, acetonitrile, dimethyl formamide and mixtures of these solvents.
  • Exemplary reactive diluents are glycidyl ethers.
  • the diluent can be present 0 to 50 % by weight of the composition.
  • the electrically conductive adhesive composition of the present invention can be prepared using conventional resin paste mixing/blending equipment.
  • the compositions are optionally prepared utilizing a conventional three-roll mill.
  • the resin components including the epoxide-modified polyurethane, hardener, adhesion promoter, optional epoxy - resin, and optional catalyst are first blended ant the resulting resin composition blend is combined with the conductive filler.
  • the resulting conductive adhesive paste is cured and then tested for impact performance and contact resistance shift during elevated temperature and humidity aging.
  • the invention is exemplified by the following non-limiting examples.
  • EXAMPLE 1 Preparation of an Epoxide-modified Polyurethane (EPU): 2 equivalents of 4,4'- diphenylmethane diisocyanate (MDI) and 1 equivalent polyTBF 2000 (PolyTBF 2000 from BASF) were added to a three-neck flask with a mechanical stirrer and a nitrogen inlet. The mixture was stirred at room temperature for about 5 hours. Then 2 equivalents of glycerol diglycidyl ether were added and mixed. The reaction was continued for another 15 hours at room temperature. As descried in Example 2, the resulting product was an EPU useful in making electrically conductive adhesives.
  • MDI 4,4'- diphenylmethane diisocyanate
  • PolyTBF 2000 PolyTBF 2000 from BASF
  • EXAMPLE 2 Formulating Conductive Adhesives:
  • the EPU resin was prepared as detailed in Example 1.
  • RSL 1738 is a bispehnol F type epoxy resin with an epoxy equivalent weight of 171. It is a product of Shell Chemical Company.
  • MHHPA is methylhexahydrophthalic anhydride available from Aldrich Chemical Company.
  • SILQUEST A-187 is a silane from OSI Specialties.
  • the Ag flake is a product of Degussa Corporation.
  • the EPU resin, RSL1738, MHHPA, 2-ethyl-4-methylimidazole, and SILQUEST A - 187 were blended first to form a resin and then mixed with the Ag flake. The mixture of the resin and the Ag flake was mixed using a three-roll mill until they formed a homogeneous paste.
  • EXAMPLE 3 Impact Performance Test Drop tests were done based on the standard procedure set by National Center of Manufacturing and Science (NCMS). 44 I/O plastic leaded chip carriers, PLCC 44 with J leads, were used in this test. FR4 printed circuit boards (PCB) which were coated either with Sn Pb or copper and had dimensions of 4 cm wide and 8 cm long. A layer of conductive adhesive paste (6 mil thick) was dispensed on the PCB, and then placed the PLCC 44 on the patch of adhesives paste. The samples were cured at 150°C for one hour. After the samples were kept at room temperature for 72 hours, drop test was conducted.
  • NCMS National Center of Manufacturing and Science

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Abstract

L'invention concerne un adhésif électroconducteur présentant une résistance aux impacts suffisante pour résister à un impact brusque lorsque des composants montés en surface dans un module électronique tombent. Cet adhésif comprend (a) une résine de polyuréthanne modifié en époxy, (b) un agent de réticulation tel qu'un anhydride, (c) un accélérateur d'adhérence tel qu'un silane, (d) un élément de remplissage conducteur et, éventuellement, une ou plusieurs résine époxyde. L'adhésif peut éventuellement comprendre un ou plusieurs éléments (e) une résine époxyde, (f) un catalyseur et (g) un diluant.
PCT/US2000/026549 1999-09-27 2000-09-27 Adhesif electroconducteur contenant du polyurethanne modifie en epoxy WO2001023466A1 (fr)

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EP1498441A1 (fr) * 2003-07-16 2005-01-19 Sika Technology AG Compositions réticulables à la chaleur comprenant un modificateur de résistance au choc à basse température
CN100375152C (zh) * 2002-10-15 2008-03-12 新科实业有限公司 用于磁头组件的导电粘合剂
EP1916272A1 (fr) * 2006-10-24 2008-04-30 Sika Technology AG Compositions d'epoxy contenant des prépolymères de polyuréthane blocqués et terminés par époxy.
EP1972646A1 (fr) * 2007-03-20 2008-09-24 Sika Technology AG Polymères terminés par des groupes époxy, leur préparation et leur utilisation comme modificateurs résistants aux chocs
WO2009094295A1 (fr) * 2008-01-22 2009-07-30 Dow Global Technologies Inc. Adhésifs structuraux en résine époxy contenant des agents de durcissement élastomères allongés par polyphénol à fonctionnalité époxyde
EP2143745A1 (fr) * 2008-07-09 2010-01-13 Sika Technology AG Polymères avec fonctions hybride
US7786214B2 (en) 2002-05-03 2010-08-31 Sika Technology Ag Composition of epoxy resin, epoxy adduct, urea derivative thixotropic agent and curing agent
EP2336262A1 (fr) * 2009-12-18 2011-06-22 Sika Technology AG Adhesion par sertissage au pli
US8028800B2 (en) 2009-04-10 2011-10-04 Saint-Gobain Performance Plastics Rencol Limited Acoustic damping compositions
US8062468B2 (en) 2005-07-05 2011-11-22 Sika Technology Ag Low-temperature impact resistant thermosetting epoxide resin compositions with solid epoxide resins
WO2015173722A1 (fr) * 2014-05-12 2015-11-19 Stora Enso Oyj Composition d'élastomère électriquement dissipatif comprenant du carbone conducteur pulvérulent issu de la lignine, procédé de production et de cette composition
WO2015173723A1 (fr) * 2014-05-12 2015-11-19 Stora Enso Oyj Composition polymère électriquement dissipative comprenant une poudre de carbone conductrice issue de la lignine, procédé pour sa fabrication et utilisation correspondante
US9221969B2 (en) 2002-12-17 2015-12-29 Sika Technology Ag Thermally hardenable epoxy resin composition having an improved impact resistance at low temperatures
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CN110603607A (zh) * 2018-04-12 2019-12-20 首尔大学校产学协力团 铜基导电浆料及其制备方法
US10683441B2 (en) 2016-03-02 2020-06-16 3M Innovative Properties Company Composition including epoxy adhesive and aluminum flakes and method for using the same
DE102020204215A1 (de) 2020-04-01 2021-10-07 Rampf Holding GmbH + Co. KG Leitfähiges Polyurethan
CN114479364A (zh) * 2022-01-17 2022-05-13 深圳市姿彩科技有限公司 一种端烯基聚酯接枝碳纳米管改性光固化树脂和制备方法

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WO2004003048A1 (fr) * 2002-07-01 2004-01-08 Huntsman Advanced Materials (Switzerland) Gmbh Monoépoxydes polyéther uréthanne contenant de l'isocyanato
CN100375152C (zh) * 2002-10-15 2008-03-12 新科实业有限公司 用于磁头组件的导电粘合剂
US9221969B2 (en) 2002-12-17 2015-12-29 Sika Technology Ag Thermally hardenable epoxy resin composition having an improved impact resistance at low temperatures
EP1498441A1 (fr) * 2003-07-16 2005-01-19 Sika Technology AG Compositions réticulables à la chaleur comprenant un modificateur de résistance au choc à basse température
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