WO2025166327A1 - Compositions adhésives thermoconductrices - Google Patents

Compositions adhésives thermoconductrices

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Publication number
WO2025166327A1
WO2025166327A1 PCT/US2025/014264 US2025014264W WO2025166327A1 WO 2025166327 A1 WO2025166327 A1 WO 2025166327A1 US 2025014264 W US2025014264 W US 2025014264W WO 2025166327 A1 WO2025166327 A1 WO 2025166327A1
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WIPO (PCT)
Prior art keywords
component
thermally conductive
epoxy resin
carbonate
curable composition
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Pending
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PCT/US2025/014264
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English (en)
Inventor
John TIMMERMAN
Nicole A. MURLEY
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of WO2025166327A1 publication Critical patent/WO2025166327A1/fr
Pending legal-status Critical Current
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Classifications

    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
    • C08K5/1565—Five-membered rings
    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the present invention relates to epoxy -based compositions generally, and more particularly to thermally conductive epoxy adhesives that utilize bio-based components to promote epoxy-amine cure reactions and simultaneously maintain low pre-cure viscosities.
  • Conductive compositions are widely used in the fabrication and assembly of semiconductor packages and microelectronic devices.
  • metallic solder alloy paste or preform
  • solder for affixation such as the use of lead and flux agents, as well as high processing temperatures, has driven the use of conductive adhesives for component affixation in electronic packages.
  • Attachment of electronic components, such as semiconductor dies, to a substrate in an electronic package is typically accomplished through the use of an adhesive that bonds the electronic component to the substrate surface.
  • Numerous adhesives have been used over the years for this purpose, and are known as die attach adhesives or films to bond integrated circuit chips to substrates, lid attach adhesives or films to adhere metal lids to substrates, and assembly- conductive adhesives to bond circuit assemblies to the substrate board.
  • Epoxies are commonly used as adhesives in electronic apparatus assembly. Where conductivity is beneficial, such epoxy adhesives may be filled with conductive particulate such as ceramics and metals. Some epoxy adhesives may be readily formed through a cure reaction of epoxy resin and primary amines. The epoxy/amine reaction can be accelerated by many means, commonly through the use of phenols and tertiary amines. Although these conventional reaction accelerator materials have proven to work well, they are hazardous in their manufacture and use, and require special handling equipment and procedures to ensure safety.
  • the compositions of the invention utilize a combination of a carbonate with hydroxyl functionality and a mono or multifunctional alcohol. This multicomponent combination surprisingly exhibits both cure acceleration and diluent properties while also having low or no toxicity.
  • the combination cure accelerator of the invention may be bio-based, by being derived from living or once-living organisms.
  • the combination cure accelerator of the invention may be used alone, or in combination with traditional phenol/amine accelerators.
  • the combination cure accelerator of the invention may be particularly suited to materials that contain a large proportion of solids, in that the diluent properties permit the material to flow easily for dispensation procedures.
  • a curable composition in one embodiment, includes a first part including a liquid epoxy resin, and a second part including an amine component that is reactable with the epoxy resin.
  • the curable composition further includes a reaction accelerator for accelerating a cure reaction between the epoxy resin and the amine component.
  • the reaction accelerator includes a first component and a second component, with the first component including a carbonate with hydroxyl functionality.
  • the second component of the reaction accelerator includes a polyhydric alcohol.
  • the curable composition preferably exhibits a viscosity of less than 600 Pa*s at 25 °C and at a shear rate of 1 s’ 1 .
  • the first part includes one or both of the first and second components. In some embodiments, the first part includes the first component, and the second part includes the second component. [0010]
  • the second component may include the polyhydric alcohol at a concentration of between 1 and 20 phr of the second component. In some embodiments, the polyhydric alcohol includes glycerol.
  • the first component may include glycerol carbonate at a concentration of between 1 and 15 phr of the first component.
  • the curable composition may include at least 80 wt.% of thermally conductive particulate filler, and may further include one or more of a tertiary amine, a phenol, and a polyol.
  • a thermally conductive adhesive is formed from a curable composition including an epoxy resin, an amine component reactable with the epoxy resin, a thermally conductive particulate filler, and a reaction accelerator.
  • the reaction accelerator may include a first component having 1-15 phr of a carbonate with hydroxyl functionality, and a second component having 1-20 phr of a polyhydric alcohol.
  • the curable composition includes between 50-90 wt.% of the thermally conductive particulate filler.
  • the filler may be selected from alumina, alumina trihydrate, aluminum nitride, boron nitride, graphite, diamond, carbon fibers, carbon nanotubes, zinc oxide, magnesium oxide, magnesium hydroxide, silicon carbide, gold, silver, copper, platinum, palladium, nickel, aluminum, indium, alloys thereof, and other combinations thereof.
  • the curable composition may include between 0.1 and 5 wt.% of the carbonate with hydroxyl functionality, between 0.1 and 5 wt.% of the polyhydric alcohol, between 1 and 5wt.% of the liquid epoxy resin, and between 1 and 10 wt.% of the amine component.
  • the curable composition includes between 0.1 and 3 wt.% of at least one of a tertiary amine and a phenolic functional curing agent.
  • the carbonate with hydroxyl functionality includes glycerol carbonate
  • the polyhydric alcohol includes glycerol
  • a method for producing a thermally conductive adhesive includes preparing a composition including a liquid epoxy resin, an amine reactable with the epoxy resin, a thermally conductive particulate filler, and a reaction accelerator having a first component including a biobased multifunctional alcohol carbonate, and a second component including at least one of a biobased monofuctional alcohol and a bio-based multifunctional alcohol.
  • the method further includes reacting the liquid epoxy resin with the amine component.
  • a gel time of the reaction between the liquid epoxy resin and the amine component at 25 °C is less than 600 minutes.
  • the bio-based multifunctional alcohol carbonate includes a cyclic carbonate with hydroxyl functionality
  • the at least one of the bio-based monofunctional alcohol and bio-based multifunctional alcohol includes a polyhydric alcohol selected from glycerol, 1,2,4 butane triol, 1,2,6 hexane triol, ethylene glycol, and combinations thereof.
  • the composition may include between 1-20 phr of the polyhydric alcohol and between 1-15 phr of the cyclic carbonate.
  • the liquid epoxy resin may be in a first part of the composition, and the amine component may be in a second part of the composition that is initially separate from the first part.
  • the method includes reacting the liquid epoxy resin with the amine component by mixing the first and second parts together.
  • a composition, and in some embodiments, an adhesive composition for use in electronic apparatus includes a curable resin system involving an epoxy resin and a complimentary amine component that is reactable with the epoxy resin.
  • the curable resin may therefore contain an epoxy resin, and a curing agent may be effective in curing the epoxy resin.
  • An amine useful in reacting with the epoxy resin is a primary amine.
  • compositions of the present invention involve an epoxy/amine reaction to form an epoxy adhesive that may be used in various applications.
  • the compositions employ a reaction accelerator that exhibits dual functionality as a diluent to maintain low pre-cure viscosities. Consequently, the compositions are particularly suited to highly filled materials, such as thermally conductive adhesives, or processes like VARTM or RTM.
  • Other applications include reinforced composites, such as carbon fiber reinforced epoxies.
  • the materials of the present invention may exhibit thermal conductivities in the range of at least 2 W/m*K, and in some embodiments at least 5 W/m*K.
  • compositions of the present invention may, in some embodiments, be provided in a 2-part system, reactable upon mixture of an epoxy resin with a suitable amine component.
  • the compositions may be provided in a 1-part system including reaction inhibitors that are denatured with exposure to an activator such as actinic radiation and/or heat.
  • the epoxy resin materials of the present invention may be any of a liquid, solid, semisold, and a solid dissolved or suspended in a liquid such as a solvent, each at 25 °C.
  • the epoxy resin materials of the present invention may preferably be in a liquid state at 25 °C to minimize pre-cure viscosity.
  • the epoxy resin may include a combination of distinct epoxy resins that are curable into a material of desired properties.
  • a wide variety of epoxy-functionalized resins are contemplated for use in the curable compositions of the present invention.
  • liquid-type epoxy resins based on bisphenol A liquid-type epoxy resins based on bisphenol F, multifunctional epoxy resins based on phenol novolac resin, dicyclopentadiene-type epoxy resins, naphthalene-type epoxy resins, and the like.
  • epoxy-functionalized resins contemplated for use herein include the diepoxide of the cycloaliphatic alcohol, hydrogenated bisphenol A (commercially available as EPALLOY 5000), a difunctional cycloaliphatic glycidyl ester of hexahydrophthallic anhydride (commercially available as EPALLOY 5200), EPICLON EXA-835LV, EPICLON HP-7200L, and the like, as well as mixtures of any two or more thereof.
  • the curable composition may include a combination of two or more different epoxy-functionalized resins, including two or more different bisphenol-based epoxies.
  • the bisphenol-based epoxies may be selected from bisphenol A, bisphenol F, or bisphenol S epoxies, and combinations thereof.
  • two or more different bisphenol epoxies within the same type of resin such A, F, or S may be used.
  • bisphenol epoxies contemplated for use herein include bisphenol-F-type epoxies (such as RE-404-S from Nippon Kayaku, Japan, and EPICLON 830 (RE1801), 830S (RE1815), 830A (RE1826) and 83OW from Dai Nippon Ink & Chemicals, Inc., and RSL 1738 and YL-983U from Resolution) and bisphenol- A-type epoxies (such as YL-979 and 980 from Resolution).
  • bisphenol-F-type epoxies such as RE-404-S from Nippon Kayaku, Japan
  • EPICLON 830 (RE1801), 830S (RE1815), 830A (RE1826) and 83OW from Dai Nippon Ink & Chemicals, Inc., and RSL 1738 and YL-983U from Resolution
  • bisphenol- A-type epoxies such as YL-979 and 980 from Resolution
  • Epon 828, Epon 826, Epon 862 (all from Hexion Co., Ltd.), HELOXY 62, HELOXY 8, HELOXY 61, HELOXY 116, HELOXY 65, HELOXY 48, HELOXY 505 (all from Westlake Epoxy), DER 331, DER 383, DER 332, DER 330-EL, DER 331-EL, DER 354, DER 321, DER 324, DER 29, DER 353 (all from Dow Chemical Co.), JER YX8000, JER RXE21, JER YL 6753, JER YL6800, JER YL980, JER 825, and JER 630 (all from Japan Epoxy Resins Co).
  • the bisphenol epoxies available commercially from Dai Nippon and noted above are promoted as liquid undiluted epichlorohydrin-bisphenol F epoxies having much lower viscosities than conventional epoxies based on bisphenol A epoxies and have physical properties similar to liquid bisphenol A epoxies.
  • Bisphenol F epoxy has lower viscosity than bisphenol A epoxies, all else being the same between the two types of epoxies, which affords a lower viscosity and thus a fast flow underfill sealant material.
  • the Epoxy Equivalent Weight (EEW), which is the molecular weight divided by the number of epoxy groups of these four bisphenol F epoxies is between 165 and 180.
  • the viscosity at 25°C is between 3,000 and 4,500 cps (except for RE1801 whose upper viscosity limit is 4,000 cps).
  • the hydrolyzable chloride content is reported as 200 ppm for RE1815 and 830W, and that for RE1826 as 100 ppm.
  • the bisphenol epoxies available commercially from Resolution and noted above are promoted as low chloride containing liquid epoxies.
  • the bisphenol A epoxies have an EEW (g/eq) of between 180 and 195 and a viscosity at 25°C of between 100 and 250 cP.
  • the total chloride content for YL-979 is reported as between 500 and 700 ppm, and that for YL-980 as between 100 and 300 ppm.
  • the bisphenol F epoxies have an EEW (g/eq) of between 165 and 180 and a viscosity at 25°C of between 30 and 60.
  • the total chloride content for RSL-1738 is reported as between 500 and 700 ppm, and that for YL-983U as between 150 and 350 ppm.
  • Monofunctional, difunctional or multifunctional reactive diluents may be used to adjust the viscosity and/or lower the glass transition temperature (Tg) of the resulting resin material.
  • exemplary reactive diluents include butyl glycidyl ether, cresyl glycidyl ether, o-cresyl glycidyl ether, polyethylene glycol glycidyl ether, polypropylene glycol glycidyl ether, and the like.
  • Other or additional reactive diluents useful in the present compositions are described herein, including reactive diluents that act as reaction accelerators.
  • epoxies suitable for use herein include polyglycidyl derivatives of phenolic compounds, such as those available commercially under the tradename EPON, such as EPON 828, EPON 1001, EPON 1009, and EPON 1031 from Resolution; DER 331, DER 332, DER 334, and DER 542 from Dow Chemical Co.; and BREN-S from Nippon Kayaku.
  • EPON polyglycidyl derivatives of phenolic compounds
  • EPON such as EPON 828, EPON 1001, EPON 1009, and EPON 1031 from Resolution
  • DER 331, DER 332, DER 334, and DER 542 from Dow Chemical Co.
  • BREN-S from Nippon Kayaku
  • Other suitable epoxies include polyepoxides prepared from polyols and the like and polyglycidyl derivatives of phenol-formaldehyde novolacs, the latter of such as DEN 431, DEN 438, and DEN 439 from Dow Chemical.
  • Cresol analogs are also available commercially under the tradename ARALDITE, such as ARALDITE ECN 1235, ARALDITE ECN 1273, and ARALDITE ECN 1299 from Ciba Specialty Chemicals Corporation.
  • SU-8 is a bisphenol-A-type epoxy novolac available from Resolution.
  • Polyglycidyl adducts of amines, aminoalcohols and polycarboxylic acids are also useful in this invention, commercially available resins of which include GLYAMINE 135, GLYAMINE 125, and GLYAMINE 115 from F.I.C. Corporation; ARALDITE MY-720, ARALDITE 0500, and ARALDITE 0510 from Ciba Specialty Chemicals and PGA-X and PGA-C from the Sherwin-Williams Co.
  • the epoxy component employed herein is a silane modified epoxy, e.g., a composition of matter that includes:
  • Ri is alkyl, alkenyl, hydroxy, carboxy and halogen, and x here is 1-4;
  • R 1 is an oxirane-containing moiety
  • R 2 is an alkyl or alkoxy-substituted alkyl, aryl, or aralkyl group having from one to ten carbon atoms; and (C) reaction products of components (A) and (B).
  • silane-modified epoxy is formed as the reaction product of an aromatic epoxy, such as a bisphenol A, E, F or S epoxy or biphenyl epoxy, and epoxy silane where the epoxy silane is embraced by the following structure:
  • R 1 is an oxirane-containing moiety, examples of which include 2- (ethoxymethyl)oxirane, 2-(propoxymethyl)oxirane, 2-(methoxymethyl)oxirane, and 2-(3-methoxypropyl)oxirane and
  • R 2 is an alkyl or alkoxy-substituted alkyl, aryl, or aralkyl group having from one to ten carbon atoms.
  • R 1 is 2-(ethoxymethyl)oxirane and R 2 is methyl.
  • Ri is alkyl, alkenyl, hydroxy, carboxy or halogen, and x is 1-4.
  • the siloxane modified epoxy resin has the structure:
  • the siloxane modified epoxy resin is produced by contacting a combination of the following components under conditions suitable to promote the reaction thereof:
  • the silane modified epoxy may also be a combination of the aromatic epoxy, the epoxy silane, and reaction products of the aromatic epoxy and the epoxy silane.
  • the reaction products may be prepared from the aromatic epoxy and epoxy silane in a weight ratio of 1 : 100 to 100:1, such as a weight ratio of 1:10 to 10:1.
  • the epoxy resins of the present compositions are liquid at 25 °C and at 1 ATM. In other embodiments, the epoxy resins of the present compositions include one or more of liquid, solid, semi-solid, and solvent-based suspension at 25 °C.
  • the epoxy resins of the present invention may be present in a range of between 0.5 and 15 wt.% of the total composition. In some embodiments, the epoxy resins of the present invention may be present in a range of between 1 and 10 wt.% of the total composition. In some embodiments, the epoxy resins of the present invention may be present in a range of between 3 and 10 wt.% of the total composition.
  • the epoxy resins of the present invention may be provided in a first part of a multi-part composition, and preferably in a first part of a two-part composition. In some embodiments, the first part may be mixed with the second part of the composition to cure the epoxy resin with a curing agent that is initially provided in the second part of the composition.
  • the first part may be mixed with the second part in a 1 : 1 w:w ratio.
  • cure is intended to mean a cross-linking reaction to form a tri-dimensional polymer network.
  • the curable compositions of the invention also include one or more amines to participate in an epoxy resin cure reaction.
  • the compositions include one or more primary amines that promote the polymerization of the epoxy resins.
  • one or more amine components, such as a primary amine component may be present in a range of between 0.5 and 15 wt.% of the total composition.
  • one or more amine components, such as a primary amine component may be present in a range of between 1 and 10 wt.% of the total composition.
  • one or more amine components, such as a primary amine component may be present in a range of between 2 and 10 wt.% of the total composition.
  • the amine component of the present invention may be provided in a second part of a multi-part composition, and preferably in a second part of a two-part composition.
  • the second part may be mixed with an epoxy resincontaining first pail of a two-part composition.
  • the second part may be mixed with the first part of the composition to cure the epoxy resin of the first part with the amine component of the second part.
  • the amine component may include an amine that is liquid at 25 °C and at 1 ATM.
  • An example liquid amine is a dimer diamine, such as PRIAMINE 1074 from Cargill Co poration.
  • the curable compositions of the invention may further include designated curing agents in addition to the amine component described above.
  • the curing agent may be an amine other than the amine component.
  • Curing agents contemplated for use in the practice of the present invention include ureas, aliphatic and aromatic amines, polyamides, imidazoles, dicyandiamides, hydrazides, urea-amine hybrid curing systems, free radical initiators, organic bases, transition metal catalysts, phenols, acid anhydrides, Lewis acids, Lewis bases, and the like. See, for example, U.S. Pat. No. 5,397,618, the entire contents of which are hereby incorporated by reference herein.
  • Example curing agents in the compositions of the present invention include the following structures:
  • Curing agents may be present in the compositions of the invention in a range of between 0.1 and 10 wt.%. In some embodiments, the curing agents may be present in a range of between 0.1 and 5 wt.% of the total composition. In some embodiments, the curing agents may be present in a range of between 0.2 and 3 wt.% of the total composition. [0047] In some embodiments, the curing agents may include an epoxy hardener, such as a tertiary amine, a phonolic-functional hardener, a polyol, and the like. In some embodiments, the curing agents may include a free-radical initiator.
  • the free-radical initiator may be present in the compositions of the present invention in a range of between 0.1 and 5 wt.%. In some embodiments, the free-radical initiator may be present in a range of between 0.1 and 3 wt.% of the total composition. In some embodiments, the free-radical initiator may be present in a range of between 0.1 and 1 wt.% of the total composition.
  • Conductive fillers contemplated for use herein include, for example, gold, silver, copper, platinum, palladium, nickel, aluminum, indium, alloy of nickel (e.g., alloy 42), alloy of zinc, alloy of iron, alloy of indium, silver-plated copper, silver-plated aluminum, bismuth, tin, bismuth-tin alloy, silver-plated fiber, silver-plated graphite, silver-plated silicon carbide, silver- plated boron nitride, silver-plated diamond, silver-plated alumina, silver-plated alloy 42, graphene, silver-plated graphene, graphene nanoplatelets, single and multi-wall carbon nanotubes, carbon fibers, silver-coated polymer, cadmium and alloys of cadmium, lead and alloys of lead, antimony and alloys of antimony, boron nitride, aluminum nitride, alumina, alumina trihydrate, silicon, silicon carbide, graphite, diamond, magnesium oxide, magnesium hydroxide, zinc
  • the particulate thermally conductive filler may be substantially spherical, plate-like, rod-like, or combinations thereof. It is contemplated that a particle size distribution may be employed to fit the parameters of any particular application, although certain particle size distributions may be found to be more effective than others.
  • Thermally conductive particles used in the compositions of the present invention may be present in the range of between 40 and 95 wt.%. In some embodiments, the thermally conductive particles may be present in the range of between 50 and 90 wt.% of the total composition. In some embodiments, the thermally conductive particles may be present in the range of between 60 and 90 wt.% of the total composition. In some embodiments, the thermally conductive particles may be present in the range of between 70 and 90 wt.% of the total composition. In some embodiments, the thermally conductive particles may be present in the range of between 80 and 90 wt.% of the total composition.
  • the thermally conductive particles may be present in the range of at least 80 wt.% of the total composition.
  • the thermally conductive particles used in the compositions of the present invention have an average particle size (dso) in the range of between 0.1 and 100 micrometers. In some embodiments, the average particle size is in the range of between 0.1 and 50 micrometers. In some embodiments, the average particle size is in the range of between 0.1 and 25 micrometers. In some embodiments, the average particle size is in the range of between 0.1 and 10 micrometers. In some embodiments, the average particle size is in the range of between 0.1 and 5 micrometers.
  • the particulate thermally conductive filler may comprise a multi-modal particle size distribution, having discrete concentrations of particles with different average particle sizes.
  • a first portion of the thermally conductive filler may have an average particle size (dso) of less than 1 micrometer, and a second portion of the thermally conductive filler may have an average particle size (dso) of greater than 1 micrometer.
  • the first portion of the thermally conductive filler may comprise between 20 and 40 percent by weight of the total thermally conductive particulate filler.
  • the first portion of the thermally conductive filler may comprise between 25 and 35 percent by weight of the total thermally conductive particulate filler. Applicant has found that such particle size distributions can promote high thermal conductivity values without detracting from the desired physical properties of the composition.
  • the curable compositions of the present invention when cured, exhibit a thermal conductivity of at least 1 W/m*K, more preferably at least 2 W/m*K, and more preferably at least 5 W/m*K.
  • the thermally conductive particulate filler may be subjected to surface treatment or surface modification.
  • Example surface treatment and surface modification include treatment with a silane coupling agent, phosphoric acid or a phosphoric acid compound, or a surfactant.
  • the silane coupling agent may include at least one hydrolysable group such as an alkoxy group and an aryloxy group bonded to a silicon atom.
  • Other examples include an alkyl group, and alkenyl group, and any aryl group bonded to the silicon atom.
  • the thermally conductive particulate filler may be blended with the curable resin and the curing agent by mixing the components in a mechanical mixer as needed to achieve a desired extent of dispersion of the particulate filler with the curable resin.
  • a reaction accelerator is preferably used in the present compositions to accelerate the cross-linking polymerization reaction of the curable resin, in this case between the epoxy resin and the amine component.
  • various cure accelerators are known for curable epoxy resins
  • the present compositions utilize a unique combination of materials that suitable accelerate the epoxy cure reaction while also acting as a diluent to maintain low pre-cure viscosity in the curable composition.
  • the combination cure accelerator of the present invention may preferably be bio-based so as to reduce or eliminate the hazards associated with conventional cure accelerators.
  • bio-based is intended to mean a material that is intentionally produced from substances derived from living, or once-living, organisms. In a particular embodiment, the term “bio-based” is intended to mean a material that is intentionally produced solely from plant-based sources.
  • a useful epoxy resin cure accelerator for epoxy/amine systems includes a first component having a carbonate with hydroxyl functionality, and a second component having at least one of a monofunctional alcohol and a multifunctional alcohol. It is known to use alcohols as cure accelerators, and have the potential to be bio-based. However, alcohols typically yield an unacceptable pre-cure viscosity increase, particularly in highly filled systems. Additionally, carbonates are known to react with amines on their own, rather than to support the amine-epoxy polymerization reaction. It is therefore a surprising finding to be able to harness the benefits of each of the alcohols and carbonates by employing them in combination.
  • Carbonates with hydroxyl functionality include multifunctional alcohol carbonates, and preferably bio-based multifunctional alcohol carbonates.
  • the carbonates with hydroxyl functionality are cyclic carbonates with hydroxyl functionality.
  • 5-membered cyclic carbonates with hydroxyl functionality may be formed by reacting hydroxyl functional molecules with an oxirane ring with carbon dioxide.
  • a general structure for a cyclic carbonate with hydroxyl functionality is as follows:
  • ⁇ may be any aliphatic group with less than six carbon atoms.
  • Particularly useful cyclic carbonates with hydroxyl functionality include, for example, glycerol carbonate, propanediol carbonate, and methyl glycerol carbonate.
  • the second component of the reaction accelerator includes a monofunctional or multifunctional alcohol that coordinates with the first component to provide the desired epoxy/amine cure reaction acceleration and pre-cure viscosity properties.
  • the at least one monofunctional or multifunctional alcohol is bio-based.
  • Useful alcohols are polyhydric alcohols that are liquid at 25 °C and at 1 ATM.
  • Example polyhydric alcohols useful as the second component of the reaction accelerator include glycerol, 1,2,4 butanetriol, 1,2,6 hexane triol, and ethylene glycol.
  • the reaction accelerator may be provided within specific concentration ranges, with respect to the total composition, with respect to the resins of the composition, and among the first and second components of the reaction accelerator.
  • the carbonate with hydroxyl functionality may be provided in a range of between 1 and 15 pails per hundred resin (phr) of the first part of the composition.
  • the carbonate with hydroxyl functionality may be provided in a range of between 1 and 10 phr of the first part of the composition.
  • the carbonate with hydroxyl functionality may be provided in a range of between 2 and 10 phr of the first part of the composition.
  • the term “phr” is intended to mean parts per hundred parts of the liquid components of the respective part of the composition. In the case of the carbonate with hydroxyl functionality, the term “phr” is parts of the carbonate per hundred parts of the total liquid components of the first part of the two part composition.
  • the carbonate with hydroxyl functionality may be provided in a range of between 0.1 and 8 wt.% of the total composition. In some embodiments, the carbonate with hydroxyl functionality may be provided in a range of between 0.1 and 5 wt.% of the total composition. In some embodiments, the carbonate with hydroxyl functionality may be provided in a range of between 0.1 and 2 wt.% of the total composition. In some embodiments, the carbonate with hydroxyl functionality may be provided in a range of between 0.1 and 1 wt.% of the total composition.
  • the polyhydric alcohol may be provided in a range of between 1 and 20 phr of the second part of the composition. In some embodiments, the polyhydric alcohol may be provided in a range of between 2 and 20 phr of the second part of the composition. In some embodiments, the polyhydric alcohol may be provided in a range of between 2 and 15 phr of the second part of the composition. In some embodiments, the polyhydric alcohol may be provided in a range of between 5 and 15 phr of the second part of the composition.
  • the polyhydric alcohol may be provided in a range of between 0.1 and 8 wt.% of the total composition. In some embodiments, the polyhydric alcohol may be provided in a range of between 0.1 and 5 wt.% of the total composition. In some embodiments, the polyhydric alcohol may be provided in a range of between 0.1 and 2 wt.% of the total composition. In some embodiments, the polyhydric alcohol may be provided in a range of between 0.1 and 1 wt.% of the total composition.
  • the compositions of the present invention preferably exhibit a pre-cure viscosity of less than 600 Pa*s at 25 °C and at a shear rate of 1 s’ 1 .
  • the pre-cure viscosity is between 100-599 Pa*s at 25 °C and at a shear rate of 1 s' 1 .
  • the pre-cure viscosity is between 200 and 500 Pa*s at 25 °C and at a shear rate of 1 s' 1 .
  • Liquid viscosity may be tested in a flow mode with the following conditions: 25°C; 25mm diameter parallel plate rheometer with a 1mm gap, and a one minute exposure to each shear rate of interest.
  • compositions of the present invention may further exhibit a gel time of less than 600 minutes at 25°C. In some embodiments, the compositions of the present invention may exhibit a gel time of between 50 and 599 minutes at 25°C. In some embodiments, the compositions of the present invention may exhibit a gel time of between 300 and 500 minutes at 25°C.
  • Gel time is generally considered the time required in the epoxy cure reaction to obtain significant thickening of the material. More specifically, the gel time can be determined by the time to reach a peak in the first derivative of the storage modulus during dynamic testing.
  • Gel time may be tested by a parallel plate rheometer set to a 1 mm gap, set to a preshear level of 1.0 s' 1 for 5 seconds, with a strain of 0.1% strain/ 1.0 Hz until a torque limit of 5,000 pN*m is achieved. The test is then continued using a stress control of 5000 p.N*m/l Hz.
  • suitable flow additives include silicone polymers, alkylol ammonium salt of acid, phosphoric acid esters of ketoxime or mixtures thereof.
  • Suitable adhesion promoters include various forms of silane.
  • Suitable conductivity additives include anhydride, glutaric acid, citric acid, phosphoric acid and other acid catalysts.
  • Suitable toughening agents include additives which enhance the impact resistance of the formulation to which they are introduced or generally increase the energy required to propagate a crack in the material.
  • Suitable rheology modifiers include fumed silica and other particulate materials as well as molecular species designed to modify the surface chemistry of fillers or alter the intermolecular environment of the composition.
  • the curable compositions of the present invention when cured, may form a film-like adhesive.
  • the term “film” means a thin film having a thickness of less than 250 micrometers.
  • the film formed from the curable compositions of the present invention, alone or in combination, may be disposed at a surface of a substrate, such as a silicon substrate of an electronic package.
  • the film may also be applied only a surface of a release-treated substrate liner for ease of handling and application to the package substrate.
  • Example release-treated films include release-treated polypropylene, release-treated polyethylene, and release-treated polyethylene terephthalate.
  • the curable compositions of the present invention when cured, may form adhesives in non-film form.
  • the curable compositions of the present invention exhibit good flowability at relatively low temperatures, such as room temperature. This facilitates processing of the compositions by liquid dispensation onto various substrates, including those which are temperature-sensitive.
  • the adhesives of the present invention may be characterized by various tensile properties tested pursuant to ASTM D638 at 25°C and a 0.2 in/min rate, and after a cure period of 24 hours at 25°C.
  • the cured adhesives may exhibit an elongation at break of between 1 and 20%.
  • the cured adhesives may exhibit an elongation at break of between 2 and 15%.
  • the cured adhesives may exhibit an elongation at break of between 4 and 12%.
  • the adhesives of the present invention may also be characterized by Young’s modulus, with the adhesives exhibiting a Young’s modulus of less than 1 GPa at 25°C, preferably less than 500 MPa at 25°C, and more preferably less than 250 MPa at 25°C.
  • the adhesives of the present invention may further exhibit an adhesive strength of at least 1 Pa*s, preferably at least 2 Pa*s, preferably between 2 and 10 Pa*s, and preferably between 4 and 6 Pa*s.
  • the examples further report lap shear strength values, which may be obtained through ASTM C961, but modified to use a 0.1 in/min pull rate and minimum bond line thickness.
  • EPON-862 is a liquid diglycidyl ether of bisphenol F with an epoxy equivalent weight (EEW) of 165-173.
  • EPON-826 is a liquid diglycidyl ether of bisphenol A with an EEW of 178-186.
  • HELOXY 62 is a liquid monofunctional o-cresyl glycidyl ether with an EEW of 175- 195
  • HELOXY 505 is a liquid trifunctional epoxy resin of 9-octadecenoic acid, 12-(2- oxiranyhnethoxy)- 1,2, 3 -propanetriyl ester, homopolymer with an EEW of 500-600.
  • CARDOLITE NX-2024 is a liquid cardanol with a viscosity of 45-60 cPs at 25°C.
  • BYK 9076 is an alkyl ammonium salt of a high molecular weight copolymer, and acts as a wetting and dispersing additive.
  • QYH 40 is a spherical alumina.
  • MARTINAL TM-2550 is a surface treated aluminum hydroxide.
  • AEROSIL R974 is a hydrophobic fumed silica treated with dimethyl dichlorosilane.
  • Yellow Iron Oxide is used as a pigment.
  • ANC AMINE K54 is a tris-(dimethylaminomethyl) phenol
  • PRIAMINE 1074 is an amine of C36-dimer fatty acid, diamine hydrogenated.
  • Examples 1 A and IB contain 5 phr of the conventional CARDOLITE NX-2024 reaction accelerator in both parts A and B.
  • Example 1 A further includes 10 phr of the ANCAMINE K54 curing agent added to part B only.
  • Example 1 The materials produced in Example 1 demonstrates low viscosity and high elongation at break, but a gel time that is too long for the target application.
  • Examples 2A and 2B replace the conventional reaction accelerator with glycerol.
  • Examples 2 A and 2B demonstrate a significant reduction in gel time. However, these example compositions also demonstrate an increase in precure viscosity and a reduction in modulus and glass transition temperature (T g ).
  • Examples 3A and 3B replace the conventional reaction accelerator with glycerol carbonate.
  • Examples 3A and 3B demonstrate an improvement in both gel time and modulus, but also exhibit reduced flexibility as measured by the elongation at break.
  • Examples 4A and 4B demonstrate a balance of reduced gel time, increased modulus, and flexibility. The glass transition temperatures are higher than the comparison Examples. Thus, Examples 4A and 4B demonstrate low pre-cure viscosity and reduced gel time by using a biobased reaction accelerator, while maintaining important physical properties of the cured adhesive produced with conventional materials. Further changes to viscosity could be made by adding or adjusting the amount of low viscosity reactive diluents, such as polyethylene glycol or polypropylene glycol.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)

Abstract

Un adhésif époxy peut être formé à partir d'une composition époxy/amine durcissable, la polymérisation de l'époxy étant favorisée par un accélérateur de réaction ayant un premier composant comprenant un carbonate ayant une fonctionnalité hydroxyle, et un second composant comprenant un alcool monofonctionnel et/ou un alcool multifonctionnel. L'accélérateur de réaction peut être biosourcé pour réduire ou éliminer les risques chimiques.
PCT/US2025/014264 2024-02-02 2025-02-03 Compositions adhésives thermoconductrices Pending WO2025166327A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080039555A1 (en) * 2006-08-10 2008-02-14 Michel Ruyters Thermally conductive material
US20100099842A1 (en) * 2007-02-22 2010-04-22 Huntsman Petrochemical Corporation Accelerators for polymerization of epoxy resins
US20130203894A1 (en) * 2010-03-11 2013-08-08 Huntsman Petrochemical Llc Cycloaliphatic carbonates as reactive diluents in epoxy resins
CN114940808A (zh) * 2022-07-14 2022-08-26 湖北瀚飞新材料科技有限公司 一种可循环利用的环氧树脂Vitrimer材料及其制备方法
CN116332895A (zh) * 2023-03-16 2023-06-27 中国科学院山西煤炭化学研究所 一种活性环氧树脂稀释剂及其制备方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080039555A1 (en) * 2006-08-10 2008-02-14 Michel Ruyters Thermally conductive material
US20100099842A1 (en) * 2007-02-22 2010-04-22 Huntsman Petrochemical Corporation Accelerators for polymerization of epoxy resins
US20130203894A1 (en) * 2010-03-11 2013-08-08 Huntsman Petrochemical Llc Cycloaliphatic carbonates as reactive diluents in epoxy resins
CN114940808A (zh) * 2022-07-14 2022-08-26 湖北瀚飞新材料科技有限公司 一种可循环利用的环氧树脂Vitrimer材料及其制备方法
CN116332895A (zh) * 2023-03-16 2023-06-27 中国科学院山西煤炭化学研究所 一种活性环氧树脂稀释剂及其制备方法和应用

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