WO2007100329A1 - Adhesive composition containing cyclic siloxanes - Google Patents

Adhesive composition containing cyclic siloxanes Download PDF

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Publication number
WO2007100329A1
WO2007100329A1 PCT/US2006/007458 US2006007458W WO2007100329A1 WO 2007100329 A1 WO2007100329 A1 WO 2007100329A1 US 2006007458 W US2006007458 W US 2006007458W WO 2007100329 A1 WO2007100329 A1 WO 2007100329A1
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Prior art keywords
compound
substrate
substituted
composition
die
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PCT/US2006/007458
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English (en)
French (fr)
Inventor
Farhad G. Mizori
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Designer Molecules, Inc.
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Priority to PCT/US2006/007458 priority Critical patent/WO2007100329A1/en
Priority to CN200680019952.1A priority patent/CN101223181A/zh
Publication of WO2007100329A1 publication Critical patent/WO2007100329A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/2919—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01005—Boron [B]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01006—Carbon [C]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01013—Aluminum [Al]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/0102—Calcium [Ca]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01029—Copper [Cu]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01046—Palladium [Pd]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01079—Gold [Au]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/0665—Epoxy resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/10251—Elemental semiconductors, i.e. Group IV
    • H01L2924/10253—Silicon [Si]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/14—Integrated circuits

Definitions

  • the present invention relates generally to adhesive compositions, and more particularly to adhesive compositions containing cyclic siloxanes.
  • Adhesive compositions are used for a variety of purposes in the fabrication and assembly of semiconductor packages and microelectronic devices. The more prominent uses include bonding of electronic elements such as integrated circuit chips to lead frames or other substrates, and bonding of circuit packages or assemblies to printed wire boards. Adhesives useful for electronic packaging applications typically exhibit properties such as good mechanical strength, curing properties that do not affect the component or the carrier, and thixotropic properties compatible with application to microelectronic and semiconductor components.
  • Adhesives used in the electronic packaging industry typically contain a thermosetting resin combined with a filler and some type of curing initiator. These resins are primarily used in the electronics industry for the preparation of non-hermetic electronic packages. Adhesives useful for electronic packaging applications typically exhibit properties such as good mechanical strength, curing properties that do not affect the function of the component or the carrier, and thixotropic properties compatible with application to microelectronic and semiconductor components. Examples of such packages are ball grid array (BGA) assemblies, super ball grid arrays, IC memory cards, chip carriers, hybrid circuits, chip-on-board, multi-chip modules, pin grid arrays, and the like. [0004] For all these applications, the microelectronics industry continues to require new resins that are able to meet increasing demands and varying specifications. Accordingly, there is a need for the development of materials to address the requirements of this rapidly evolving industry.
  • the invention is based on the discovery that certain well-defined funtionalized cyclic siloxanes are useful as thermosetting resins for the electronic packaging industry.
  • the functionalized cyclic siloxane compounds described herein can be cured in a variety of ways, depending on the polymerizable moiety incorporated into the compound.
  • Invention cyclic siloxanes are readily prepared via hydrosilation of polyalkyl(hydro)cyclosiloxanes with appropriately functionalized alkenes and/or alkynes.
  • A is a siloxane ring
  • R is C 1 to about C 20 alkyl
  • each L is independently a substituted or uns ⁇ bstituted alkylene, substituted or unsubstituted oxyalkylene, or covalent bond
  • at least one E is a polymerizable moiety
  • n is 3 to about 6.
  • die-attach pastes including a) 2 weight percent to about 98 weight percent (wt %) of at least one compound as set forth above, or combinations thereof, based on total weight of the composition. b) 0 to about 90 wt% of a filler; c) 0.1 wt % to about 5 wt % of at least one curing initiator, based on total weight of the composition; d) 0.1 wt% to about 4 wt%, of at least one coupling agent, based on total weight of the composition.
  • the invention provides functionalized cyclic siloxanes that are useful as thermosetting resins for the electronic packaging industry.
  • the functionalized cyclic siloxanes described herein are prepared via hydrosilation of appropriately functionalized alkenes and/or alkynes with polyalkyl(hydro)cyclosiloxanes.
  • the polyalkyl(hydro)cyclosiloxanes are commercially available and can be used as a mixture of cyclic species or can be purified by distillation prior to the hydrosilation reaction. Hydrosilation is achieved using well-known catalysts such as, for example, platinum, and the like.
  • the compounds described herein can be tailored to address the particular needs of the microelectronic packaging industry.
  • Important properties for resins used in the microelectronic packaging industry include, for example, crosslink density, hydrophobicity, glass transition temperature (T g ), coefficient of thermal expansion (CTE), and the like.
  • the term “functionalized cyclic siloxane” refers to a compound having a siloxane ring, as well as a polymerizable moiety.
  • the term “polymerizable moiety” refers to a moiety having at least one unit of unsaturation that is capable of participating in a polymerization reaction. Typically, the unit of unsaturation is a carbon-carbon double bond.
  • the term “polymerizable moiety” refers to a ring-opening moiety, such as, for example, epoxy, oxetane, oxazoline, benzoxazine, and the like.
  • the term “polymerizable moiety” refers to a moiety that forms a ring upon polymerization, such as, for example, cyanate esters, propargyl ethers, and the like.
  • aliphatic refers to any alkyl, alkenyl, cycloalkyl, or cycloalkenyl moiety.
  • alkyl refers to straight or branched chain hydrocarbyl groups having from 1 up to about 100 carbon atoms. Whenever it appears herein, a numerical range, such as “1 to 100" or “C 1 -C 100 ", refers to each integer in the given range; e.g., "C 1 -C 100 alkyl” means that an alkyl group may comprise only 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 100 carbon atoms, although the term “alkyl” also includes instances where no numerical range of carbon atoms is designated).
  • Substituted alkyl refers to alkyl moieties bearing substituents including alkyl, alkenyl, alkynyl, hydroxy, oxo, alkoxy, mercapto, cycloalkyl, substituted cycloalkyl, heterocyclic, substituted heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, substituted aryloxy, halogen, haloalkyl, cyano, nitro, nitrone, amino, amido, -C(O)H, -C(O)-, -C(O)-, -S-, -S(O) 2 , -OC(O)-O-, -NR-C(O), - NR-C(O)-NR, -OC(O)-NR, wherein R is H or lower alkyl, acyl, oxyacyl, carboxyl, carbamate, sulfonyl,
  • cycloalkyl refers to cyclic ring-containing groups typically containing in the range of about 3 up to about 8 carbon atoms
  • substituted cycloalkyl refers to cycloalkyl groups further bearing one or more substituents as set forth above.
  • aryl refers to aromatic groups having in the range of 6 up to 14 carbon atoms and “substituted aryl” refers to aryl groups further bearing one or more substituents as set forth above.
  • heterocyclic refers to cyclic (i.e., ring-containing) groups containing one or more heteroatoms (e.g., N, O, S, or the like) as part of the ring structure, and having in the range of 3 up to 14 carbon atoms and "substituted heterocyclic” refers to heterocyclic groups further bearing one or more substituents as set forth above.
  • heterocyclic is also intended to refer to heteroaromatic moieties.
  • alkenyl refers to straight or branched chain hydrocarbyl groups having at least one carbon-carbon double bond, and having in the range of about 2 up to about 100 carbon atoms
  • substituted alkenyl refers to alkenyl groups further bearing one or more substituents as set forth above.
  • alkylene refers to a divalent alkyl moiety
  • oxyalkylene refers to an alkylene moiety containing at least one oxygen atom instead of a methylene (CH 2 ) unit.
  • substituted alkylene and substituted oxyalkylene refer to alkylene and oxyalkylene groups further bearing one or more substituents as set forth above.
  • arylene refers to a divalent aryl moiety.
  • substituted arylene refers to arylene moieties bearing one or more substituents as set forth above.
  • acrylate refers to a compound bearing at least one moiety having the structure:
  • methacrylate refers to a compound bearing at least one moiety having the structure:
  • maleimide refers to a compound bearing at least one moiety having the structure:
  • epoxy refers to a compound bearing at least one moiety having the structure:
  • vinyl ether refers to a compound bearing at least one moiety having the structure:
  • acrylamide refers to a compound bearing at least one moiety having the structure:
  • methacrylamide refers to a compound bearing at least one moiety having the structure:
  • A is a siloxane ring
  • R is C 1 to about C 20 alkyl, each L is independently a substituted or unsubstiruted alkylene, substituted or unsubstiruted oxyalkylene, or covalent bond, at least one E is a polymerizable moiety, and n is 3 to about 6. [0030] In some embodiments, R is C 1 to about C 10 alkyl. In other embodiments,
  • R is C 1 to about C 5 alkyl. In still other embodiments, R is C 1 to about C 3 alkyl. In some embodiments, R is methyl.
  • linkers L are contemplated for use in the practice of the invention. Indeed, any moiety that can be used to link the polymerizable moiety to the siloxane ring is contemplated for use in the practice of the invention.
  • L is a direct bond, linking the polymerizable moiety to the siloxane ring.
  • L is a C 1 to about C 20 substituted or unsubstituted alkylene or oxyalkylene. In other embodiments, L is a C 1 to about C 10 substituted or unsubstituted alkylene or oxyalkylene.
  • the linker L may optionally bear a wide variety of substituents, including, but not limited to, alkyl, alkenyl, alkynyl, hydroxy, oxo, alkoxy, mercapto, cycloalkyl, substituted cycloalkyl, heterocyclic, substituted heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, substituted aryloxy, halogen, haloalkyl, cyano, nitro, nitrone, amino, amido, -C(O)H, -C(O)-, -C(O)-, -S-, -S(O) 2 , -OC(O)-O-, -NR- C(O), -NR-C(O)-NR, -OC(O)-NR, wherein R is H or lower alkyl, acyl, oxyacyl, carboxyl, carbamate, sulfon
  • the polymerizable moiety E can be chosen from a wide variety of reactive groups. Indeed, the selection of E will depend on the type of thermosetting chemistry desired in the ultimate adhesive. For example, for an adhesive composition that is to be cured by a free-radical mechanism, a typical selection for E is acrylate, methacrylate, cyanoacrylate, maleimide, acrylamide, and the like.
  • E is selected from epoxies, imides, cyanate esters, vinyl ethers, vinyl esters, vinyl acetates, esters, ureas, amides, olefins (such as ethylenes, propylenes, and the like), cyclic olefins (such as norbornenyl, and the like) siloxanes, styrenes, oxazolines, benzoxazines, oxetanes, and the like, or combinations thereof.
  • olefins such as ethylenes, propylenes, and the like
  • cyclic olefins such as norbornenyl, and the like
  • siloxanes such as ethylenes, propylenes, and the like
  • styrenes such as ethylenes, propylenes, and the like
  • oxazolines such as norbornenyl, and the like
  • benzoxazines oxetanes, and the
  • n can oe a moiety mat is used to manipulate hydrophobicity or crosslink density of the final resin.
  • moieties contemplated as component E include, alkyl, fluoroalkyl, perfluoroalkyl, and the like.
  • curing mechanisms will be known to the skilled artisan, including, but not limited to free radical, ring-opening, ring-closing, ene reactions, and the like.
  • each E is independently a free- radical polymerizable moiety, a ring-opening polymerizable moiety, or a ring-closing polymerizable moiety.
  • each E is independently a free-radical polymerizable moiety such as, for example, acrylate, methacrylate, maleimide, acrylamide, methacrylamide, styrenic, vinyl ester, olefin, cyclic olefin (such as norbornyl, and the like), allyl, vinyl ether, itaconate, fumarate, and the like.
  • each E is independently a ring-opening polymerizable moiety such as, for example, epoxy, oxetane, oxazoline, benzoxazine, and the like.
  • each E is independently a ring-closing polymerizable moiety such as, for example, cyanate ester, propargyl ether, and the like.
  • exemplary invention compounds include, but are not limited to, compounds having the structures set forth below:
  • Compound 9 Indeed, compounds containing 2 or more alkene and/or alkyne units can be hydrosilated to produce dimers, trimers, and other oligomeric functionalized polycyclic siloxanes. Dendrimeric functionalized polyyclic siloxanes are also contemplated for use in the practice of the invention.
  • adhesive compositions including a functionalized polycyclic siloxane compound of the invention and at least one curing initiator.
  • the functionalized polycyclic siloxane compound is present in the composition from about about 2 weight percent to about 98 weight percent (wt %) based on total weight of the composition.
  • there is at least additional compound that can co-cure with the functionalized polycyclic siloxane is typically present in the composition from about 10 wt% to about 90 wt% based on total weight of the composition.
  • Such additional compounds include, for example, epoxies (such as phenolics, novalacs (both phenolic and cresolic) and the like), imides, monomaleimides, bismaleimides, polyrnaleimides, cyanate esters, vinyl ethers, vinyl esters, vinyl acetates, esters, ureas, amides, olefins (such as ethylenes, propylenes, and the like) siloxanes, cyanoacrylates, styrenes, oxazolines, benzoxazines, oxetanes, and the like, or combinations thereof.
  • epoxies such as phenolics, novalacs (both phenolic and cresolic) and the like
  • imides monomaleimides, bismaleimides, polyrnaleimides, cyanate esters, vinyl ethers, vinyl esters, vinyl acetates, esters, ureas, amides, olef
  • the at least one curing initiator is typically present in the composition from about 0.1 wt % to about 5 wt % based on total weight of the composition.
  • the curing initiator is a free-radical initiator.
  • the term "free radical initiator” refers to any chemical species which, upon exposure to sufficient energy (e.g., light, heat, or the like), decomposes into two parts which are uncharged, but which each possess at least one unpaired electron.
  • Free radical initiators contemplated for use in the practice of the present invention are compounds which decompose (i.e., have a half life in the range of about 10 hours) at temperatures in the range of about 7O 0 C up to about 18O 0 C.
  • Exemplary free radical initiators contemplated for use in the practice of the present invention include peroxides (e.g., dicumyl peroxide, dibenzoyl peroxide, 2- butanone peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, 2,5-bis(tert- butylperoxy)-2,5-dimethylhexane, bis(tert-butyl peroxyisopropyl)benzene, and tert-butyl hydroperoxide), azo compounds (e.g., 2,2'-azobis(2-methyl-propanenitrile), 2,2'-azobis(2- methylbutanenitrile), and l,r-azobis(cyclohexanecarbonitrile)), and the like.
  • peroxides e.g., dicumyl peroxide, dibenzoyl peroxide, 2- butanone peroxide, tert-butyl perbenzoate, di-ter
  • free radical initiator also includes photoinitiators.
  • the curing process can be initiated by UV radiation.
  • the photoinitiator is present at a concentration of 0.1 wt% to 5 wt% based on the total weight of the organic compounds in the composition (excluding any filler).
  • the photoinitiator comprises 0.1 wt% to 3.0 wt%, based on the total weight of the organic compounds in the composition.
  • Photoinitiators include benzoin derivatives, benzilketals, ⁇ , ⁇ -dialkoxyacetophenones, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, acylphosphine oxides, titanocene compounds, combinations of benzophenones and amines or Michler's ketone, and the like.
  • die-attach pastes comprising: a) about 2 weight percent to about 98 weight percent (wt %) of at least one invention functionalized polycyclic siloxane compound, based on total weight of the composition; b) 0 wt% to about 90 wt% of a filler; c) about 0.1 wt % to about 5 wt % of at least one curing initiator, based on total weight of the composition; and d) about 0.1 wt% to about 4 wt%, of at least one coupling agent, based on total weight of the composition.
  • the die-attach pastes described herein may further comprise additional compounds that can co-cure with the functionalized polycyclic siloxane.
  • additional compounds include, for example, epoxies (such as phenolics, novalacs (both phenolic and cresolic) and the like), imides, monomaleimides, bismaleimides, polymaleimides, cyanate esters, vinyl ethers, vinyl esters, vinyl acetates, esters, ureas, amides, olefins (such as ethylenes, propylenes, and the like) siloxanes, cyanoacrylates, styrenes, oxazolines, benzoxazines, oxetanes, and the like, or combinations thereof.
  • epoxies such as phenolics, novalacs (both phenolic and cresolic) and the like
  • imides monomaleimides, bismaleimides, polymaleimides, cyanate esters, vinyl ethers
  • Fillers contemplated for use in the practice of the present invention can be electrically conductive and/or thermally conductive.
  • the fillers may act to modify the rheology of the resulting composition or die-attach paste.
  • suitable electrically conductive fillers which can be employed in the practice of the present invention include silver, nickel, copper, aluminum, palladium, gold, graphite, metal-coated graphite (e.g., nickel-coated graphite, copper-coated graphite, and the like), and the like.
  • suitable thermally conductive fillers which can be employed in the practice of the present invention include graphite, aluminum nitride, silicon carbide, boron nitride, diamond dust, alumina, and the like.
  • Compounds that act primarily to modify rheology include polysiloxanes (such as polydimethyl siloxanes) silica, fumed silica, alumina, titania, and the like.
  • the term "coupling agent” refers to chemical species that are capable of bonding to a mineral surface and which also contain polymerizably reactive functional group(s) so as to enable interaction with the adhesive composition and/or die-attach paste. Coupling agents thus facilitate linkage of the die-attach paste to the substrate to which it is applied.
  • Exemplary coupling agents contemplated for use in the practice of the present invention include silicate esters, metal acrylate salts (e.g., aluminum methacrylate), titanates (e.g., titanium methacryloxyethylacetoacetate triisopropoxide), or compounds that contain a copolymerizable group and a chelating ligand (e.g., phosphine, mercaptan, acetoacetate, and the like), hi some embodiments, the coupling agents contain both a co-polymerizable function (e.g., vinyl moiety, acrylate moiety, methacrylate moiety, and the like), as well as a silicate ester function.
  • metal acrylate salts e.g., aluminum methacrylate
  • titanates e.g., titanium methacryloxyethylacetoacetate triisopropoxide
  • a chelating ligand e.g., phosphine, mercaptan, ace
  • silicate ester portion of the coupling agent is capable of condensing with metal hydroxides present on the mineral surface of substrate, while the co-polymerizable function is capable of co- polymerizing with the other reactive components of invention die-attach paste.
  • coupling agents contemplated for use in the practice of the invention are oligomeric silicate coupling agents such as poly(methoxyvinylsiloxane).
  • both photoinitiation and thermal initiation may be desirable.
  • curing of a photoinitiator-containing adhesive can be started by UV irradiation, and in a later processing step, curing can be completed by the application of heat to accomplish a free-radical cure.
  • Both UV and thermal initiators may therefore be added to the adhesive composition.
  • the adhesive compositions and/or die-attach pastes will cure within a temperature range of 80-220 0 C, and curing will be effected within a length of time of less than 1 minute to 60 minutes.
  • the time and temperature curing profile for each adhesive composition will vary, and different compositions can be designed to provide the curing profile that will be suited to the particular industrial manufacturing process.
  • the adhesive compositions and/or die-attach pastes may contain compounds that lend additional flexibility and toughness to the resultant cured adhesive.
  • Such compounds may be any thermoset or thermoplastic material having a Tg of 50° C or less, and typically will be a polymeric material characterized by free rotation about the chemical bonds, the presence of ether groups, and the absence of ring structures.
  • Suitable such modifiers include polyacrylates, poly(butadiene), polyTHF (polymerized tetrahydrofuran, also known as poly(l,4- butanediol)), CTBN (carboxy-terminated butadiene-acrylonitrile) rubber, and polypropylene glycol.
  • toughening compounds may be in an amount up to about 15 percent by weight of the maleimide and other monofunctional vinyl compound.
  • Inhibitors for free-radial cure may also be added to the adhesive compositions and die-attach pastes described herein to extend the useful shelf life of compositions containing the functionalized polycyclic siloxane compounds described herein.
  • inhibitors examples include hindered phenols such as 2,6-di-tert-butyl-4- methylphenol; 2,6-di-tert-butyl-4-methoxyphenol; tert-butyl hydroquinone; tetrakis(methylene(3 , 5 -di-tert-butyl-4-hydroxyhydrocinnamate))benzene; 2,2 ' - methylenebisC ⁇ -tert-butyl-p-cresol); and l,3,5-trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4- hydroxybenzyl)benzene.
  • hindered phenols such as 2,6-di-tert-butyl-4- methylphenol; 2,6-di-tert-butyl-4-methoxyphenol; tert-butyl hydroquinone; tetrakis(methylene(3 , 5 -di-tert-butyl
  • hydrogen-donating antioxidants include derivatives of p-phenylenediamine and diphenylamine. It is also well know in the art that hydrogen- donating antioxidants may be synergistically combined with quinones, and metal deactivators to make a very efficient inhibitor package. Examples of suitable quinones include benzoquinone, 2-tertbutyl-l,4-benzoquinone; 2-phenyl-l,4- benzoquinone; naphthoquinone, and 2,5-dichloro-l,4-benzoquinone.
  • metal deactivators examples includeN,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine; oxalyl bis(benzylidenehydrazide); and N-phenyl-N'-(4-toluenesulfonyl)-p- phenylenediamine.
  • Nitroxyl radical compounds such as TEMPO (2,2,6,6-tetramethyl-l- piperidnyloxy, free radical) are also effective as inhibitors at low concentrations.
  • the total amount of antioxidant plus synergists typically falls in the range of 100 to 2000 ppm relative to the weight of total base resin.
  • Other additives, such as adhesion promoters, in types and amounts known in the art, may also be added.
  • the adhesive compositions and die-attach pastes described herein will perform within the commercially acceptable range for die-attach adhesives.
  • Commerically acceptable values for die shear for the adhesives on a 80 x 80 mil 2 silicon die are in the range of greater than or equal to 1 kg at room temperature, and greater than or equal to 0.5 kg at 240° C.
  • Acceptable values for warpage for a 500 x 500 mil 2 die are in the range of less than or equal to 70 Nm at room temperature.
  • assemblies of components adhered together employing the above-described adhesive compositions and/or die-attach pastes.
  • assemblies comprising a first article adhered to a second article by a cured aliquot of the above-described adhesive composition are provided.
  • Articles of the present invention can be any article of manufacture for which adhesion to another article is desired.
  • Articles particularly contemplated for assembly employing invention compositions include electronic articles such as memory devices, ASIC devices, microprocessors, flash memory devices, and the like.
  • Microelectronic devices contemplated for use with invention die-attach pastes include copper lead frames, Alloy 42 lead frames, silicon dice, gallium arsenide dice, germanium dice, and the like.
  • Conditions suitable to cure invention die-attach pastes include subjecting the above-described assembly to a temperature of less than about 200 0 C for about 0.5 up to about 2 minutes. This rapid, short duration heating can be accomplished in a variety of ways, e.g., with an in-line heated rail, a belt furnace, or the like, as will be well known to the skilled artisan.
  • the pastes can be oven cured at 150-220 0 C.
  • Example 1 A 500-mL round bottomed flask with a Teflon-coated stir bar was charged with 30.0 g (500 mmol Si-H) of tetramethylcyclosiloxane along with toluene (200 g) and two crystals of chloroplatinic acid. The solution was warmed to around 50°C. A pressure equalized dropping funnel was fitted on to the flask. To the funnel was added allyl glycidyl ether (500 mmol, 57.0 g), which was added dropwise over 30 minutes to the stirred solution. The exothermic reaction started to subside after about one hour.
  • allyl glycidyl ether 500 mmol, 57.0 g
  • the dropping funnel was replaced with a reflux condenser and the solution was refluxed for 2 hours to complete the hydrosilation. After cooling the solution was filtered through 20 g of silica gel to remove the catalyst and decolorize the solution. Removal of the solvent afforded about 80 g of a clear fluid material.
  • Example 2 80 g of the tetra-epoxy compound made in example 1 was charged into a 1-L 2-neck flask equipped with a Teflon-coated stir bar, a reflux condenser and a gas dispersion tube. Toluene (200 g) was added to the flask along with methacrylic acid (175 mmol, 15.0 g). To the flask was also added 500 ppm (0.05 g) of BHT and O.lg of dimethyl aminopyridine (DMAP). The solution was stirred at approximately 100 0 C for 2 hours while a small amount of air was pumped into the solution to prevent polymerization of the product.
  • DMAP dimethyl aminopyridine
  • the work-up of the product consisted of washing the solution in a separatory funnel with saturated NaHCO 3 solution to remove the excess methacrylic acid, drying over MgSO 4 , followed by filtering over 20 g of silica gel. The removal of the solvent afforded 84 g of a clear low viscosity liquid.
  • Example 3 A 500-mL round-bottomed flask with a Teflon-coated stir bar was charged with 20.0 g (333 mmol of Si-H) of tetramethylcyclosiloxane, along with 200 g of toluene and two crystals of chloroplatinic acid and 500 ppm (0.03 g) of BHT. The solution was heated slightly to about 50°C. To a pressure equalized dropping funnel was added vinylnorbornene (333 mmol, 40.0 g), which was added drop wise to the heated solution over 30 minutes. The exothermic reaction subsided after about one hour.
  • the dropping funnel was replaced with a reflux condenser and the solution was refluxed for 2 hours to complete the hydrosilation. After cooling, the solution was filtered over 15 g of silica gel to decolorize the solution. Removal of the solvent afforded 55 g of a thick clear resin.
  • Example 4 A 500-mL round bottomed flask with a Teflon-coated stir bar was charged with 30.0 g (500 mmol Si-H) of tetramethylcyclosiloxane along with toluene (200 g), two crystals of chloroplatinic acid, and 500 ppm (0.05 g) of BHT. To a pressure equalized dropping funnel was added allyl glycidyl ether (250 mmol 28.5 g). The tetramethylcyclosiloxane solution was heated to around 50 0 C, while the allyl glycidyl ether was added dropwise over 30 minutes.
  • the dropping funnel is charged with vinylnorbornene (250 mmol 30.0 g). This reagent is also slowly added over 30 minutes. After the addition is complete the dropping funnel is replaced with a reflux condenser and the solution is refluxed for 2 hours to complete the hydrosilation. After cooling the solution is filtered through 20 g of silica gel to remove the catalyst and to help decolorize the solution. After removal of the solvent using a rotary evaporator approximately 80 g of a thick viscous clear liquid was obtained.
  • Example 5 A 500-mL round-bottomed flask equipped with a Teflon-coated stir bar and a pressure equalized dropping funnel was charged with 20.0 g (333 mmol of Sill) of tetramethylcyclosiloxane. To the flask were also added toluene (150 g) and two crystals of chlroplatinic acid. To the dropping funnel was added allyl glycidyl ether (223 mmol, 25.4 g). The solution was heated to around 50 0 C, while the allyl glycidyl ether was added dropwise over 30 minutes.
  • Example 6 A 500-mL round-bottomed flask equipped with a Teflon-coated stir bar and a pressure equalized dropping funnel was charged with 24.0 g (400 mmol of Si- H) of tetramethylcyclosiloxane. To the flask were also added toluene (200 g) and two crystals of chlroplatinic acid. To the dropping funnel was added allyl glycidyl ether (200 mmol, 22.8 g). The solution was heated to around 50°C, while the allyl glycidyl ether was added dropwise over 30 minutes.
  • the dropping funnel was charged with vinyl-norbornene (200 mmol, 24.0 g), which was added dropwise to the solution over 30 minutes.
  • the dropping funnel was replaced with a reflux condenser and the solution was refluxed for 2 hours to complete the reaction.
  • the cooled solution was filtered through 10 g of silica gel to remove the color and catalyst. After removal of the solvent 80 g of a thin clear liquid was obtained.
  • Example 8 A 500-mL round bottomed-flask equipped with a Teflon-coated stir bar and pressure equalized dropping funnel was charged with 24.0 g (400 mmol Si-H) of tetramethylcyclosiloxane. To the flask were also added toluene (200 g) and two crystals of chloroplatinic acid. The solution was heated to 50 0 C, while 1-tetradecene (200 mmol 39.2 g) was added dropwise to the reaction over 30 minutes. After the exotherm subsided the dropping funnel was charged with allyl glycidyl ether (200 mmol, 23.0 g), which was added dropwise the reaction over 30 minutes.
  • the dropping funnel was replaced with a reflux condenser and the solution was refluxed for 2 hours to complete the hydrosilation. After cooling the solution was filtered through 20 g of silica gel. Removal of the solvent afforded 80 g of clear low viscosity liquid.
  • Example 9 A 500-mL round bottomed flask with a Teflon-coated stir bar was charged with 24.0 g (400 mmol Si-H) of tetramethylcyclosiloxane, along with toluene (150 g) and two crystals of chloroplatinic acid. To the flask was also added bisphenol-A diallyl ether (100 mmol, 15.4 g). The flask was warmed to about 50°C where the exothermic hydrosilation reaction started to occur and the temperature rose to around 70 0 C. After the exothermic reaction subsided, a pressure equalized dropping funnel was added fitted on the flask.
  • allyl glycidyl ether 300 mmol, 34.2 g
  • the dropping funnel was replaced with a reflux condenser and the solution was refluxed for 2 hours to complete the hydrosilation.
  • the solution was filtered through 20 g of silica gel to decolorize. Approximately 70 g of a clear fluid material was obtained after removal of the solvent.
  • Example 10 A 500-mL round-bottomed flask equipped with a Teflon-coated stir bar and a pressure equalized dropping funnel was charged with 18.0 g (300 mmol Sill) of tetramethylcyclosiloxane. To the flask was added toluene (200 g) of and two crystals of chloroplatinic acid. The solution was stirred and heated to 50°C, while vinyl- triethoxysilane (225 mmol, 43.7 g) was added over 30 minutes to the solution.
  • Example 11 A 500-mL round-bottomed flask equipped with a Teflon-coated stir bar and reflux condenser was charged with 24.0 g (400 mmol Si-H) of tetramethylcyclosiloxane, toluene (200 g), 1-tetradecene (200 mmol, 39.2 g), and two crystals of chloroplatinic acid. The solution was heated to 50°C, and the exothermic reaction started to consume the alkene. The solution was allowed to reflux for 3 hours to complete the reaction.
  • the solution was allowed to cool to room temperature when allylamine (230 mmol, 13.0 g) was added to the flask along with two more crystals of chloroplatinic acid, followed by overnight reflux to complete the hydrosilation.
  • the solution was then filtered through 20 g of silica gel to decolorize the intermediate. The removal of the solvent afforded 47 g of a thin liquid.
  • the conversion to the maleimide was done by adding triethylamine (20 g), niethanesulfonic acid (25 g), and toluene (150 g) to the intermediate in a 500 mL round bottomed flask equipped with a stir bar and a dean-stark trap with reflux condenser.
  • Example 12 A 500-mL round-bottomed flask equipped with a Teflon-coated stir bar and reflux condenser was charged with 24.0 g (400 mmol Si-H) of tetramethylcyclosiloxane, toluene (200 g, 200 mmol), t-butylstyrene (32.0 g), and two crystals of chloroplatinic acid. The solution was heated to 5O 0 C, and the exothermic reaction started to consume the alkene. The solution was allowed to reflux for 3 hours to complete the reaction.
  • the solution was allowed to cool to room temperature when allylamine (210 mmol, 12.0 g) was added to the flask along with two more crystals of chloroplatinic acid, followed by overnight reflux to complete the hydrosilation.
  • the solution was then filtered through 1O g of silica gel to decolorize the intermediate. The removal of the solvent afforded 60 g of an orange liquid.
  • the conversion to the maleimide was done by adding 20 g of triethylamine, 27 g of methanesulfonic acid along with a 150 g of toluene to the intermediate in a 500 mL round bottomed flask equipped with a stir bar and a dean-stark trap with reflux condenser.
  • Example 13 A 500-mL round-bottomed flask equipped with a Teflon-coated stir bar and a reflux condenser was charged with 8.75 g (146 mmol Si-H) of tetramethylcyclosiloxane. To the flask were also added vinyl cyclohexene-oxide (108 mmol, 13.4 g), toluene (100 g) and two crystals of chloroplatinic acid. The solution was stirred and refluxed for 3 hours to complete the hydrosilation. After cooling to room temperature, BHT (200 ppm) was added to the flask along with allylmethacrylate (38 mmol, 4.8 g).
  • a gas dispersion tube was inserted into the flask and a small amount of air was bubbled into the stirred solution, while heating to 80°C for 2 hours to complete the hydrosilation.
  • the cooled solution was filtered through 1O g of silica gel, and after removal of the solvent 27 g of a viscous clear liquid was collected.
  • Example 14_ A 500-mL round-bottomed flask equipped with a Teflon-coated stir bar and pressure equalized dropping funnel was charged with 24.0 g (400 mmol Si-H) of tetramethylcyclosiloxane, toluene (150 g), and two crystals of chloroplatinic acid. The solution was heated to 50°C, while allyl glycidyl ether (200 mmol, 22.8 g) was added dropwise to the solution over 30 minutes. After an hour, allylmethacrylate (200 mmol 25.2 g) and BHT (500 ppm) was added to the flask.
  • allylmethacrylate 200 mmol 25.2 g
  • BHT 500 ppm
  • a gas dispersion tube was inserted into the solution and air was admitted into the solution while heating for 3 hours at 100° C to complete the hydrosilation. After cooling, the solution was filtered through 20 g of silica gel. The removal of the solvent under reduced pressure afforded 65 g of a thin yellow liquid.
  • Example 15 A 500-mL round-bottomed flask equipped with a Teflon-coated stir bar and a reflux condenser was charged with 24.0 g (400 mmol Si-H) of tetramethylcyclosiloxane. To the flask was added vinyl cyclohexene-oxide (200 mmol 24.8 g), toluene (200 g), and two crystals of chloroplatinic acid. The solution was stirred and refluxed for 3 hours to complete the hydrosilation.

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