Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08L79/085—Unsaturated polyimide precursors
• • 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
  • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
  • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
• • 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
  • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
  • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C09J179/085—Unsaturated polyimide precursors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/30—Die-attach connectors
• • 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
  • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting
  • H10W72/073—Connecting or disconnecting of die-attach connectors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting
  • H10W72/073—Connecting or disconnecting of die-attach connectors
  • H10W72/07331—Connecting techniques
  • H10W72/07337—Connecting techniques using a polymer adhesive, e.g. an adhesive based on silicone or epoxy
  • H10W72/07339—Connecting techniques using a polymer adhesive, e.g. an adhesive based on silicone or epoxy hardening the adhesive by cooling, e.g. thermoplastics
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/30—Die-attach connectors
  • H10W72/351—Materials of die-attach connectors
  • H10W72/353—Materials of die-attach connectors not comprising solid metals or solid metalloids, e.g. ceramics
  • H10W72/354—Materials of die-attach connectors not comprising solid metals or solid metalloids, e.g. ceramics comprising polymers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W90/00—Package configurations

Definitions

• the present invention relates to film adhesive compositions, and more particularly to the use of film adhesive compositions in stacked die microelectronic packaging applications.
• film adhesive compositions comprising at least one macromonomer having at least one unit of ethylenic unsaturation, at least one thermoplastic elastomer co-curable with the macromonomer, and at least one cure initiator.
• invention compositions are useful as adhesives in the microelectronics industry.
• invention film adhesives may be used to produce microelectronic assemblies with very thin bond lines without compromising adhesive strength.
• invention film adhesive compositions for adhesively attaching a device to a substrate
• methods employing invention film adhesive compositions for adhesively attaching at least two semiconductor dice to a substrate in a stacked arrangement are provided.
• assemblies comprising a first article adhered to a second article by invention film adhesive compositions.
• adhesive compositions comprising at least one macromonomer having at least one unit of ethylenic unsaturation, at least one thermoplastic elastomer co-curable with the macromonomer, and at least one cure initiator.
• macromonomer refers to a compound having properties suitable for use in invention film adhesive compositions.
• macromonomers contemplated for use in the practice of the present invention typically are low melting point solids having low vapor pressures.
• macromonomers contemplated for use in the practice of the present invention may be liquids having a molecular weight of at least about 500 grams/mole.
• unit of ethylenic unsaturation refers to unsaturation comprising localized (i.e., non-aromatic) carbon-carbon double bonds, as shown below:
• co-curable refers to the ability of a thermoplastic elastomer to undergo copolymerization with a macromonomer to form a three-dimensional polymeric network.
• Macromonomers contemplated for use in the practice of the present invention include, for example, maleimides, nadimides, itaconimides, vinyl compounds, allylated amides, and the like, hi one embodiment, maleimide, nadimide, and itaconimide macromonomers contemplated for use in the practice of the present invention include compounds having, respectively, the following structures I, II, and III:
• J is a monovalent or polyvalent radical selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, polysiloxane, polysiloxane-polyurethane block copolymer, and combinations of two or more thereof, optionally containing one or more linkers selected from the group consisting of a covalentbond, -O-, -S-, -NR-, -O-C(O)-, -O-C(O)-O-, -O-C(O)-NR-, -NR-C(O)-, -NR-C(O)-O-, -NR-C(O)-NR-, -S-C(O)-, -S-C(O)-O-, -S-C(O)-O-,
• hydrocarbyl comprises any organic radical wherein the backbone thereof comprises carbon and hydrogen only.
• hydrocarbyl embraces alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, alkylaryl, arylalkyl, arylalkenyl, alkenylaryl, arylalkynyl, alkynylaryl, and the like.
• substituted hydrocarbyl comprises any of the above- referenced hydrocarbyl groups further bearing one or more substituents selected from hydroxy, alkoxy (of a lower alkyl group), mercapto (of a lower alkyl group), cycloalkyl, substituted cycloalkyl, heterocyclic, substituted heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, substituted aryloxy, halogen, trifluoromethyl, cyano, nitro, nitrone, amino, amido, — C(O)H, acyl, oxyacyl, carboxyl, carbamate, dithiocarbamoyl, sulfonyl, sulfonamide, sulfuryl, and the like.
• alkyl refers to saturated straight or branched chain hydrocarbon radical having in the range of 1 up to about 500 carbon atoms.
• Lower alkyl refers to alkyl groups having in the range of 1 up to about 5 carbon atoms.
• Substituted alkyl refers to alkyl groups further bearing one or more substituents as set forth above.
• alkenyl refers to straight or branched chain hydrocarbyl groups having at least one carbon — carbon double bond, and typically having in the range of about 2 up to 500 carbon atoms
• substituted alkenyl refers to alkenyl groups further bearing one or more substituents as set forth above.
• alkynyl refers to straight or branched chain hydrocarbyl groups having at least one carbon — carbon triple bond, and typically having in the range of about 2 up to 500 carbon atoms
• substituted alkynyl refers to alkynyl groups further bearing one or more substituents as set forth above.
• cycloalkyl refers to a cyclic ring-containing groups 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.
• cycloalkenyl refers to cyclic ring-containing groups containing in the range of 3 up to 20 carbon atoms and having at least one carbon-carbon double bond
• substituted cycloalkenyl refers to cycloalkenyl 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.
• alkylaryl refers to alkyl-substituted aryl groups
• substituted alkylaryl refers to alkylaryl groups further bearing one or more substituents as set forth above.
• arylalkyl refers to aryl-substituted alkyl groups
• substituted arylalkyl refers to arylalkyl groups further bearing one or more substituents as set forth above.
• arylalkenyl refers to aryl-substituted alkenyl groups and "substituted arylalkenyl” refers to arylalkenyl groups further bearing one or more substituents as set forth above.
• alkenylaryl refers to alkenyl-substituted aryl groups and “substituted alkenylaryl” refers to alkenylaryl groups further bearing one or more substituents as set forth above.
• arylalkynyl refers to aryl-substituted alkynyl groups and "substituted arylalkynyl” refers to arylalkynyl groups further bearing one or more substituents as set forth above.
• alkynylaryl refers to alkynyl-substituted aryl groups and “substituted alkynylaryl” refers to alkynylaryl 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 1 up to 14 carbon atoms and "substituted heterocyclic” refers to heterocyclic groups further bearing one or more substituents as set forth above.
• exemplary heterocyclic moieties include saturated rings, unsaturated rings, and aromatic heteroatom-containing ring systems, e.g., epoxy, tetrahydrofuran, oxazoline, oxazine, pyrrole, pyridine, furan, tetrazole, and the like.
• hydrocarbylene refers to divalent straight or branched chain hydrocarbyl groups including alkylene groups, alkenylene groups, alkynylene groups, cycloalkylene groups, heterocycloalkylene groups, arylene groups, heteroarylene groups, alkylarylene groups, arylalkylene groups, arylalkenylene groups, arylalkynylene groups, alkenylarylene groups, alkynylarylene groups, and the like; and "substituted hydrocarbylene” refers to hydrocarbylene groups further bearing one or more substituents as set forth above.
• alkylene refers to saturated, divalent straight or branched chain hydrocarbyl groups typically having in the range of about 2 up to about 500 carbon atoms
• substituted alkylene refers to alkylene groups further bearing one or more substituents as set forth above.
• alkenylene refers to divalent straight or branched chain hydrocarbyl groups having at least one carbon — carbon double bond, and typically having in the range of about 2 up to 500 carbon atoms
• substituted alkenylene refers to alkenylene groups further bearing one or more substituents as set forth above.
• alkynylene refers to divalent straight or branched chain hydrocarbyl groups having at least one carbon-carbon triple bond, and typically having in the range of about 2 up to 500 carbon atoms
• substituted alkynylene refers to alkynylene groups further bearing one or more substituents as set forth above.
• cycloalkylene refers to divalent ring-containing groups containing in the range of about 3 up to about 8 carbon atoms
• substituted cycloalkylene refers to cycloalkylene groups further bearing one or more substituents as set forth above.
• heterocycloalkylene refers to divalent 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 1 up to 14 carbon atoms and "substituted heterocycloalkylene” refers to heterocycloalkylene groups further bearing one or more substituents as set forth above.
• cycloalkenylene refers to divalent ring-containing groups containing in the range of about 3 up to about 8 carbon atoms and having at least one carbon-carbon double bond
• substituted cycloalkenylene refers to cycloalkenylene groups further bearing one or more substituents as set forth above.
• arylene refers to divalent aromatic groups typically having in the range of 6 up to 14 carbon atoms and "substituted arylene” refers to arylene groups further bearing one or more substituents as set forth above.
• alkylarylene refers to alkyl-substituted divalent aryl groups typically having in the range of about 7 up to 16 carbon atoms and "substituted alkylarylene” refers to alkylarylene groups further bearing one or more substituents as set forth above.
• arylalkylene refers to aryl-substituted divalent alkyl groups typically having in the range of about 7 up to 16 carbon atoms and "substituted arylalkylene” refers to arylalkylene groups further bearing one or more substituents as set forth above.
• arylalkenylene refers to aryl-substituted divalent alkenyl groups typically having in the range of about 8 up to 16 carbon atoms and "substituted arylalkenylene” refers to arylalkenylene groups further bearing one or more substituents as set forth above.
• arylalkynylene refers to aryl-substituted divalent alkynyl groups typically having in the range of about 8 up to 16 carbon atoms and "substituted arylalkynylene” refers to arylalkynylene group further bearing one or more substituents as set forth above.
• alkenylarylene refers to alkenyl-substituted divalent aryl groups typically having in the range of about 7 up to 16 carbon atoms and "substituted alkenylarylene” refers to alkenylarylene groups further bearing one or more substituents as set forth above.
• alkynylarylene refers to alkynyl-substituted divalent aryl groups typically having in the range of about 7 up to 16 carbon atoms and "substituted alkynylarylene” refers to alkynylarylene groups further bearing one or more substituents as set forth above.
• heteroarylene refers to divalent aromatic groups containing one or more heteroatoms (e.g., N, O, S or the like) as part of the aromatic ring, and typically having in the range of 3 up to 14 carbon atoms and "substituted heteroarylene” refers to heteroarylene groups further bearing one or more substituents as set forth above.
• polysiloxane-polyurethane block copolymers refer to polymers containing both at least one polysiloxane (soft) block and at least one polyurethane (hard) block.
• linkers to form the "J" appendage of a maleimide, nadimide or itaconimide group
• linkers can be produced, such as, for example, oxyalkyl, thioalkyl, aminoalkyl, carboxylalkyl, oxyalkenyl, thioalkenyl, aminoalkenyl, carboxyalkenyl, oxyalkynyl, thioalkynyl, aminoalkynyl, carboxyalkynyl, oxycycloalkyl, thiocycloalkyl, aminocycloalkyl, carboxycycloalkyl, oxycloalkenyl, thiocycloalkenyl, aminocycloalkenyl, carboxycycloalkenyl, heterocyclic, oxyheterocyclic, thioheter
• maleimides, nadimides, and itaconimides contemplated for use in the practice of the present invention have the structures I, II, or III wherein,
• each Ar is a monosubstituted, disubstituted or trisubstituted aromatic or heteroaromatic ring having in the range of 3 up to 10 carbon atoms, and Z is:
• polyalkylene oxides having the structure: -[(CR 2 ) r -O-] q -(CR 2 ) s - wherein each R is independently defined as above, r and s are each defined as above, and q falls in the range of 1 up to 50;
• each R is independently defined as above, t falls in the range of 2 up to 10, u falls in the range of 2 up to 10, and Ar is as defined above;
• E is -O- or -NR 5 -, wherein R 5 is hydrogen or lower alkyl
• J is of sufficient length to render liquid the maleimide, nadimide, itaconimide or combinations of two or more thereof.
• m 1, 2 or 3
• J is a branched chain alkyl, alkylene or alkylene oxide of sufficient length and branching to render liquid the maleimide, nadimide, itacommide or combinations of two or more thereof.
• Preferred maleimides, nadimides, and itaconimides contemplated for use in the practice of the present invention include, for example, maleimides, nadimides, and itaconimides having the following structures:
• Vinyl macromonomers contemplated for use in the practice of the present invention include compounds having the following structure:
• each R is independently selected from hydrogen or lower alkyl
• each Q is independently selected from -O-, -O-C(O)-, -C(O)- or -C(O)-O-, and
• Y is a monovalent or a polyvalent moiety comprising organic or organosiloxane radicals, and combinations of two or more thereof.
• Y is a monovalent or polyvalent radical selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, polysiloxane, polysiloxane-polyurethane block copolymer, and combinations of two or more thereof, optionally containing one or more linkers selected from the group consisting of a covalent bond, -O-, -S-, -NR-, -O-C(O)-, -O-C(O)-O-, -O-C(O)-NR-, -NR-C(O)-, -NR-C(O)-O-, -NR-C(O)-NR-, -S-C(O)-, -S-C(O)-O-, -S-C(O)-O-,
• Y is
• each Ar is a monosubstituted, disubstituted or trisubstituted aromatic or heteroaromatic ring having in the range of 3 up to 10 carbon atoms, and Z is:
• polyalkylene oxides having the structure: -[(CR 2 ) r -O-] q -(CR 2 ) s - wherein each R is independently defined as above, r and s are each defined as above, and q falls in the range of 1 up to 50;
• each R is independently defined as above, t falls in the range of 2 up to 10, u falls in the range of 2 up to 10, and Ar is as defined above;
• E is -O- or -NR 5 -, wherein R 5 is hydrogen or lower alkyl
• a siloxane having the structure: -(C(R 3 ) 2 ) d - [Si(R 4 ) 2 -O] r Si(R 4 ) 2 -(C(R 3 ) 2 )e-, -(C(R 3 ) 2 ) d -C(R 3 )-C(O)O- (C(R 3 ) 2 ) d -[Si(R 4 ) 2 -O] r Si(R 4 ) 2 -(C(R 3 ) 2 ) e -O(O)C-(C(R 3 ) 2 ) e - , or -(C(R 3 ) 2 ) d -C(R 3 )-O(O)C-(C(R 3 ) 2 ) d -[Si(R 4 ) 2 -O] r Si(R 4 ) 2 -(C(R 3 ) 2 ) d -[Si(R 4
• each R 6 is independently hydrogen or lower alkyl; each R is independently an alkyl, aryl, or arylalkyl group having 1 to 18 carbon atoms; each R is an alkyl or alkyloxy chain having up to about 100 atoms in the chain, optionally substituted with Ar;
• Allylated amide macromonomers contemplated for use in the practice of the present invention include compounds having the following structure:
• R' is hydrogen, up to about Cis alkyl or oxyalkyl, allyl, aryl, or substituted aryl, m is 1-6, and
• X is is a monovalent or a polyvalent moiety comprising organic or organosiloxane radicals, and combinations of two or more thereof.
• X is a monovalent or polyvalent radical selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, polysiloxane, polysiloxane-polyurethane block copolymer, and combinations of two or more thereof, optionally containing one or more linkers selected from the group consisting of a covalent bond, -O-, -S-, -NR-, -O-C(O)-, -O-C(O)-O-, -O-C(O)-NR-, -NR-C(O)-, -NR-C(O)-O-, -NR-C(O)-NR-, -S-C(O)-, -S-C(O)-O-, -S-C(O)-O-,
• Ar-C-O-Z-O-C-Ar- wherein each Ar is a monosubstituted, disubstituted or trisubstituted aromatic or heteroaromatic ring having in the range of 3 up to 10 carbon atoms, and Z is:
• polyalkylene oxides having the structure: -[(CR 2 ) r -O-] q -(CR 2 ) s - wherein each R is independently defined as above, r and s are each defined as above, and q falls in the range of 1 up to 50;
• each R is independently defined as above, t falls in the range of 2 up to 10, u falls in the range of 2 up to 10, and Ar is as defined above;
• E is -O- or -NR 5 -, wherein R 5 is hydrogen or lower alkyl; and is
• Thermoplastic elastomers contemplated for use in the practice of the present invention are typically block copolymers.
• the block copolymers have at least one unit of the general formula (A-B), or (A-B-A), wherein A is a non-elastomeric polymer block and B is an elastomeric polymer block.
• Block copolymers contemplated for use in the practice of the present invention preferably have low dielectric constants.
• thermoplastic elastomers contemplated for use in the practice of the present invention contain pendant and/or terminal units of ethylenic unsaturation, and therefore are able to cure with other components in the adhesive composition, such as the unsaturated macromonomer.
• the non-elastomeric polymer block (A) is the polymerization product of one or more optionally substituted aromatic hydrocarbons containing at least one unit of ethylenic unsaturation.
• Aromatic hydrocarbons contemplated for use in the practice of the present invention include, for example, optionally substituted styrene, optionally substituted stilbene, and the like.
• Substituents contemplated for optional use in the practice of the present invention include for example, alkyl, alkenyl, alkynyl, hydroxy, alkoxy, alkenoxy, and the like.
• the aromatic hydrocarbon is optionally substituted styrene.
• the elastomeric polymer block (B) is typically the polymerization or copolymerization product of optionally substituted olefin monomers and/or optionally substituted conjugated diene monomers.
• Olefin monomers contemplated for use in the practice of the present invention typically contain from 2 up to about 20 carbon atoms.
• the olefin monomers contain from 2 up to about 12 carbon atoms.
• the olefin monomers include, for example, ethylene, propylene, butylene, isobutylene, acrylonitrile, (meth)acrylate, and the like. Most preferably, the olefin monomer is acrylonitrile.
• Conjugated diene monomers contemplated for use in the practice of the present invention typically contain from 4 up to about 20 carbon atoms.
• the conjugated diene monomers contain from 4 up to about 12 carbon atoms.
• the conjugated diene monomers include, for example, butadiene, isoprene, dimethylbutadiene, and the like. Most preferably, the conjugated diene monomer is butadiene.
• the structure of the elastomeric segments can be optionally modified to increase adhesive strength of invention compositions.
• the elastomeric segments of the block copolymers e.g., the polybutadiene segments
• the elastomeric segments of the block copolymers may be modified via a thermally induced ene-reaction with maleic anhydride (for a review of the ene-reaction, see, for example, Oppolzer, W., Snieckus, V., Angew. Chem. Int. Ed. Engl., 1978, 17, 476).
• Such modification has a particularly positive impact on hot die-shear values.
• Thermoplastic elastomers contemplated for use in the practice of the present invention include, for example, polystyrene-polybutadiene-polystyrene block copolymers, polystyrene-polyisoprene-polystyrene block copolymers, polystyrene-polydimethylbutadiene- polystyrene block copolymers, polybutadiene-polyacrylonitrile block copolymers, and the like.
• the block copolymer is a polystyrene-polybutadiene-polystyrene block copolymer or a polybutadiene-polyacrylonitrile block copolymer.
• thermoplastic elastomers include poly(olefms), poly(dienes), poly eptides), poly(esters), poly(ethers), poly(oxides), poly(sulfides), poly(amines), and the like. More specific examples of such thermoplastic elastomers include syndiotactic polybutadiene, alpha-polyisoprene, poly(2-butyl-2-methyl-beta-alanine), poly(decamethylene 4-octendioate), poly(butylvinyl ether), poly(decamethylene oxide), poly(hexamethylene sulfide), poly(ethylene amine), and the like.
• elastomers include poly(olefms), poly(dienes), poly eptides), poly(esters), poly(ethers), poly(oxides), poly(sulfides), poly(amines), and the like.
• More specific examples of such thermoplastic elastomers include syndiotactic polybutadiene, al
• Adhesive compositions of the invention also contain in the range of 0.2 up to 2 weight % of at least one free radical initiator, wherein weight % (wt %) is based on the total weight of the composition.
• free radical initiator refers to any chemical species which, .upon exposure to sufficient energy (e.g., light, heat, or the like), decomposes into at least two species which are uncharged, but which each possesses at least one unpaired election.
• Preferred 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 70 up to 180° C.
• Free-radical cure initiators contemplated for use in the practice of the present invention include for example, peroxides (e.g., peroxy esters, peroxy carbonates, hydroperoxides, alkylperoxides, arylperoxides, and the like), azo compounds, and the like.
• peroxides e.g., peroxy esters, peroxy carbonates, hydroperoxides, alkylperoxides, arylperoxides, and the like
• azo compounds e.g., azo compounds, and the like.
• Presently preferred peroxides contemplated for use in the practice of the present invention include 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, tert-butyl hydroperoxide, and the like.
• Presently preferred azo compounds contemplated for use in the practice of the present invention include 2,2'- azobis(2-methylpropanenitrile), 2,2'-azobis(2-methylbutanenitrile), 1,1'- azobis(cyclohexanecarbonitrile), and the like.
• Adhesive compositions contemplated for use in the practice of the present invention typically contain in the range of about 10 wt % up to about 95 wt % thermoplastic elastomer, in the range of about 5 wt % up to about 90 wt % macromonomer having at least one unit of ethylenic unsaturation, and in the range of about 0.5 wt % up to about 2.0 wt % a cure initiator, wherein weight % is based on the total weight of the composition.
• the macromonomer having at least one unit of ethylenic unsaturation is present in the range of about 10 wt % up to about 80 wt %.
• Adhesive compositions according to the invention optionally further contain in the range of about 0.1 up to about 10 wt % of at least one coupling agent, based on the total weight of the composition.
• the coupling agent is present in the range of about 0.2 wt % up to about 5 wt %.
• Coupling agents contemplated for use in the practice of the present invention include siloxanes, silicate esters, metal acrylate salts, titanates, and the like.
• Film adhesive compositions according to the invention may optionally contain a filler.
• Fillers contemplated for optional use in the practice of the present invention may optionally be conductive (electrically and/or thermally).
• Electrically conductive fillers contemplated for use in the practice of the present invention include, for example, silver, nickel, gold, cobalt, copper, aluminum, graphite, silver-coated graphite, nickel-coated graphite, alloys of such metals, and the like, as well as mixtures thereof.
• Both powder and flake forms of filler maybe used in the adhesive compositions of the present invention.
• the flake has a thickness of less than about 2 microns, with planar dimensions of about 20 to about 25 microns.
• Flake employed herein preferably has a surface area of about 0.15 to 5.0 m 2 /g and a tap density of about 0.4 up to about 5.5 g/cc. It is presently preferred that powder employed in the practice of the invention has a diameter of about 0.5 to 15 microns. If present, the filler typically comprises in the range of about 1 wt % up to about 95 wt % of the film adhesive composition, wherein weight % is based on the total weight of the composition.
• Thermally conductive fillers contemplated for optional use in the practice of the present invention include, for example, aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesia, silica, alumina, and the like.
• the particle size of these fillers will be in the range of about 5 up to about 30 microns. Most preferably, the particle size of these fillers will be about 20 microns.
• Electrically and/or thermally conductive fillers are optionally (and preferably) rendered substantially free of catalytically active metal ions by treatment with chelating agents, reducing agents, nonionic lubricating agents, or mixtures of such agents. Such treatment is described in U.S. Patent No. 5,447,988, which is incorporated by reference herein in its entirety.
• a filler may be used that is neither an electrical nor thermal conductor.
• Such fillers may be desirable to impart some other property to the film adhesive composition, such as, for example, reduced thermal expansion of the cured adhesive, reduced dielectric constant, improved toughness, increased hydrophobicity, and the like.
• examples of such fillers include perfluorinated hydrocarbon polymers (i.e., TEFLONTM), thermoplastic polymers, thermoplastic elastomers, mica, fused silica, glass powder, and the like.
• film adhesive compositions contemplated for use in the practice of the present invention contain in the range of about 5 wt % up to about 90 wt% thermoplastic elastomer, in the range of about 5 wt % up to about 90 wt% macromonomer containing at least one unit of ethylenic unsaturation, in the range of about 0.5 wt % up to about 2.0 wt % cure initiator, in the range of about 0.5 wt % up to about 5 wt % coupling agent, and in the range of about 1 wt % up to about 95 wt% filler, wherein weight % is based on the total weight of the composition.
• a device for adhesively attaching a device to a substrate comprising subjecting a sufficient quantity of an invention film adhesive composition positioned between a substrate and a device to conditions suitable to cure the film adhesive composition.
• Devices contemplated for use in the practice of the present invention include any surface mount component such as, for example, semiconductor die, resistors, capacitors, and the like.
• devices contemplated for use in the practice of invention methods are semiconductor dies.
• Substrates contemplated for use include metal substrates (e.g., lead frames), organic substrates (e.g., laminates, ball grid arrays, polyamide films), and the like.
• Conditions suitable to cure invention film adhesive compositions comprise subjecting invention film adhesive compositions to a temperature of at least about 60° C but less than about 300° C for about 0.25 up to about 2 minutes. In some such embodiments, the cure temperature is in the range of about 75° C up to about 200 ° C. 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.
• conditions suitable to cure invention film adhesive compositions comprise subjecting invention film adhesive compositions to a temperature in the range of about 60°C up to about 200°C for a period of about 15 minutes up to about 60 minutes.
• These conditions can be readily produced in a variety of ways, such, for example, by placing invention film adhesive compositions in a curing oven.
• conditions suitable to cure invention film adhesive compositions may further comprise subjecting invention film adhesive compositions to a pre- cure at a temperature high enough to increase the viscosity of the liquid adhesive and reduce tackiness but low enough to prevent a complete cure.
• Such pre-cured adhesive film compositions may then undergo a final cure as described above to give the fully cured adhesive.
• assemblies comprising a first article permanently adhered to a second article by a sufficient quantity of an invention adhesive composition.
• An adhesive composition according to the present invention was prepared as follows.
• Invention Film Adhesive Composition 1 was prepared using the styrene-butadiene block copolymer KRATONTM D-l 102 as the thermoplastic elastomeric component.
• Octadecyhnaleimide and X-BMI (X-BMI is the 1,20-bismaleimido derivative of 10,11- dioctyl-eicosane) were employed as macromonomers.
• the maleimides used in the following invention film adhesive compositions were prepared according to the procedure set forth in U.S. Patent No. 5,973,166, the entire contents of which are incorporated by reference herein.
• Preparation of Film Adhesive Composition 1 began by dissolving octadecylmaleimide in xylene. KRATON was added to this solution and allowed to dissolve completely before the remaining components were added.
• a film of Invention Film Adhesive Composition 1 was cast onto a glass substrate and dried overnight. A silicon die was then placed onto the film, and the film- coated substrate was heated to 80°C for 1 to 3 seconds. This assembly was finally cured at 185°C for 30 minutes.
• Composition 1 has superior adhesive strength compared to an analogous non-film forming composition. .

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• Polymers & Plastics (AREA)
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• 2002
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