WO2009078878A1 - Composés ayant un squelette oxyde de diphényle et un groupe fonctionnel maléimide - Google Patents

Composés ayant un squelette oxyde de diphényle et un groupe fonctionnel maléimide Download PDF

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Publication number
WO2009078878A1
WO2009078878A1 PCT/US2007/088130 US2007088130W WO2009078878A1 WO 2009078878 A1 WO2009078878 A1 WO 2009078878A1 US 2007088130 W US2007088130 W US 2007088130W WO 2009078878 A1 WO2009078878 A1 WO 2009078878A1
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WIPO (PCT)
Prior art keywords
hydrocarbon chain
compound
curable composition
backbone
substrate
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Application number
PCT/US2007/088130
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English (en)
Inventor
Osama M. Musa
Brian Marr
Original Assignee
Henkel Ag & Co. Kgaa
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Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Priority to PCT/US2007/088130 priority Critical patent/WO2009078878A1/fr
Priority to TW097117989A priority patent/TW200927778A/zh
Publication of WO2009078878A1 publication Critical patent/WO2009078878A1/fr
Priority to US12/818,225 priority patent/US20100311207A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
    • 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
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • 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
    • H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
    • H01L2924/097—Glass-ceramics, e.g. devitrified glass
    • H01L2924/09701—Low temperature co-fired ceramic [LTCC]

Definitions

  • This invention relates to compounds having a diphenyl oxide backbone, which compounds are useful as adhesives, coatings, and encapsulants. These compounds are particularly useful for various fabrication steps in semiconductor packaging.
  • Adhesives for use on metal, glass, and plastic surfaces have many applications within various industries Adhesion to these surfaces in general is difficult and new compounds or formulations are sought for both quick and strong adherence. Such compounds would be particularly useful within the semiconductor packaging industry.
  • Common steps in the fabrication of semiconductor packages involve affixing semiconductor devices onto substrates or encapsulating or coating parts, or all, of the device.
  • the more prominent steps that use adhesives, coatings or encapsulants are the bonding of integrated circuit chips to lead frames or other substrates, the bonding of circuit packages or assemblies to printed wire boards, the encapsulation of solder balls used as electrical connections, and the coating of via holes.
  • the components of the package are prepared from different materials, such as metal, glass, silicon, and plastic, and the adhesive or encapsulant must bond to the surface of each. Moreover, the adhesive or encapsulant must maintain its bond to both materials through temperature and humidity cycles Thus, there is always a need for new compounds and formulations to provide good adhesion to a variety of surfaces, within the semiconductor packaging industry and within other industries using components that must adhere to a surface
  • This invention is a compound having a diphenyl oxide (DPO) backbone, and pendant from the backbone at least one hydrocarbon chain, the hydrocarbon chain containing an ester functionality and being terminated with a maleimide functional group.
  • the compound may further have pendant from the backbone at least one additional hydrocarbon chain, the additional hydrocarbon chain containing an ester functionality and being terminated with a group other than a maleimide.
  • this invention is a curable composition containing the inventive compound; an article having deposited thereon the inventive compound or curable composition; and a process for making a semiconductor device using the inventive compound or curable composition.
  • this invention is a compound having a diphenyl oxide (DPO) backbone, and pendant from the backbone at least one hydrocarbon chain, the hydrocarbon chain containing an ester functionality and being terminated with a maleimide functional group.
  • the compound may further have pendant from the backbone at least one additional hydrocarbon chain, the additional hydrocarbon chain containing an ester functionality and being terminated with a group other than a maleimide.
  • the group other than the maleimide may be either reactive or non-reactive.
  • reactive is meant that the group is capable of reacting with another organic compound to form a new covalent bond, for example, such as can be formed by the reaction of two carbon to carbon double bonds under free radical initiation, or by a ring opening mechanism of an epoxide, oxetane, triazole, cyanurate, or oxazoline.
  • additional group other than the maleimide, those groups may be all reactive, all non-reactive, or a combination of reactive and non-reactive.
  • the additional functional group is selected from the group consisting of acrylate, methacrylate, maleate, fumarate, styrenic, cinnamyl, or any combination of these.
  • this invention is a curable composition
  • a curable composition comprising one or more other curable resins in addition to the compound having the diphenyl oxide backbone and maleimide functionality, with or without a group other than the maleimide functionality.
  • the additional curable resin may be the major component or just a minor component of the curable composition.
  • the curable composition may also comprise curing agents, adhesion promoters, fillers, wetting agents, fluxing agents, and other such components commonly used in curable compositions Curable compositions are used, for example, in adhesive, coating, and encapsulation formulations
  • this invention is an article, for example a semiconductor device, on which has been deposited the DPO compound or curable composition containing the DPO compound.
  • this invention is a process for making a semiconductor device comprising the steps of (i) providing a semiconductor wafer having a front side that is active and opposed to the front side a back side that is inactive, (ii) providing a curable composition comprising a compound having a diphenyl oxide backbone and pendant from the backbone at least one hydrocarbon chain, the hydrocarbon chain containing an ester functionality and being terminated with a maleimide functional group, (iii) applying the curable composition to the back side of the semiconductor wafer to form an adhesive layer having an exposed side opposite the front side of the semiconductor wafer, (iv) B-staging the adhesive layer to form a B-staged wafer, (v) dicing the B-staged wafer into at least one semiconductor die having an adhesive layer on the back side of the semiconductor die, (vi) contacting the semiconductor die to a substrate such that the adhesive layer is disposed between the semiconductor die and the substrate, and (vn) curing the adhesive for a time and temperature to adhere
  • B-staging (and its variants) is used to refer to the processing of a material by heat or irradiation so that if the material is dissolved or dispersed in a solvent, the solvent is evaporated off with or without partial curing of the material, or if the material is neat with no solvent, the material is partially cured to a tacky or more hardened state If the material is a flow-able adhesive, B-staging will provide extremely low flow without fully curing, such that additional curing may be performed after the adhesive is used to join one article to another The reduction in flow may be accomplished by evaporation of a solvent, partial advancement or curing of a resin or polymer, or both
  • this invention is a process for underfilling a flip chip semiconductor device comprising the steps of (t) providing a flip chip die that has been attached to a substrate such that there is a gap between the flip chip die and the substrate, (n) dispensing a curable composition comprising a compound having a diphenyl oxide backbone and pendant from the backbone at least one hydrocarbon chain, the hydrocarbon chain containing an ester functionality and being terminated with a maleimide functional group, onto the substrate along at least one side of the fhp chip die, (in) allowing the curable composition to flow into the gap between the flip chip die and the substrate, and ( ⁇ v) curing the curable composition
  • the DPO compound may contain groups other than the maleimide as described above, and the curable composition may contain other resins
  • this invention is a process for attaching a semiconductor die to a substrate comprising the steps of ( ⁇ ) providing a semiconductor die, a substrate and a curable composition comprising a compound having a diphenyl oxide backbone and pendant from the backbone at least one hydrocarbon chain, the hydrocarbon chain containing an ester functionality and being terminated with a maleimide functional group, (n) applying the curable composition to the substrate, the die, or both, (in) joining the semiconductor die to the substrate with the curable composition disposed between them, and ( ⁇ v) curing the curable composition
  • the DPO compound may contain groups other than the maleimide as described above, and the curable composition may contain other resins
  • the compound having a diphenyl oxide backbone and pendant from the backbone at least one hydrocarbon chain, the hydrocarbon chain containing an ester functionality and being terminated with a maieimide functional group is prepared from the reaction of diphenyl oxide, formaldehyde or paraformaldehyde, and a compound containing both carboxylic acid and maleimide functionality If groups other than the maleimide are desired, the reaction mix will further contain a compound containing carboxylic acid and the group other than the maleimide
  • the compound containing both carboxylic acid and maleimide functionality will have a hydrocarbon chain linking the acid and maleimide functionality, and the compound containing both carboxylic acid and a group other than the maleimide, will have a hydrocarbon chain linking the acid and group other than the maleimide functionality
  • the hydrocarbon chain in either case will typically contain linear methylene groups forming the chain, although the chain may have cyclic aliphatic groups, aromatic groups, or heteroatoms incorporated into the chain
  • the length of the chain can be varied to design specific molecular weights and performance properties and is limited only by the availability or synthetic feasibility of the starting carboxylic acid containing the maleimide functionality or group other than maleimide
  • a higher molecular weight hydrocarbon chain pendant from the backbone will give higher modulus at elevated temperatures
  • the groups other than the maleimide, also pendant from the DPO backbone will give specific properties depending on the choice of the practitioner as one skilled in the art would know how to choose
  • the DPO backbone may also be tailored to suit the needs of the practitioner For instance, a longer DPO backbone will provide enhanced toughening properties
  • the preparation of the compound can be carried out using well-known free radical polymerization procedures, using solution, emulsion, or bulk polymerization techniques
  • the compound is formed by removal of the solvent, coagulation of the latex, or melt-processing of the neat polymer
  • the compound of this invention may form a curable composition either by itself or combined with other components
  • the curable composition that comprises only the compound of this invention cures upon the application of heat, which causes initiation of free-radical curing
  • the curable composition may be formulated to include, in addition to the inventive compound, other resins or polymers, fillers and additives including curing agents, adhesion promoters, fluxing agents, anti-foaming agents, solvents, and the like
  • Resins and polymers used in the formulation, in addition to the inventive compound may be solid, liquid or a combination of the two Suitable additional resms and polymers include but are not limited to epoxies, acrylates and methacrylates maleimides bismaleimides, vinyl ethers, polyesters, poly(butad ⁇ enes), siliconized olefins, silicone resins, siloxanes, styre ⁇ e resins and cyanate ester resins
  • Exemplary solid aromatic bismaleimide (BIvII) resin powders for use in formulations with the inventive compounds are those having the structure in which X is an aromatic group.
  • Bismaleimide resins having these X bridging groups are commercially available, and can be obtained, for example, from Sartomer (USA) or HOS-Technic GmbH (Austria).
  • X 1 is an aliphatic or aromatic group.
  • exemplary X 1 entities include, poly(butadienes), poly(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether. These types of resins are commercially available and can be obtained, for example, from National Starch and Chemical Company and Dainippon Ink and Chemical, Inc.
  • C 36 represents a linear or branched chain (with or without cyclic moieties) of 36 carbon atoms
  • X 2 is an aromatic or aliphatic group
  • X 2 entities include poly(butad ⁇ enes), poiy(carbonates), poly(urethanes), poly(ethers) poly(esters), simpie hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide carbamate, urea, or ether.
  • Exemplary X /3 entities include poly(butad ⁇ enes), poly(carbonates), poly(urethanes), poly(ethers), poiy(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl amide, carbamate, urea or ether
  • Commercially available resins include cycSohena ⁇ edimethanol divinylether, dodecylvinylether, cyclohexyl vinylether 2- ethylhexyl vinylether dipropyleneglycol divinylether, hexanediol divinylether, octadecylvinylether, and butandiol divinylether available from international Speciaiity Products (ISP); Vectomer 4010, 4020, 4030, 4040, 4051 , 4210, 4220, 4230, 4060, 5015 available from Sigma-AIdrich, Inc.
  • Suitable poly(butadiene) resins for use in formulations with the inventive compounds include poly(butadie ⁇ es), epoxidized poly(butadienes), maleic poly(butadienes), acrylated poly(butadienes), butadiene-styrene copolymers, and butadiene-acryionitrile copolymers.
  • Suitable epoxy resins for use in formulations containing the inventive compounds include bisphenol, naphthalene, and aliphatic type epoxies
  • Commercialiy available materials include bisphenol type epoxy resins (Epiclon 830LVP, 830CRP, 835LV, 850CRP) available from Dainippon Ink & Chemicals, Inc.; naphthalene type epoxy (Epicion HP4032) available from Dainippon Ink & Chemicals, Inc.; aliphatic epoxy resins (Araidite CY179, 184, 192, 175, 179) available from Ciba Specialty Chemicals, (Epoxy 1234, 249, 206) available from Union Carbide Corporation, and (EHPE-3150) available from Daicel Chemical Industries, Ltd.
  • epoxy resins include cycloaliphatic epoxy resins, bisphenol-A type epoxy resins, bisphenoi-F type epoxy resins, epoxy novolac resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene-phenol type epoxy resins, reactive epoxy diluents, and mixtures thereof.
  • Suitable siliconized olefin resins for use in the formulations containing the inventive compounds are obtained by the selective hydrosilation reaction of silicone and divinyl materials, having the generic structure, [0024] in which (I 1 is 2 or more, n 2 is 1 or more and
  • Suitable silicone resins for use in formulations with the inventive compounds include reactive silicone resins having the generic structure
  • n is 0 or any integer
  • X s are hydrogen, methyl, amine, epoxy, carboxyl, hydroxy, acrylate, methacrylate, mercapto, phenol, or vinyl functional groups
  • R 2 and R 3 can be -H, -CH 3 , vinyl, phenyl, or any hydrocarbon structure with more than two carbons.
  • X 3 entities include poly(butadienes), poly(carbonates), poiy(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether. These resins are commercially available and can be obtained, for example, from National Starch and Chemical Company or Sigma-Ald ⁇ ch Co.
  • Exemplary X 7 entities include bisphenol, phenol or cresol novolac, dicyclopentadie ⁇ e, polybutadiene, polycarbonate, polyurethane, polyether, or polyester.
  • Additional polymers suitable for use in formulations with the inventive compounds include polyamide, phenoxy, polybenzoxazine, polyether sulfone, polyimide, benzoxazine, vinyl ether, polyoiefin, polybenzoxyzole, polyester, polystyrene, polycarbonate, polypropylene, polyvinyl chloride), polyisobutylene, polyacrylonitrile, po!y(methyl methacrylate), polyvinyl acetate), poly(2-vinylpridine), cis-1 ,4-polyisoprene, 3,4-polychloroprene, vinyl copolymer, poly(ethylene oxide), poly(ethylene glycol), polyformaldehyde, polyacetaldehyde, poly(b-propiolacetone), poly(10-deca ⁇ oate), poly(ethylene terephthalate), polycaprolactam, poly(11-undecanoamide), poly(m- phenylene-terephthalamide), poly(
  • Suitable materials for inclusion in adhesive, coating, and encapsulant compositions containing the inventive compounds include rubber polymers such as block copolymers of monovinyl aromatic hydrocarbons and conjugated diene, e.g., styrene-butadiene, styrene-butadiene-styrene (SBS), styrene-isopre ⁇ e-styrene (SIS), styrene-ethylene-butylene-styrene (SEBS), and styrene-ethylene-propylene-styrene (SEPS).
  • rubber polymers such as block copolymers of monovinyl aromatic hydrocarbons and conjugated diene, e.g., styrene-butadiene, styrene-butadiene-styrene (SBS), styrene-isopre ⁇ e-styrene (SIS), styrene-ethylene-butylene
  • compositions containing the inventive compounds include ethyiene-vinyl acetate polymers, other ethylene esters and copolymers, e.g., ethylene methacrylate, ethylene n-butyl acrylate and ethylene acrylic acid; poiyolefins such as polyethylene and polypropylene; polyvinyl acetate and random copolymers thereof; polyacrylates; polyamides, polyesters, and polyvinyl alcohols and copolymers thereof.
  • Suitable thermoplastic rubbers for use in formulations containing the inventive compounds include carboxy terminated butadiene-nit ⁇ le (CTBN)/epoxy adduct, acrylate rubber, vinyl-terminated butadiene rubber, and nitrile butadiene rubber (NBR).
  • CTBN epoxy adduct consists of about 20-80 wt% CTBN and about 20- 80 wt% diglycidyl ether bisphenol A: bisphenol A epoxy (DGEBA)
  • DGEBA bisphenol A epoxy
  • CTBN materials are available from Noveon Inc.
  • a variety of bisphenol A epoxy materials are available from Dainippon Ink and Chemicals, Inc.
  • Shell Chemicals NBR rubbers are commercially available from Zeon Corporation
  • Suitable siloxanes for use in formulations containing the inventive compounds include elastome ⁇ c polymers comprising a backbone and pendant from the backbone at least one siloxane moiety that imparts permeability, and at least one reactive moiety capable of reacting to form a new covalent bond.
  • suitable siloxanes include elastomeric polymers prepared from.
  • a curing agent may be used to initiate, propagate, catalyze, accelerate, or otherwise facilitate the curing of the inventive compound and/or of any additional resins or polymers included in the formulation. Selection of a curing agent is dependent on the inventive compound, resins, and polymers used and the processing conditions employed.
  • the compositions may use aromatic amines, alycyclic amines, aliphatic amines, tertiary phosphines, triazines, metal salts, aromatic hydroxyl compounds, or a combination of these. Appropriateness of the type and amount of curing agents used for specific compositions is disclosed in the open literature and is within the expertise of one skilled in the art.
  • curing agents include imidazoles, such as 2-methylimidazole, 2-undecyl ⁇ midazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2-ethyl 4- methylimidazole, 1-benzy[-2-methylimidazole, 1-propyl-2-methylim ⁇ dazole, 1- cyanoethyl-2-methylimidazole, i-cyanoethyl ⁇ -ethyM-methylimidazole, 1-cyanoethyl-2- undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2- methylimidazole and addition product of an imidazole and trimellitic acid; tertiary amines, such as N,N-dimethyl be ⁇ zylamine, N,N-dimethylaniline, N,N-dimethyltoluidine t N,N-di
  • Suitable curing accelerators may be selected from the group consisting of triphenylphosphme, alkyl-substituted imidazoles, imidazolium salts, onium salts, quartenary phosphonium compounds, onium borates, metal chelates, 1 ,8- diazacyclo[5.4.0]undex-7-ene or a mixture thereof
  • Curing agents for the inventive compound must be a free radical initiator.
  • Curing agents for additional resins or polymers in the composition can be either a free radical initiator or cationic initiator, depending on whether a radical or ionic curing resins are chosen. If a free radical initiator is used, it will be present in an effective amount. An effective amount typically is 0.1 to 10 percent by weight of the organic compounds (excluding any filler).
  • Appropriate free-radical initiators include peroxides, such as butyl peroctoates and dicumyl peroxide, and azo compounds, such as 2 I 2'-azobis(2-methyl- propanenit ⁇ le) and 2,2'-azobis(2-methyl-butanenitrile).
  • Preferred cationic curing agents include dicyandiamide, phenol novolak, adipic dihydrazide, diallyl melamine, diamino malconitrile, BF3-am ⁇ ne complexes, amine salts and modified imidazole compounds.
  • Metal compounds also can be employed as cure accelerators for cyanate ester systems and include, but are not limited to, metal napthenates, metal acetylacetonates (chelates), metal octoates, metal acetates, metal halides, metal imidazole complexes, and metal amine complexes.
  • Other cure accelerators that may be included in the coating formulation include triphenylphosphine, alkyl-substituted imidazoles, imidazolium salts, and onium borates
  • both cationic and free radical initiation may be desirable, in which case both free radical cure and ionic cure resins can be used in the composition.
  • These compositions would contain effective amounts of initiators for each type of resin. Such a composition would permit, for example, the curing process to be started by cationic initiation using UV irradiation, and in a later processing step, to be completed by free radical initiation upon the application of heat.
  • B-staging (and its variants) is used to refer to the processing of a materia! by heat or irradiation so that if the material is solubilized or dispersed in a solvent, the solvent is evaporated off with or without partial curing of the material, or if the material is neat with no solvent, the material is partially cured to a tacky or more hardened state.
  • B- staging will provide extremely low flow without fully curing, such that additional curing may be performed after the adhesive is used to join one article to another.
  • the reduction in flow may be accomplished by evaporation of a solvent, partial advancement or curing of a resin or polymer, or both.
  • the time and temperature required to achieve this will vary according to the solvent and composition used and can be determined by the practitioner without undue experimentation.
  • the drying and/or B- staging may be done as a step separate from the curing of the end use composition, or it may be done as a separate process step.
  • composition does not contain solvent it may still be desirable to B-stage, or partially advance, the material. This may be done prior to cure to effect hardening of the curable composition to a non-tacky state so that additional processing may be done before the curable composition is fully cured.
  • the curable composition may be cured either in an individual process step or in conjunction with another processing operation such as wirebonding or solder reflow.
  • the cure may be done at the wafer level or at the die level, depending on the purpose of the composition, the makeup of the composition, and the manufacturing process employed.
  • Heat curing of the curable composition will generally take place within a range of 80°-250 D C, and curing will be effected within a time period ranging from few seconds up to 120 minutes, depending on the particular compound and curing agents chosen
  • the time and temperature curing profile for each composition will vary, and different compositions can be designed to provide the curing profile that will be suited to the particular industrial manufacturing process.
  • one or more fillers or spacers, or both may be included in the curable composition and usually are added for improved Theological properties, stress reduction, and bondline control.
  • suitable nonconductive fillers include alumina, aluminum hydroxide, silica, vermiculite, mica, wollastonite, calcium carbonate, titama, sand, glass, barium sulfate, zirconium, carbon black, organic fillers, and halogenated ethylene polymers, such as, tetrafluoroethylene, t ⁇ fluoroethylene, vinylidene fluoride, vinyl fluoride, vinylidene chloride, and vinyl chloride
  • Exemplary electrically or thermally conductive fillers include carbon black, graphite, gold, silver, copper, platinum, palladium, nickel, aluminum, silicon carbide, boron nitride, diamond, and alumina The particles may be of any appropriate size ranging from nano size to several mm, depending on whether they are used as fillers or
  • suitable fluxing agents include compounds that contain one or more hydroxyl groups (-OH), or carboxyhc (-COOH) groups or both, such as are present in organic carboxylic acids, anhydrides, and alcohols
  • Exemplary fluxing agents are, for example, rosin gum, dodecanedioic acid (commercially available as Corfree M2 from Aldrich), sebasic acid, polysebasic polyanhydnde, maleic acid, hexahydrophthalic anhydride, methyl hexahydrophthahc anhydride, ethylene glycol, glycerin, tartaric acid, adipic acid, citric acid, malic acid, gluta ⁇ c acid, glycerol, 3- [bis(glyc ⁇ dyl oxy methyl)methoxy]-1 ,2- propane diol, D- ⁇ bose, D-ceflobiose, cellulose, 3- cycio-hexene-l,l- dim
  • Suitable coupling agents are epoxy silanes, amine siianes agent, or mercapto silanes Coupling agents, if used, will be used in an effective amount, and a typical effective amount is an amount up to 5% by weight (excluding any filler content).
  • the curable composition may also contain a surfactant Suitable surfactants include organic acrylic polymers, silicones, polyethylene glycol, polyoxyethylene/polyoxypropylene block copolymers, ethylene diamine based polyoxyethyiene/polyoxypropylene block copolymers, polyol-based polyoxyalkylenes, fatty alcohol-based polyoxyalkylenes, fatty alcohol polyoxyalkylene alkyl ethers, and mixtures thereof
  • Surfactants if used, will be used in an effective amount, and a typical effective amount is an amount up to 5% by weight (excluding any filler content)
  • wetting agents also may be included in the curable composition Wetting agent selection will depend on the application requirements and the resin chemistry utilized Wetting agents if used, will be used in an effective amount and a typical effective amount is up to 5% by weight (excluding any filler content)
  • suitable wetting agents include Fluorad FC-4430 Fluorosurfactant available from 3M Cla ⁇ ant Fluowet OTN, BYK W-990, Surfynol 104 Surfactant Crompton Silwet L-7280, Triton X100 available from Rhom and Haas, Propylene glycol with a preferable Mw greater than 240, Gama-Butyroiactone, castor oil, glycerin or other fatty acids, and sila ⁇ es
  • a flow control agent also may be included in the curable composition
  • Flow control agent selection will depend on the application requirements and resin chemistry employed Fiow control agents, if used, will be present in an effective amount an effective amount is an amount up to 5% by weight (excluding any filler content)
  • suitable flow control agents include Cab-O-Sil TS720 available from Cabot, Aerosil R202 or R972 available from Degussa fumed silicas, fumed aluminas, or fumed metal oxides
  • Some curable compositions may include an adhesion promoter and selection of an appropriate adhesion promoter will depend on the application requirements and resin chemistry employed Adhesion promoters, if used, will be used in an effective amount and an effective amount is an amount up to 5% by weight (excluding any filler content)
  • suitable adhesion promoters include silane coupling agents such as Z6040 epoxy silane or Z6020 amine silane available from Dow Corning, A186 Silane, A187 Silane, A174 Silane, or A1289 available from OSI Silquest, Organosilane SI264 available from Degussa, Johoku Chemical CBT-1 Carbobenzotriazole available from Johoku Chemical, functional benzot ⁇ azoles, thiazoles, titanates, and zirconates
  • An air release agent is another optional component to the curable composition
  • Air release agent selection will depend on the application requirements and resin chemistry employed Air release agents, if used, will be used in an effective amount and an effective amount will be an amount up to 5% by weight (excluding any filler content)
  • suitable air release agents include Antifoam 1400 available from Dow Corning, DuPont Modoflow, and BYK A-510
  • these curable compositions are formulated with tackifying resins in order to improve adhesion and introduce tack; examples of tackifying resins include naturaliy-occurring resins and modified naturally-occurring resins; polyterpene resins; phenolic modified terpene resins; coumarons-indene resins, aliphatic and aromatic petroleum hydrocarbon resins; phthalate esters; hydrogenated hydrocarbons, hydrogenated rosins and hydrogenated rosin esters.
  • diluents such as liquid polybutene or polypropylene, petroleum waxes such as paraffin and microcrystal ⁇ ne waxes, polyethylene greases, hydrogenated animal, fish and vegetable fats, mineral oil and synthetic waxes, naphthenic or paraffinic mineral oils.
  • monofunctional reactive diluents can be included in the curable composition to incrementally delay an increase in viscosity without adversely affecting the physical properties of the cured coating.
  • Suitable diluents include p-tert- butyl-phenyl glycidyl ether, ally! glycidyl ether, glycerol diblycidyl ether, glycidyl ether of alkyl phenol (commercially available from Cardolite Corporation as Cardolite NC513), and Butanediodiglycidylether (commercially available as BDGE from Aldrich).
  • additives such as stabilizers, antioxidants, impact modifiers, and colorants, in types and amounts known in the art, may also be added to the curable composition.
  • Common solvents that readily dissolve the resins, and with a proper boiling point ranging from 25 ⁇ C to 200 °C can be used in the curable composition.
  • solvents that may be utilized include ketones, esters, alcohols, ethers, and other common solvents that are stable. Suitable solvents include y-butyrolactone, propylene glycol methyl ethyl acetate (PGMEA), and 4-methyl-2-pentanone.
  • Curing can take place by thermal exposure, ultraviolet (UV) or microwave irradiation, or a combination of these. Curing conditions will be tailored to the specific formulation and can be readily determined by the practitioner. Furthermore, the curable composition may be B-stageable or not, depending on the application requirements.
  • UV ultraviolet
  • microwave irradiation or a combination of these. Curing conditions will be tailored to the specific formulation and can be readily determined by the practitioner. Furthermore, the curable composition may be B-stageable or not, depending on the application requirements.
  • the compound and/or curable composition of this invention may be used as an adhesive, coating, or encapsulant They are especially useful for electronic device construction within the semiconductor packaging industry because of their inherent temperature resistance as well as the ability to include functionalities to tailor such properties as adhesion, toughness, conductivity, melting point, high temperature modulus, and solubility.
  • the curable composition is used to affix a semiconductor device onto a substrate or to encapsulate or coat parts, or all, of the device.
  • the inventive compound and curable composition have particular utility for the bonding of integrated circuit chips (semiconductor dies) to substrates including glass, ceramic, organic, and metal leadframes.
  • the inventive compound and curable composition are also useful for the bonding of circuit packages or assemblies to printed wire boards, the encapsulation of solder balls used as electrical connections, and the coating of via holes.
  • the compound of this invention is particularly useful in curable compositions for capillary underfill of flip-chip devices.
  • flip-chip technology the active side of the semiconductor die is bumped with metallic solder balls and flipped so that the solder balls can be aligned and placed in contact with corresponding electrical terminals on the substrate. Electrical connection is realized when the solder is reflowed to form metallurgical joints with the substrates.
  • the coefficients of thermal expansion (CTE) of the semiconductor die, solder, and substrate are dissimilar and this mismatch stresses the solder joints, which ultimately can lead to failure of the semiconductor package.
  • Organic materials are used to underfill the gap between the die and the substrate to offset the CTE mismatch and to provide enforcement to the solder joints.
  • Such underfill materials can be applied through a capillary effect, by dispensing the material along the edges of the die- substrate assembly after solder reflow and letting the material flow into the gap between the die and substrate. The underfill is then cured, typically by the application of heat.
  • shrinkage voids This phenomenon, which is often seen in acrylate-based underfill formulations, is caused by the shrinkage of the underfill during cure and results in a void, or gap, between the underfill and either the solder balls, substrate, semiconductor die, or a combination of these. Such voids are undesirable, as they can ultimately lead to device failure
  • the compound of this invention may be designed to be an oligomer that has a high molecular weight and fewer reaction points compared to a monomer. Such a compound will not shrink as much during cure and will give superior shrinkage void performance compared to, for instance, acrylate monomers.
  • Tg glass transition temperature
  • the compound of this invention may also be used in wafer backside coating applications.
  • wafer backside coating is a printable, B-stage-able adhesive formulation that is coated on the backside of a semiconductor wafer by screen or stencil printing. After printing, the coated wafer is heated to evaporate solvent and/or partially advance the resin, so that the coating is hardened to a non-tacky state. The wafer is then laminated onto dicing tape, diced, and singulated into individual dies with an adhesive layer on the die backside. The die can then be attached to a substrate using heat and pressure After die attach, the adhesive is typically cured in either a snap or oven cure process. Coatings comprising the compound of this invention can give higher thermal conductivity for these types of applications as compared to prior art formulations. This attribute can be an advantage in many die attach applications.
  • m and n are integers that will vary with the proportion of starting materials, and typically will each be, independently, any integer within the range of 1 to 100, provided that n is greater than m. It will be understood by those skilled in the art that the level of substitution of the dependent hydrocarbon chains containing the ester and maleimide groups and groups other than maleimide on the DPO backbone can be calculated, although the exact location on the DPO backbone cannot be precisely determined.
  • EXAMPLE 1 PREPARATION OF COMPOUND FROM DIPHENYL OXIDE (DPO), PARAFORMALDEHYDE, AND MALEMIDO CAPROIC ACID (MCA)
  • the reaction was kept within the temperature range of 105°- 110°C for one hour. At this point, the reaction turned cloudy orange-gold The reaction was stopped and left to cool over night, which resulted in a mixture of crystalline solids and clear gold syrup. Next, the mixture was poured into 700 mL of swirling methanol, mixed well and left to sit over night.
  • a light gold paste formed in a hazy-gold liquor.
  • the paste was rinsed several times with methanol and then dissolved in 400 mL of dichloromethane. Insoluble flocculent was filtered out and the remaining clear yellow solution washed three times with 300 mL of distilled water. Emulsions were formed by the washes, which were broken with the addition of saturated sodium chloride solution.
  • EXAMPLE 3 PREPARATION OF COMPOUND FROM DIPHENYL OXIDE (DPO), PARAFORMALDEHYDE, MCA AND 2-ETHYL BUTYRIC ACID.
  • reaction changed from a gold-colored to an orange-colored mixture. Some sublimate formed and was knocked back down into the reaction flask. The reaction was kept at 105°-112 ° C for a total of one hour. At this point, the reaction was a clear gold solution with some white sublimate in the condenser. The reaction was stopped and left to cool.
  • the reaction mixture then was poured into 2100 mL of swirling methanol and mixed well for 10 minutes. A light ivory suspension formed. After the solids settled out, the methanol was observed to be a deep gold color and was decanted off The solids were washed with methanol and decanted three more times. Residual methanol was removed via vacuum filtration leaving a tacky ivory cake with gold residue (37grams moist). The cake was dissolved in dichioromethane resulting in 10OmL of a slightly hazy gold solution. The soiutio ⁇ was added to 900 mL of methanol and mixed mechanically for 15 minutes. A white suspension formed and was allowed to settle for one hour. The methanol solution was decanted off the white solids and residual solvent was removed via vacuum filtration.
  • EXAMPLE 4 PREPARATION OF COMPOUND FROM DIPHENYL OXIDE (DPO), PARAFORMALDEHYDE, MCA AND PHENYLACETIC ACID
  • the reaction was kept at 105°-110°C for a total of one hour. As the sublimate formed, it was knocked back down into the reaction. By the end of the heating time, the reaction was a clear orange solution. The reaction was stopped and left to cool. The reaction mixture was poured over five minutes into 1500 mL of swirling methanol and mixed well for ten minutes
  • a light ivory suspension was formed. After the lumpy ivory solids settled out, the solvent, which had become a cloudy light gold, was decanted off. The solids were further washed with methanol and decanted three more times. The solids were dissolved in 250 mL of dichloromethane and this solution was added to 1500 mL of swirling methanol, ivory-colored solids precipitated out and were allowed to settle for one hour. The methanol solution was decanted off the white solids. The solids were then dissolved in 500 mL in dichloromethane and filtered to remove light insolubles. The product solution was then washed vigorously in a separatory funnel with 1000 mL of a brine solution.
  • a light ivory suspension was formed. After the solids settled out, the solvent was decanted off. The solids were then washed with methanol and decanted three more times. Residual methanol was removed via vacuum filtration leaving a sticky light gold cake (75 grams moist). The cake was dissolved in 700 mL of dichloromethane. The product solution was washed vigorously in a separatory funnel with 1300 mL of a brine solution. The resulting emulsion was allowed to separate over 2 5 hours. The organic solution was collected from the funnel and the white aqueous layer was discarded. The solution was then dried over 40 grams of magnesium sulfate and filtered. The volume was increased to 700 mL with the addition of dichloromethane.
  • DPO (89.1 grams, 0.5237 mol), paraformaldehyde (49.7 grams), p-tolue ⁇ e sulfonic acid mo ⁇ ohydrate (9.97 grams, 0.0524 moi), cyclohexylacetic acid (81.9 grams, 0.5761 mol) and maleimidocaproic acid (MCA) (121.6 grams, 0.5761 mo! were charged to a 1 L 4-neck round-bottom reaction flask equipped with a condenser, thermometer and mechanical mixer. The flask was placed in an oil bath preheated to 130 ° C and the contents heated with mixing at 300 rpm. Reflux was achieved within 15 minutes at 105°C.
  • the reaction changed from a gold mixture to an opaque orange dispersion. Sublimate formed and was knocked down back into the reaction. The reaction was kept at 105°-110 ° C for a total of one hour. At this point, the reaction was cloudy orange-gold. The reaction was stopped and left to cool. Next, the mixture was poured into 1600 mL of swirling methanol and mixed well for 10 minutes. A light ivory suspension was formed. After the solids settled out, the methanol was decanted off. The solids were then washed with 10OmL of methanol and decanted three more times. The oligomeric material was dried and then characterized by 1 H- NMR, Figure 6.

Abstract

La présente invention concerne un composé ayant un squelette oxyde de diphényle, et, rattachée à ce squelette, au moins une chaîne hydrocarbonée, la chaîne hydrocarbonée contenant une fonctionnalité ester et étant terminée avec un groupe fonctionnel maléimide. Ce composé est préparé à partir de la réaction de l'oxyde de diphényle, du formaldéhyde ou du paraformaldéhyde, et d'un composé contenant à la fois les fonctionnalités acide carboxylique et maléimide. Des composés exemplaires comprennent des composés dans lesquels m et n sont indépendamment un entier allant de 1 à 100, à condition que n soit supérieur à m.
PCT/US2007/088130 2007-12-19 2007-12-19 Composés ayant un squelette oxyde de diphényle et un groupe fonctionnel maléimide WO2009078878A1 (fr)

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TW097117989A TW200927778A (en) 2007-12-19 2008-05-16 Compounds having a diphenyl oxide backbone and maleimide functional group
US12/818,225 US20100311207A1 (en) 2007-12-19 2010-06-18 Compounds Having A Diphenyl Oxide Backbone and Maleimide Functional Group

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