WO2001074798A1 - Reworkable composition of oxirane(s) or thiirane(s)-containing resin and curing agent - Google Patents

Reworkable composition of oxirane(s) or thiirane(s)-containing resin and curing agent Download PDF

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Publication number
WO2001074798A1
WO2001074798A1 PCT/US2001/008624 US0108624W WO0174798A1 WO 2001074798 A1 WO2001074798 A1 WO 2001074798A1 US 0108624 W US0108624 W US 0108624W WO 0174798 A1 WO0174798 A1 WO 0174798A1
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WO
WIPO (PCT)
Prior art keywords
methyl
dimethyl
trimethyl
dodecatetraene
ethyl
Prior art date
Application number
PCT/US2001/008624
Other languages
French (fr)
Inventor
Philip T. Klemarczyk
Andrew D. Messana
Afranio Torres-Filho
Erin K. Yaeger
Takahisa Doba
Original Assignee
Loctite Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Loctite Corporation filed Critical Loctite Corporation
Priority to US10/182,450 priority Critical patent/US7012120B2/en
Priority to MXPA02009639A priority patent/MXPA02009639A/en
Priority to CA002403595A priority patent/CA2403595A1/en
Priority to JP2001572491A priority patent/JP2003529643A/en
Priority to AU2001247541A priority patent/AU2001247541A1/en
Priority to EP01920494A priority patent/EP1268457A4/en
Publication of WO2001074798A1 publication Critical patent/WO2001074798A1/en
Priority to US12/004,343 priority patent/US8053587B2/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/28—Ethers with hydroxy compounds containing oxirane rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • C08G75/08—Polythioethers from cyclic thioethers from thiiranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • 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
    • H01L2924/01012—Magnesium [Mg]
    • 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
    • H01L2924/01019—Potassium [K]
    • 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
    • H01L2924/01077—Iridium [Ir]

Definitions

  • thermosetting resin compositions useful for instance, in mounting onto a circuit board semiconductor devices, such as chip size or chip scale packages (“CSPs”), ball grid arrays (“BGAs”), land grid arrays (“LGAs”) and the like, each of which having a semiconductor chip, such as large scale integration (“LSI”), on a carrier substrate.
  • CSPs chip size or chip scale packages
  • BGAs ball grid arrays
  • LGAs land grid arrays
  • the compositions of 'this invention are reworkable when subjected to appropriate conditions.
  • CSPs, BGAs and LGAs are being used to reduce the size of packages substantially to that of bare chips.
  • Such CSPs, BGAs, LGAs improve the characteristics of the electronic device while retaining many of their operating features, thus serving to protect semiconductor bare chips, such as LSIs, and facilitate testing thereof.
  • the CSP/BGA/LGA assembly is connected to electrical conductors on a circuit board by use of a solder connection or the like.
  • a solder connection or the like.
  • the reliability of the solder connection between the circuit board and the CSP/BGA/LGA often becomes suspect .
  • a sealing resin often referred to as underfill sealing
  • thermosetting resins are typically used as the underfill sealing material, in the event of a failure after the CSP/BGA/LGA assembly is mounted on the circuit board, it is very difficult to replace the CSP/BGA/LGA assembly without destroying or scrapping the structure in its entirety.
  • Publication No. 102343/93 involves a mounting process where a bare chip is fixed and connected to a circuit board by use of a photocurable adhesive, where, in the event of failure, this bare chip is removed therefrom.
  • this technique is limited to those instances where the circuit board includes a transparent substrate (e.g. , glass) which permits exposure to light from the back side, and the resulting structure exhibits poor heat shock properties.
  • Japanese Laid-Open Patent Publication No. 69280/94 discloses a process where a bare chip is fixed and connected to a substrate by use of a resin capable of hardening at a predetermined temperature. In the event of failure, this bare chip is removed from the substrate by softening the resin at a temperature higher than the predetermined temperature.
  • no specific resin is disclosed, and there is no disclosure about treating the resin which remains on the substrate. Thus, the disclosed process is at best incomplete .
  • Japanese Laid-Open Patent Publication No. 251516/93 also discloses a mounting process using bisphenol A type epoxy resin (CV5183 or CV5183S; manufactured by Matsushita Electric Industrial Co., Ltd.).
  • CV5183 or CV5183S manufactured by Matsushita Electric Industrial Co., Ltd.
  • the removal process so disclosed does not consistently permit easy removal of the chip, the curing step is lengthy at elevated temperatures, and the process generally results in poor productivity.
  • thermoplastic underfill resins are known for use in semiconductor chip attachment. See U.S. Patent No. 5,783,867 (Belke, Jr.). However, such thermoplastic resins tend to leak under relatively modest temperature conditions. In contrast, thermosetting resins cure into a matrix which ordinarily have greater thermal stability under end use operating temperatures .
  • U.S. Patent Nos . 5,512,613 (Afzali-Ardakani), 5,560,934 (Afzali-Ardakani) and 5,932,682 (Buchwalter), each refer to a reworkable thermoset composition based on a diepoxide component in which the organic linking moiety connecting the two epoxy groups of the diepoxide includes an acid cleavable acyclic acetal group.
  • acid cleavable acyclic acetal groups forming the bases of the reworkable composition, a cured thermoset need only be introduced to an acidic environment in order to achieve softening and a loss of much of its adhesiveness.
  • U.S. Patent No. 5,760,337 (Iyer) refers to thermally reworkable crosslinked resins to fill the gap created between a semiconductor device and a substrate to which it is attached. These resins are produced by reacting a dienophile (with a functionality greater than 1) with a 2.5-dialkyl substituted furan-containing polymer.
  • thermosetting resin composition capable of sealing underfilling between a semiconductor device including a semiconductor chip mounted on a carrier substrate and a circuit board to which said semiconductor device is electrically connected.
  • the composition includes about 100 parts by weight of an epoxy resin, about 3 to about 60 parts by weight of a curing agent, and about 1 to about 90 parts by weight of a plasticizer.
  • the area around the cured thermoset is to be heated at a temperature of about 190 to about 260°C for a period of time ranging from about 10 seconds to about 1 minute in order to achieve softening and a loss of much of its adhesiveness.
  • an underfilling sealing material to provide good productivity, thermal shock and mechnaical stress absorbing properties, while allowing the substrates with which it is to be used to be readily processed and easily separated from a semiconductor device without application of too extreme conditions that may compromise the integrity of the semiconductor devices remaining on the substrate or the substrate itself.
  • thermosetting resin composition which includes broadly a curable resin component, at least a portion of which is a compound having at least one linkage selected from oxiranes, thiiranes, and combinations thereof, substituted on at least three of the substitutable positions on the oxirane and/or thiirane carbons, respectively, with an alkyl, alkenyl or aryl substituent having a carbon content of one to about twelve carbon atoms, with or without substitution or interruption by one or more heteroatoms or halogens, as appropriate; and a curing agent component including an anhydride component, a nitrogen-containing component, such as amine or aza compounds, amide compounds, and/or imidazole compounds, or combinations thereof.
  • a curable resin component at least a portion of which is a compound having at least one linkage selected from oxiranes, thiiranes, and combinations thereof, substituted on at least three of the substitutable positions on the oxirane and/or thiirane carbons, respectively,
  • the present invention also provides novel diepoxide-containing compounds, the structures for which are described in detail herein.
  • Reaction products of these compositions are capable of softening under exposure to elevated temperature conditions, such as in excess of the tempertures used to cure the composition. Such temperature exposure provides the reworkable aspect of the reaction products of the inventive compositions.
  • the remaining components, discussed below, provide the physical properties and characteristics for the compositions and reaction products to render the compositions attractive for commercial use, particularly in the microelectronics industry.
  • the inventive compositions are useful as an underfilling sealing resin, and enables a semiconductor device, such as a CSP/BGA/LGA assembly which includes a semiconductor chip mounted on a carrier substrate, to be securely connected to a circuit board by short-time heat curing and with good productivity.
  • Reaction products of the inventive compositions demonstrate excellent heat shock properties, and permit the semiconductor device to be easily removed from the circuit board by localized heating in excess of the temperature at which the composion cures, in the event of semiconductor device or connection failure. This makes it possible to reuse the circuit board (with the remaining functioning semiconductor devices still electrically attached) and thereby achieve an improvement in the yield of the production process and a reduction in production cost.
  • compositions of this invention may also be used for microelectronic applications beyond sealing underfill, such as with glob top, die attachment and other applications for thermosetting compositions.
  • FIG. 1 depicts a cross-sectional view showing an example of the mounting structure in which the thermosetting resin composition of the present invention is used.
  • FIG. 2 depicts a flow diagram of a procedure useful to rework a cured thermosetting resin composition in accordance with the present invention, so as to remove a semiconductor device from a circuit board to which it had been attached.
  • FIG. 3 depicts a TGA curve of cured reaction products of compositions based on limonene diepoxide (square), Compound XVI of U.S. Patent Nos. 5,948,922 (Ober) and 5,973,033 (Ober) (circle), commercially available diepoxidized dicycloaliphatic ester (ERL 4221) (closed square) and commercially available diglycidyl ether of bisphenol F epoxy resin (RE-404-S) (asterisk) , cured with an anhydride curing agent .
  • RE-404-S diglycidyl ether of bisphenol F epoxy resin
  • FIG. 4 depicts a TGA curve of cured reaction products of compositions based on terpinene diepoxide (square), Compound XVI of the '922 and '033 patents
  • FIG. 5 depicts a TGA curve of cured reaction products of compositions based on limonene diepoxide and RE- 404-S at different ratios, and RE-404-S (asterisk) , cured with an imidazole/dicyandiamide curing agent .
  • FIG. 6 depicts a TGA curve of cured reaction products of compositions based on limonene diepoxide/RE-404- S (circle), Compound XVI of the '922 and '033 patents (square) , ERL 4221 (diamond) and RE-404-S (asterisk) , cured with an imidazole/dicyandiamide curing agent .
  • FIG. 7 depicts a TGA curve of cured reaction products of compositions based on gamma-terpinene diepoxide and RE-404-S at different ratios, and RE-404-S (asterisk) , cured with an imidazole/dicyandiamide curing agent .
  • FIG. 8 depicts a TGA curve of cured reaction products of compositions based on gamma-terpinene diepoxide/RE-404-S (circle), Compound XVI of the '922 and '033 patents (square), ERL 4221 (diamond) and RE-404-S, cured with an imidazole/dicyandiamide curing agent .
  • FIG. 9 depicts a TGA curve of cured reaction products of compositions based on methyl cyclopentadiene dimer diepoxide and RE-404-S at different ratios, and RE- 404-S (asterisk), cured with an anhydride curing agent.
  • FIG. 10 depicts a TGA curve of cured reaction products of compositions based on methyl cyclopentadiene dimer diepoxide (circle), Compound XVI of the '922 and '033 patents (square) , ERL 4221 (diamond) and RE-404-S (asterisk), cured with an anhydride curing agent.
  • FIG. 10 depicts a TGA curve of cured reaction products of compositions based on methyl cyclopentadiene dimer diepoxide (circle), Compound XVI of the '922 and '033 patents (square) , ERL 4221 (diamond) and RE-404-S (asterisk), cured with an
  • FIG. 11 depicts a TGA curve of cured reaction products of compositions based on ethylidene norbornene diepoxide and RE-404-S at different ratios, and RE-404-S (asterisk), cured with an anhydride curing agent.
  • FIG. 12 depicts a TGA curve of cured reaction products of compositions based on ethylidene norbornene diepoxide (circle), Compound XVI of the '922 and '033 patents (square) , ERL 4221 (diamond) and RE-404-S, cured with an anhydride curing agent .
  • FIG. 13 depicts a TGA curve of cured reaction products of compositions based on nopol epoxide glycidyl ether and RE-404-S at different ratios, and RE-404-S (asterisk), cured with an anhydride curing agent.
  • FIG. 14 depicts a TGA curve of cured reaction products of compositions based on nopol epoxide glycdyl ether (circle), Compound XVI of the "922 and '033 patents (square) , ERL 4221 (diamond) and RE-404-S, cured with an anhydride curing agent .
  • FIG. 15 depicts a 1 H HMR spectra of nopol glycidyl ether.
  • FIG. 16 depicts a FT-IR spectra of nopol glycidyl ether.
  • FIG. 17 depicts a ⁇ E HMR spectra of nopol epoxide glycidyl ether.
  • FIG. 18 depicts a FT-IR spectra of nopol epoxide glycidyl ether.
  • thermosetting resin compositions are useful for instance in microelectronic assembly applications, such as underfill sealants between a semiconductor device and a circuit board to which the semiconductor device is electrically connected.
  • the compositions may also be used for other microelectronic assembly applications, such as the direct chip attach applications, including glob top, and dam and fill.
  • the compositions may be used in far-flung applications, where thermosetting epoxies, or for that matter other thermosetting or thermoplastic adhesive, coating and sealant compositions, may be used.
  • the compositions may be used in the assembly of products, whose component parts have value as do the intermediate/finished products, to facilitate assembly and disassembly thereof where defective component parts are found.
  • the defective component part(s) may ⁇ be readily removed from the intermediate/finished product (s) and be replaced without having to scrap the entire intermediate/finished product (s) .
  • the speed with which the disassembly may proceed allows throughput to remain high.
  • a non-microelectronic example of such a part is the assembly of prosthetic devices.
  • the composition includes broadly (a) an epoxy resin component, at least a portion of which is a compound (I) having at least one linkage selected from oxiranes, thiiranes, and combinations thereof, substituted on at least three of the substitutable positions on the oxirane and/or thiirane carbons, respectively, with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interruption by one or more heteroatoms or halogens, as appropriate, provided that the compound I does not include as its sole component an epoxy compound within formula II:
  • each R is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, C ⁇ - 4 alkoxy, halogen, cyano and nitro
  • Ri and R 2 are each independently selected from the group consisting of hydrogen, methyl, ethyl, and propyl, provided that both Ri and R 2 cannot be hydrogen
  • R 3 is indpendently selected from propyl, and isopropyl, provided at least one of R 3a and R 3b , and at least one of R 3c and R 3d is independently selected from the group consisting of methyl, ethyl, propyl, and isopropyl
  • m is 0 or 1.
  • a curing agent component selected from anhydride (- t o l_ ⁇ o
  • weight percent such as about 15 to about 75 weight percent, desirably about 25 to about 60 weight percent, of the total of the epoxy resin component.
  • amount thereof should be in the range of from about 15 to about 60 weight percent, such as about 30 to about 50 weight percent, based on the weight of the curable resin component.
  • multifunctional epoxy resin examples include bisphenol-A-type epoxy resin, bisphenol-F-type epoxy resin (diglycidyl ether of bisphenol-F-type epoxy resin, such as RE-404-S from Nippon Kayaku, Japan) , phenol novolac- type epoxy resin, and cresol novolac-type epoxy from resin (such as "ARALDITE” ECN 1871 from Ciba Specialty Chemicals, Hawthorne, New York) .
  • bisphenol-A-type epoxy resin bisphenol-F-type epoxy resin (diglycidyl ether of bisphenol-F-type epoxy resin, such as RE-404-S from Nippon Kayaku, Japan)
  • phenol novolac- type epoxy resin such as "ARALDITE” ECN 1871 from Ciba Specialty Chemicals, Hawthorne, New York
  • epoxy resins include polyepoxy compounds based on aromatic amines and epichlorohydrin, such as N,N,N' ,N' -tetraglycidyl-4,4 ' -diaminodiphenyl methane; N- diglycidyl-4-aminophenyl glycidyl ether; and N,N,N',N'- tetraglycidyl-l,3-propylene bis-4-aminobenzoate.
  • polyepoxy compounds based on aromatic amines and epichlorohydrin such as N,N,N' ,N' -tetraglycidyl-4,4 ' -diaminodiphenyl methane; N- diglycidyl-4-aminophenyl glycidyl ether; and N,N,N',N'- tetraglycidyl-l,3-propylene bis-4-aminobenzoate.
  • epoxy resins suitable for use herein also include polyglycidyl derivatives of phenolic compounds, such as those available commercially under the tradename "EPON”, such as “EPON” 828, “EPON” 1001, “EPON” 1009, and “EPON” 1031 from Shell Chemical Co.; "DER” 331, “DER” 332, “DER” 334, and “DER” 542 from Dow Chemical Co.; and "BREN-S” from Nippon Kayaku.
  • EPON polyglycidyl derivatives of phenolic compounds
  • Suitable epoxy resins include polyepoxides prepared from polyols and the like and polyglycidyl derivatives of phenol -formaldehyde novolacs, the latter of which are available commercially under the tradename "DEN”, such as “DEN” 431, "DEN” 438, and “DEN” 439 from Dow Chemical. Cresol analogs are also available commercially under the tradename "ARALDITE”, such as “ARALDITE” ECN 1235, “ARALDITE” ECN 1273, and “ARALDITE” ECN 1299 from Ciba Specialty Chemicals.
  • SU-8 is a bisphenol-A- type epoxy novolac available from Interez, Inc.
  • Polyglycidyl adducts of amines, aminoalcohols and polycarboxylic acids are also useful in this invention, commercially available resins of which include “GLYAMINE” 135, “GLYAMINE” 125, and “GLYAMINE” 115 from F.I.C. Corporation; "ARALDITE” MY-720, “ARALDITE” 0500, and “ARALDITE” 0510 from Ciba Specialty Chemicals and PGA-X and PGA-C from the Sherwin-Williams Co.
  • Still other epoxy resins that are suitable for use herein include aliphatic epoxies with alkylene oxide residues, examples of which include, but are not limited to, mono-, di- or multi-functional epoxies containing ether linkages, such as primary, secondary and tertary alkylene diol diglycidyl ethers, and epoxies containing mono- or poly-alkylene oxide residues (such as ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, and hexylene oxide residues) .
  • aliphatic epoxies with alkylene oxide residues examples of which include, but are not limited to, mono-, di- or multi-functional epoxies containing ether linkages, such as primary, secondary and tertary alkylene diol diglycidyl ethers, and epoxies containing mono- or poly-alkylene oxide residues (such as ethylene oxide, propylene oxide, but
  • n is an integer from 1 to about 18, are each appropriate, individually or in combination, for use as at least a portion of the epoxy resin component .
  • Examples of cycloaliphatic epoxies with alkylene oxide residues include mono-, di- or multi functional cyclohexyl epoxies; hydrated bisphenol A-type epoxies; and hydrated bisphenol F-type epoxies, containing alkylene ether residues.
  • DME-100 4-cyclohexane dimethanol diglycidyl ether, available commercially from New Japan Chemical Co., Ltd.
  • aromatic epoxies with alkylene oxide residues include mono-, di- or multi-functional epoxies such as bisphenol A type epoxies; bisphenol F type epoxies; phenol novolac type epoxies; and cresol novolac type epoxies, containing alkylene ether residues.
  • epoxies examples include BEO-60E (ethoxylated bisphenol A di-glycidyl ether, available
  • n is an integer between and about 1 and 20, which for BPO-60E n is 1, and
  • n is an integer between and about 1 and 20, which for BEO-60E n is 3.
  • the inventive composition which after cure lends itself to being "reworked” under appropriate conditions, includes a compound having at least one oxirane or thiirane linkage substituted on at least three of the substitutable positions on the oxirane or thiirane carbons, respectfully, with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interuption by one or more heteroatoms or halogens.
  • oxirane or thiirane compounds When reacted with a curing agent it is believed that these oxirane or thiirane compounds form a tertiary ester (when the curing agent is anhydride based) or a tertiary ether (when the curing agent is nitrogen-based, such as with an imidazole) , which linkage is susceptible to controlled degradation under appropriate conditions, such as elevated temperature and/or acidic environment.
  • Such compounds include di- or poly-oxirane and thiirane compounds prepared from 2,10- dimethyl-6-methylene-4, 8-bis (2-methyl-l-propenyl-2, 4,7,9- undecatetraene (CAS Reg. No. 249664-51-7), 4-[(4E or 4Z)- 1, 5-dimethyl-4-heptenylidene or octenylidene] -1-methyl- cyclohexene (CAS Reg. Nos.
  • 1,3,6,10-dodecatraene (CAS Reg. Nos. 114091-33-7, 114091-32- 6), 3, 7, 11-trimethyl- (E or Z, E or Z)-l, 3, 6,10- dodecatetraene (CAS Reg. No. 113244-64-7), 4, 8-dimethyl- 1,4,7-nonatriene (CAS Reg. No. 110559-67-6), 3,7,11,15- tetramethyl-1, 3, 6, 10, 14-hexadecapentaene (CAS Reg. No.
  • 68965-68-4 2, 6, 10-trimethyl- 2,6,9-tetradecatriene (CAS Reg. No .68965-67-3) , 2,6- dimethyl- (Z or E) -2, 5-decadiene (CAS Reg. Nos. 68965-66-2, 68965-65-1), 6, 10-dimethyl-l, 6, 9-undecatrien-4-yne (CAS Reg. No. 68483-39-6), 2, 3, 6-trimethyl-2, 5-heptadiene (CAS Reg. No. 67796-57-0), 2, 4-dimethyl- (E or Z) -2, 5-heptadiene (CAS Reg. No.
  • R x and R 2 are each independently selected from hydrogen, methyl, ethyl and propyl, provided that both Ri and R 2 cannot be hydrogen
  • R 3 is independently selected from hydrogen, methyl, ethyl, propyl, and isopropyl, provided at least one of R 3a and R 3b
  • at least one of R 3c and R 3c j is independently selected from methyl, ethyl, propyl, and isopropyl
  • m is 0 or 1.
  • Particularly desirable epoxy or oxirane compounds within formula I_ include limonene diepoxide and gamma- terpinene diepoxide.
  • Limonene diepoxide may be obtained commercially from Daicel Chem. Co., Ltd., Japan under the tradename "CELLOXIDE" 3000.
  • epoxy or oxirane compounds include methyl cyclopentadiene diepoxide dimer ("MCPD dimer”), ethylidene norbornene diepoxide (“ENB diepoxide”), and nopol epoxide glycidyl ether (“NEGE”).
  • MCPD dimer methyl cyclopentadiene diepoxide dimer
  • ENB diepoxide ethylidene norbornene diepoxide
  • NEGE nopol epoxide glycidyl ether
  • the presence in the curable resin component of one or more epoxy compounds having at least one oxirane or thiirane linkage substituted on at least three of the substitutable positions on the oxirane or thiirane carbons, respectfully, with an alkyl, alkenyl or aryl substituent having a carbon content of one to about twelve carbon atoms, with or without substitution or interuption by one or more heteroatoms or halogens allows for repair, replacement, recovery and/or recycling of operative electronic components from assemblies that have become at least in part inoperative .
  • the compounds with the oxirane linkage (s) can be prepared from olefinically unsaturated compounds, many of which havine at least two olefinic linkages, with at least one of the olefinic linkages being substituted on at least three of the substitutable positions on the epoxy carbons with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interuption by one or more heteroatoms or halogens.
  • This olefinically unsaturated compound may ' then be contacted with an epoxidation agent in an amount and under conditions appropriate to react with the olefinic linkages to form an inventive compound having an oxirane linkage.
  • Appropriate epoxidation agents useful in forming oxirane rings include peracids (such as peracetic acid, . t
  • the curing agent component should include materials capable of catalyzing the polymerization of the epoxy resin component of the inventive compositions.
  • Desirable curing agents for use with the present invention include an anhydride component, a nitrogen-containing component, such as an amine compound, an amide compound, and an imidazole compound, or combinations thereof.
  • Appropriate anhydride compounds for use herein include mono- and poly-anhydrides, such as hexahydrophthalic anhydride (“HHPA”) and methyl hexahydrophthalic anhydride (“MHHPA”) (commercially available from Lindau Chemicals, Inc., Columbia, South Carolina, used individually or as a combination, which combination is available under the trade designation "LINDRIDE” 62C) and 5- (2 , 5-dioxotetrahydrol) -3- methyl-3-cyclohexene-l, 2-dicarboxylic anhydride (commercially available from ChrisKev Co., Leewood, Kansas under the trade designation B-4400) .
  • HHPA hexahydrophthalic anhydride
  • MHHPA methyl hexahydrophthalic an
  • the nitrogen-containing compound includes amine compounds such as polyamines and di-and tri-aza compounds, modified amine compounds, amide compounds, imidazole compounds, and combinations thereof.
  • amine compounds include the following alkyl poly amines: diethylenetriamine, triethylenetetraamine, diethylaminopropylamine, and quinoxaline.
  • di-or tri-aza compounds examples include:
  • DBU 1, 8-diazabicyclo [5.4.0] undec-7-ene
  • modified amine compounds include epoxy amine additives formed by the addition of an amine compound to an epoxy compound. Of course, combinations of these amine compounds are also desirable for use in the compositions of the present invention.
  • amide compounds include cyano- functionalized amides, such as dicyandiamide .
  • the imidazole compounds may be chosen from imidazole, isoimidazole, and substituted imidazoles -- such as alkyl-substituted imidazoles (e.g.
  • Examples of commercial imidazole compounds are available from Air Products, Allentown, Pennsylvania under the trade designation “CUREZOL” 1B2MZ and from Synthron, Inc., Morganton, North Carolina under the trade designation “ACTIRON” NXJ-60.
  • modified imidazole compounds include imidazole adducts formed by the addition of an imidazole compound to an epoxy compound.
  • imidazole adducts formed by the addition of an imidazole compound to an epoxy compound.
  • "AJICURE" PN-23 commercially available from Ajinomoto Co., Inc., Tokyo, Japan, is believed to be an adduct of EPON 828 (bisphenol-A-type epoxy resin, epoxy equivalent 184-194, commercially available from Shell Chemical Co.), 2-ethyl-4-methylimidazole and phthalic anhydride.
  • the adhesion promoters may be used in an amount of about 1 to about 20 weight percent, such as about 5 to about 15 weight percent, desirably about 8 to about 12 weight percent, based on the total weight of the composition.
  • Cyanate esters may also be used in the inventive compositions .
  • the cyanate esters useful as a component in the inventive compositions may be chosen from dicyanatobenzenes , tricyanatobenzenes , dicyanatonaphthalenes, tricyanatonaphthalenes, dicyanato- biphenyl, bis (cyanatophenyl) methanes and alkyl derivatives thereof, bis (dihalocyanatophenyl) propanes, bis (cyanatophenyl) ethers, bis (cyanatophenyl) sulfides, bis (cyanatophenyl) propanes, tris (cyanatophenyl) phosphites, tris (cyanatophenyl ) phosphates , bis (halocyanatophenyl) methanes, cyanated novolac, bis [cyanatophenyl (methylethylidene) ] benzene, cyanated bisphenol-terminated thermoplastic
  • aryl compounds having at least one cyanate ester group on each molecule may be generally represented by the formula Ar(OCN) m , where Ar is an aromatic radical and m is an integer from 2 to 5.
  • the aromatic radical Ar should contain at least 6 carbon atoms, and may be derived, for example, from aromatic hydrocarbons, such as benzene, biphenyl, naphthalene, anthracene, pyrene or the like.
  • the aromatic radical Ar may also be derived from a polynuclear aromatic hydrocarbon in which at least two aromatic rings are attached to each other through a bridging group.
  • the aromatic radical Ar may also contain further ring-attached, non-reactive substituents .
  • cyanate esters include, for instance, 1, 3-dicyanatobenzene; 1, 4-dicyanatobenzene; 1,3,5- tricyanatobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7- dicyanatonaphthalene ; 1,3, 6-tricyanatonaphthalene ; 4,4'- dicyanato-biphenyl; bis (4 -cyanatophenyl) methane and 3, 3 ' , 5, 5 ' -tetramethyl bis (4 -cyanatophenyl) methane; 2,2- to to * - ⁇
  • the reactive diluent should have a viscosity which is lower than that of the curable resin component. Ordinarily, the reactive diluent should have a viscosity less than about 250 cps . In the event such a monofunctional epoxy resin is included as a reactive diluent, such resin should be employed in an amount of up to about 50 weight percent, based on weight of the curable resin component.
  • the monofunctional epoxy resin should have an epoxy group with an alkyl group of about 6 to about 28 carbon atoms, examples of which include C 6 . 28 alkyl glycidyl ethers, C 6 _ 28 fatty acid glycidyl esters and C 6 . 28 alkylphenol glycidyl ethers.
  • monofunctional epoxy resin reactive diluents include those from Pacific Epoxy Polymers, Richmond, Michigan, under the trade designations PEP- 6770 (glycidyl ester of neodecandoic acid) , PEP- 6740 (phenyl glycidyl ether) and PEP- 6741 (butyl glycidyl ether) .
  • Multifunctional epoxy resin reactive diluents include those from Pacific Epoxy Polymers, under the trade designations PEP-6752 (trimethylolpropane triglycidyl ether) and PEP-6760 (diglycidyl aniline) .
  • compositions of the present invention may further include other additives, such as defoaming agents, leveling agents, dyes, and pigments.
  • photopolymerization initiators may also be incorporated therein, provided that such initiators do not adversely affect the properties of the composition or reaction products formed therefrom.
  • the present invention also includes novel diepoxide-containing compounds, set forth in detail below.
  • R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are individually selected from the group consisting of hydrogen, alkyl from one to eight carbon atoms, alkenyl from two to eight carbon atoms and combinations thereof, and X and X 1 are individually selected from O and S.
  • novel diepoxide- containing compounds include :
  • thermosetting resin compositions of this invention by selecting the types and proportions of various components to reach a viscosity at a temperature of 25°C in the range of 500 to 70,000 cps, such as 800 to 20,000 cps, depending on the amount present (if any) of an inorganic filler component, so as to improve its ability to penetrate into the space (e.g. , of 10 to 500 ⁇ xa) between the circuit board and the semiconductor device.
  • the gel times of the compositions will also be tailored to a specified period of time (such as 15 seconds, or 1 or 2 minutes) at a temperature of about 150°C.
  • the inventive compositions should show no or substantially no increase of viscosity after a period of time of about six hours. With such a gel time, the compositions penetrate into the space (e.g. , of 10 to 500 ⁇ ) between the circuit board and the semiconductor device relatively rapidly, and allow for a greater number of assemblies to be filled without observing a viscosity increase in the composition thereby rendering it less effective for application.
  • FIG. 1 shows a mounted structure (i.e. , a FC package) in which a thermosetting resin composition of the present invention has been applied and cured.
  • the FC package 4 is formed by connecting a semiconductor chip (a bare chip) 2 to a carrier substrate 1 (e.g. , a circuit board) and sealing the space therebetween suitably with a thermosetting resin composition 3.
  • the semiconductor chip 2 may be passed over a substrate bearing a conductive adhesive paste (such as a metal-filled epoxy) to form a layer thereof on the semiconductor chip 2.
  • a conductive adhesive paste such as a metal-filled epoxy
  • the layer is ordinarily formed by a printing mechanism.
  • the conductive adhesive paste may be applied on either the carrier substrate or the semiconductor chip .
  • One way to do this is with the stencil claimed and described in International Patent Publication No. PCT/FR95/00898.
  • this connection may also be made by an t t o
  • repair can be made in the following manner and as shown in the flow diagram depicted in FIG. 2.
  • the area around the semiconductor device which has failed is heated at a temperature of about 190 to about 260°C for a period of time ranging from about 10 seconds to about 2 minutes. (See FIG. 2, step 1.) Desirably, the temperature should be maintained in the range of about 210 to about 220°C and the period of time should be within the 30 seconds to 2 minute range. Localized heating is particularly desirable, such as the application of hot air to the failure site by a heating gun.
  • the semiconductor device may be pulled apart and removed from the substrate, such as with tweezers or pliers, or through automated processes.
  • a residue of the cured reaction product of the thermosetting resin composition and a residue of the solder are left on the circuit board 5.
  • the residue of the cured product of the thermosetting resin composition can be removed, for example, by scraping it off after the residue has been softened by heating it to a predetermined temperature.
  • the residue of the solder can be removed, for example, by use of a solder-absorbing braided wire. (See FIG. 2, step 2.)
  • a new semiconductor chip may be mounted azain onto the circuit board (which has been cleaned, with fluxing, as described above) in the manner as described above. (See FIG. 2, step 3.)
  • a thermosetting resin composition in accordance with this invention may be dispensed in the area between the semiconductor device and the circuit board, and cured. (See FIG. 2, step 4.) Repair of the failure site is thus completed.
  • the semiconductor device can be reused by removing the residue of the cured reaction product of the thermosetting resin composition and the residue of the solder left on the bottom of the semiconductor device in the same manner as described above .
  • the present invention will be more readily appreciated with reference to the examples which follow.
  • m-Chlorobenzoic acid was formed as a precipitate, and filtered off, with the organic filtrate - washed twice with 500 ml portions of 10% aqueous Na 2 S0 3 , twice with 500 ml portions of saturated aqueous Na 2 C0 3 solution, and twice with 500 ml portions of water.
  • the organic layer was separated, dried over anhydrous MgS0 4 , and then filtered.
  • Basic alumina 50 grams was then added to the organic filtrate, with the mixture stirred for a period of time of about 45 minutes, and then filtered.
  • the organic solvent was removed under reduced pressure, and the resulting product vacuum distilled. Limonene diepoxide was obtained in an amount of 120.7 grams (86% yield) .
  • the reaction temperature was maintained at or near about 10°C during the addition.
  • the ice/water bath was removed, and the mixture was allowed to warm to ambient temperature, while it stirred overnight.
  • the reaction mixture was then quenched with 500 ml of ice cold water, which was added over a period of time of about 15 minutes, with stirring for an adiitional period of time of about 20 minutes.
  • the mixture was transferred to a 2 liter separatory funnel, where it was twice extracted with 200 ml of diethyl ether.
  • the organic portion was then washed twice with 200 ml of sat. aq. NaCl, separated, dried over anhydrous MgS0 4/ and then filtered. After filtration, the solvent was removed under reduced pressure.
  • thermosetting resin composition (Sample No. 1) was prepared by mixing together for a period of time of about 10 minutes at room temperature in an open vessel the following components: 1. an epoxy resin component including
  • a curing agent component including 46.5 weight percent of MHHPA, 0.8 weight percent of benzyldimethyl amine, and
  • thermosetting resin composition (Sample No. 6) was prepared as described above by mixing together the following components:
  • a curing agent component including
  • Samples Nos. 7-10 were prepared as Sample No. 6, substituting for the limonene diepoxide, the same amounts of gamma-terpinene diepoxide, Compound XVI of the '922 patent, and the commercially available epoxy resins ERL-4221 and RE-404-S. [See Table 2(a) .]
  • thermosetting resin composition (Sample No. 11) was prepared with a limonene diepoxide/RE-404-S combination, designed with an imidazole/dicyandiamide cure, as described above by mixing together the following components :
  • an epoxy resin component including
  • thermosetting resin composition (Sample No. 14) was prepared with a terpinene diepoxide/RE- 404-S combination, designed with an imidazole/dicyandiamide cure, as described above by mixing together the following components :
  • a curing agent component including
  • Samples Nos. 15-16 Two additional compositions (Samples Nos. 15-16) were prepared as Sample No. 14, except that the weight percent of the terpinene diepoxide was decreased and the weight percent of the RE-404-S was increased. [See Table 2(b) .]
  • thermosetting resin composition (Sample No. 17) was prepared based on a limonene diepoxide/RE-404-S combination, designed with an imidazole/dicyandiamide cure, as described above by mixing together the following components :
  • an epoxy resin component including
  • a flowability agent including the silanes, octyl (A-137, 0.06 weight percent) and glycidyl (A-187, 0.06 weight percent), and titanate (KR-55, 0.06 weight percent).
  • Five additional compositions (Sample Nos. 18-21 and 25) were prepared along these lines, except that the limonene diepoxide/RE-404-S ratio was varied, and as to Sample Nos. 21 and 25, the weight percents of the components of the flowability agent were also varied. [See Tables 2 (b) and 2 (c) .]
  • thermosetting resin composition (Sample No. 22) was prepared based on a limonene diepoxide/RE-404-S combination, designed with an anhydride cure, as described above by mixing together the following components :
  • an epoxy resin component including
  • a flowability agent including the silanes (A-137, 0.09 weight percent) and (A-187, 0.12 weight percent), and titanate (KR-55, 0.45 weight percent); and
  • Example Nos. 23-24 Two additional compositions (Sample Nos. 23-24) were prepared along these lines, except that the limonene diepoxide/RE-404-S ratio was varied, the weight percents of the components of the anhydride cure agent were also varied, and the weight percent of the inorganic filler component were varied as well. [See Table 2(c).]
  • thermosetting resin composition (Sample No. 26) was prepared based on a limonene diepoxide (commercially available from Daicel Chem. Co., Ltd., Japan under the tradename “CELLOXIDE” 3000), designed to cure with a latent hardener (commercially available from Asahi-Ciba, Ltd., Japan under the tradename "NOVACURE” HX- 3921 HP) , and without a second epoxy resin, as described above by mixing together the following components:
  • an epoxy resin component including
  • a curing agent component including
  • Example No. 27-30 60 weight percent of "NOVACURE" HX-3921 HP.
  • Four additional compositions (Sample Nos. 27-30) were prepared along these lines, except that the limonene diepoxide/latent hardener ratio was varied, and an inorganic filler component was included in various weight percents, and a second epoxy resin was included in Sample No. 30. [See Table 2(c) .]
  • Sample Nos. 31 and 32 show thermosetting resin compositions prepared from ethylidene norbornene diepoxide and methyl cyclopentadiene dimer diepoxide, respectively, designed to cure with an anhydride curing agent .
  • Sample Nos. 33-35 show thermosetting resin compositions, based on limonene diepoxide/RE-404-S in combination at various ratios (like Sample Nos. 21-25) designed to cure with an anhydride curing agent, an imidizole curing agent, or both.
  • thermosetting resin compositions based on limonene diepoxide designed to cure with a latent hardener commercially available for Asahi-Ciba, Ltd., Japan under the tradename "NOVACURE” HX03921 HP
  • a latent hardener commercially available for Asahi-Ciba, Ltd., Japan under the tradename "NOVACURE” HX03921 HP
  • thermosetting resin composition (Sample No. 41) was prepared based on a limonene diepoxide (commercially available from Daicel Chem. Co., Ltd., Japan under the tradename “CELLOXIDE” 3000), designed to cure with a latent hardener (commercially available from Asahi-Ciba, Ltd., Japan under the tradename "NOVACURE” HX- 3921 HP) , without a second epoxy resin, as described above by mixing together the following components:
  • an epoxy resin component including
  • Example Nos. 42-49 Nine additional compositions (Sample Nos. 42-49) were prepared along these lines, except that the type and amount of the epoxy resin was varied as noted, and an inorganic filler component was included in various weight percents, and a second epoxy resin was included in Sample
  • compositions were used upon formation (see below) , they may be stored for a period of time of up to about 3 to about 6 months at a temperature of about -40°C without experiencing viscosity increase.
  • composition was transferred to a 10 ml syringe made of non-reactive plastic. Mounting/Underfill Process
  • sample Nos. 17-25 were dispensed through a 12G needle connected to the syringe into the junction between the carrier substrate and semiconductor device an assembly previously formed as above.
  • the assembly was transferred to an oven while the temperature was maintained at about 165°C.
  • the composition cured initially after about 1 minute, and thereafter cured completely after about 15 minutes at that temperature .
  • sample Nos. 1-16 were dispensed onto an aluminum dish, and cured in a step-wise manner by exposure to an elevated temperature of about 100°C for a period of time of about 2 hours, followed by exposure to an elevated temperature of about 140°C for a period of time of about 6 hours, at the end of which time the compositions were observed to have cured.
  • compositions have a variety of properties in both the uncured and cured state which are measurable and useful parameters for the end user in choosing a particular formulation for a desired need.
  • the flow rate is of interest; in reaching the cured state, the cure schedule is of interest .
  • the flow time allows the end user to determine the rapidity with which the adhesive may be applied during a fabrication process, such as a circuit assembly operation. It may be measured by passing the composition through a 25 ⁇ m gap between glass slides aligned perpendicular to one another, using metal shims as spacers. The time required for the composition to flow between the slides is then measured at a length of about one inch, "at 0.25 inch intervals. Values in seconds for the flow times of the compositions set forth above are presented as an average of three measurements below in Table 3.
  • the cure schedule refers to the time required for the onset of cure to occur at a certain temperatrue, in a specified period of time. This may be seen in more detail with regard to certain of the samples prepared in accordance with the present invention below in Table 3.
  • reaction exotherm As the composition progresses through its cure schedule, the reaction exotherm, or enthalpy, assists in determining the effectiveness of a (co) polymerization reaction.
  • the reaction exotherm here is measured by differential scanning calorimetry ("DSC") .
  • the peak temperature (“T PEAK ”) and onset temperature (“T 0NSET ”) may be determined from the DSC measurement . These values provide information for minimum reasonable curing temperatures, the curing temperature range, maximum reaction temperatures, and relative curing time at each temperature. See Tables 4a, 4(b) and 4(c) .
  • adhesion provides information on the strength of the bond formed by the cured reaction product, data for which is set forth in Table 5.
  • die shear adhesion is measured by a Sebastion 5 die shear measurement instrument, which measures the amount of shear strength (in Kgf) required to pull apart a die attached to a circuit board by the cured reaction product as an underfill sealant (without a solder mask, or chipbonding adhesive) .
  • Reworkability determines the ease with which a cured reaction product may be controllably degraded.
  • the extent to which the cured reaction product loses mass over time at an increase in temperature may be measured by thermal gravimetric analysis ("TGA"), and provides information on the temperature (or range) at which the cured reaction product degrades.
  • TGA thermal gravimetric analysis
  • FIGs . 3-4 show TGA data for cured reaction products of Sample Nos. 1-5 using an anhydride curing agent, compared with TGA data for cured reaction products of compositions based on the commercially available epoxies ERL-4221 (Sample No. 4) and RE-404-S (Sample No. 5), and Compound XVI of the '922 and '033 patents (Sample No. 3) .
  • FIGs. 5-6 show TGA data for cured reaction products of Sample Nos. 7-10 using an imidazole/dicyandiamide curing agent, compared with TGA data for cured reaction products of compositions based on the commercially available epoxies ERL-4221 (Sample No. 9) and RE-404-S (Sample No. 10), and Compound XVI of the '922 and '033 patents (Sample No. 8).
  • Reference to FIGs. 7-8 show TGA data for cured reaction products of Sample Nos.
  • FIGs. 9-10 show TGA data for anhydride cured reaction products of Sample Nos. 5 (RE-404- S) , 32 (methyl cyclopentadiene dimer diepoxide), and 50-52, having 80:20, 60:40 and 40:60 combinations of methyl cyclopentadiene dimer diepoxide/RE-404-S and RE-404-S, and for anhydride cured reaction products of methyl cyclopentadiene dimer diepoxide (Sample No. 32), the commercially available epoxies ERL-4221 (Sample No. 4) and RE-404-S (Sample No. 5), and Compound XVI of the '922 and '033 patents (Sample No. 3).
  • FIGs. 11-12 show TGA data for anhydride cured reaction products of Sample Nos. 5, 31 (ethylidene norbornene diepoxide), 53-55, having 80:20, 60:40 and 40:60 combinations of ethylidene norbornene diepoxide/RE-404-S, and RE-404-S, and anhydride cured reaction products of ethylidene norbornene diepoxide (Sample No. 31), the commercially available epoxies ERL-4221 (Sample No. 4) and RE-404-S (Sample No. 5), and Compound XVI of the '922 and '033 patents (Sample No. 3).
  • FIGs. 13-14 show TGA data for anhydride cured reaction products of Sample Nos. 5, 55-58 and 59 (nopol epoxide glycidyl ether), having 80:20, 60:40, and 40:60 combinations of nopol epoxide glycidyl ether/RE- 404-S, and RE-404-S, and anhydride cured reaction products of nopol epoxide glycidyl ether (Sample No. 59), commercially available epoxies ERL-4221 (Sample No. 4), and RE-404-S (Sample No. 5), and Compound XVI of the '922 and '033 patents (Sample Nos.
  • the TGA data indicate that cured reaction products of the inventive compositions (e.g., Sample Nos. 1-2, and 7- 8) degrade and lose mass at a temperature lower than cured reaction products of the compositions based on either of the commercially available epoxies, to which reference is made above .
  • thermosetting resin composition of this invention may be applied around the periphary of the newly-replaced semiconductor chip and cured by heating to an appropriate temperature, as described herein.

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Abstract

A composition useful as underfill sealant for the connection of a semiconductor device to a circuit board is reworkable for more easy separation from the semiconductor device and comprises a curable resin having at least one oxirane or thiirane linkage substituted on at least three of the oxirane or thiirane carbon atoms with an alkyl, alkenyl or aryl substituent along with a curing agent selected from anhydrides, amines, amides, imidazoles, and combinations thereof.

Description

REWORKABLE COMPOSITION OF OXIRANE(S) OR THIIRANE(S)-CONTAINING RESIN AND CURING AGENT
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to thermosetting resin compositions useful for instance, in mounting onto a circuit board semiconductor devices, such as chip size or chip scale packages ("CSPs"), ball grid arrays ("BGAs"), land grid arrays ("LGAs") and the like, each of which having a semiconductor chip, such as large scale integration ("LSI"), on a carrier substrate. The compositions of 'this invention are reworkable when subjected to appropriate conditions.
Brief Description of Related Technology
In recent years, the popularity of small-sized electronic appliances, such as camera-integrated video tape recorders ("VTRs") and portable telephone sets, has made size reduction of LSI devices desirable. As a result, CSPs, BGAs and LGAs are being used to reduce the size of packages substantially to that of bare chips. Such CSPs, BGAs, LGAs improve the characteristics of the electronic device while retaining many of their operating features, thus serving to protect semiconductor bare chips, such as LSIs, and facilitate testing thereof.
Ordinarily, the CSP/BGA/LGA assembly is connected to electrical conductors on a circuit board by use of a solder connection or the like. However, when the resulting CSP/BGA/LGA/circuit board structure is exposed to thermal cycling, the reliability of the solder connection between the circuit board and the CSP/BGA/LGA often becomes suspect . Recently, after a CSP/BGA/LGA assembly is mounted on a circuit board, the space between the CSP/BGA/LGA assembly and the circuit board is often now filled with a sealing resin (often referred to as underfill sealing) in order to relieve stresses caused by thermal cycling, thereby improving heat shock properties and enhancing the reliability of the structure.
However, since thermosetting resins are typically used as the underfill sealing material, in the event of a failure after the CSP/BGA/LGA assembly is mounted on the circuit board, it is very difficult to replace the CSP/BGA/LGA assembly without destroying or scrapping the structure in its entirety.
To that end, techniques for mounting a bare chip on a circuit board are accepted as substantially similar to the mounting of a CSP/BGA/LGA assembly onto a circuit board. One such technique, disclosed in Japanese Laid-Open Patent
Publication No. 102343/93, involves a mounting process where a bare chip is fixed and connected to a circuit board by use of a photocurable adhesive, where, in the event of failure, this bare chip is removed therefrom. However, this technique is limited to those instances where the circuit board includes a transparent substrate (e.g. , glass) which permits exposure to light from the back side, and the resulting structure exhibits poor heat shock properties.
Japanese Laid-Open Patent Publication No. 69280/94 discloses a process where a bare chip is fixed and connected to a substrate by use of a resin capable of hardening at a predetermined temperature. In the event of failure, this bare chip is removed from the substrate by softening the resin at a temperature higher than the predetermined temperature. However, no specific resin is disclosed, and there is no disclosure about treating the resin which remains on the substrate. Thus, the disclosed process is at best incomplete . As pointed out in Japanese Laid-Open Patent
Publication No. 77264/94, it is conventional to use a solvent to remove residual resin from a circuit board. However, swelling the resin with a solvent is a time consuming process and the corrosive organic acid ordinarily used as the solvent may reduce the reliability of the circuit board. Instead, that disclosure speaks to a method for removing residual resin by irradiation with electromagnetic radiation.
Japanese Laid-Open Patent Publication No. 251516/93 also discloses a mounting process using bisphenol A type epoxy resin (CV5183 or CV5183S; manufactured by Matsushita Electric Industrial Co., Ltd.). However, the removal process so disclosed does not consistently permit easy removal of the chip, the curing step is lengthy at elevated temperatures, and the process generally results in poor productivity.
Of course, mechanical methods of removing/replacing semiconductor chips from/on a substrate are known, such as by cutting the chip to be removed/replaced. See U.S. Patent No. 5,355,580 (Tsukada) .
Thermoplastic underfill resins are known for use in semiconductor chip attachment. See U.S. Patent No. 5,783,867 (Belke, Jr.). However, such thermoplastic resins tend to leak under relatively modest temperature conditions. In contrast, thermosetting resins cure into a matrix which ordinarily have greater thermal stability under end use operating temperatures .
U.S. Patent Nos . 5,512,613 (Afzali-Ardakani), 5,560,934 (Afzali-Ardakani) and 5,932,682 (Buchwalter), each refer to a reworkable thermoset composition based on a diepoxide component in which the organic linking moiety connecting the two epoxy groups of the diepoxide includes an acid cleavable acyclic acetal group. With such acid cleavable acyclic acetal groups forming the bases of the reworkable composition, a cured thermoset need only be introduced to an acidic environment in order to achieve softening and a loss of much of its adhesiveness.
U.S. Patent No. 5,872,158 (Kuczynski) and 6,008,266 (Kuczynski), each refer to thermosetting compositions capable of curing upon exposure to actinic radiation, which are based on acetal diacrylates and acetal diepoxides, respectively, and reaction products of which are reported to be soluble in dilute acid. U.S. Patent No. 5,760,337 (Iyer) refers to thermally reworkable crosslinked resins to fill the gap created between a semiconductor device and a substrate to which it is attached. These resins are produced by reacting a dienophile (with a functionality greater than 1) with a 2.5-dialkyl substituted furan-containing polymer.
International Patent Publication No. PCT/US98/00858 refers to a thermosetting resin composition capable of sealing underfilling between a semiconductor device including a semiconductor chip mounted on a carrier substrate and a circuit board to which said semiconductor device is electrically connected. The composition includes about 100 parts by weight of an epoxy resin, about 3 to about 60 parts by weight of a curing agent, and about 1 to about 90 parts by weight of a plasticizer. Here, the area around the cured thermoset is to be heated at a temperature of about 190 to about 260°C for a period of time ranging from about 10 seconds to about 1 minute in order to achieve softening and a loss of much of its adhesiveness.
U.S. Patent Nos. 5,948,922 (Ober) and 5,973,033 (Ober) , each refer to a certain class of compounds having tertiary oxycarbonyl linkages, and compositions based on such compounds, which when cured provide thermally decomposable compositions capable of being reworked.
Notwithstanding the state of- the art, it would be desirable for an underfilling sealing material to provide good productivity, thermal shock and mechnaical stress absorbing properties, while allowing the substrates with which it is to be used to be readily processed and easily separated from a semiconductor device without application of too extreme conditions that may compromise the integrity of the semiconductor devices remaining on the substrate or the substrate itself. In addition, it would be desirable to provide such a material which is based on an epoxy material for reworkability that may be prepared from readily available and inexpensive starting materials.
SUMMARY OF THE INVENTION
The present invention provides a thermosetting resin composition, which includes broadly a curable resin component, at least a portion of which is a compound having at least one linkage selected from oxiranes, thiiranes, and combinations thereof, substituted on at least three of the substitutable positions on the oxirane and/or thiirane carbons, respectively, with an alkyl, alkenyl or aryl substituent having a carbon content of one to about twelve carbon atoms, with or without substitution or interruption by one or more heteroatoms or halogens, as appropriate; and a curing agent component including an anhydride component, a nitrogen-containing component, such as amine or aza compounds, amide compounds, and/or imidazole compounds, or combinations thereof.
The present invention also provides novel diepoxide-containing compounds, the structures for which are described in detail herein.
Reaction products of these compositions are capable of softening under exposure to elevated temperature conditions, such as in excess of the tempertures used to cure the composition. Such temperature exposure provides the reworkable aspect of the reaction products of the inventive compositions. The remaining components, discussed below, provide the physical properties and characteristics for the compositions and reaction products to render the compositions attractive for commercial use, particularly in the microelectronics industry.
The inventive compositions are useful as an underfilling sealing resin, and enables a semiconductor device, such as a CSP/BGA/LGA assembly which includes a semiconductor chip mounted on a carrier substrate, to be securely connected to a circuit board by short-time heat curing and with good productivity. Reaction products of the inventive compositions demonstrate excellent heat shock properties, and permit the semiconductor device to be easily removed from the circuit board by localized heating in excess of the temperature at which the composion cures, in the event of semiconductor device or connection failure. This makes it possible to reuse the circuit board (with the remaining functioning semiconductor devices still electrically attached) and thereby achieve an improvement in the yield of the production process and a reduction in production cost.
The compositions of this invention may also be used for microelectronic applications beyond sealing underfill, such as with glob top, die attachment and other applications for thermosetting compositions.
Other benefits and advantages of the present invention will become more readily apparent after a reading of the "Detailed Description" section together with the figures .
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts a cross-sectional view showing an example of the mounting structure in which the thermosetting resin composition of the present invention is used.
FIG. 2 depicts a flow diagram of a procedure useful to rework a cured thermosetting resin composition in accordance with the present invention, so as to remove a semiconductor device from a circuit board to which it had been attached.
FIG. 3 depicts a TGA curve of cured reaction products of compositions based on limonene diepoxide (square), Compound XVI of U.S. Patent Nos. 5,948,922 (Ober) and 5,973,033 (Ober) (circle), commercially available diepoxidized dicycloaliphatic ester (ERL 4221) (closed square) and commercially available diglycidyl ether of bisphenol F epoxy resin (RE-404-S) (asterisk) , cured with an anhydride curing agent .
FIG. 4 depicts a TGA curve of cured reaction products of compositions based on terpinene diepoxide (square), Compound XVI of the '922 and '033 patents
(circle) , ERL 4221 (closed square) and RE-404-S (asterisk) , cured with an anhydride curing agent .
FIG. 5 depicts a TGA curve of cured reaction products of compositions based on limonene diepoxide and RE- 404-S at different ratios, and RE-404-S (asterisk) , cured with an imidazole/dicyandiamide curing agent .
FIG. 6 depicts a TGA curve of cured reaction products of compositions based on limonene diepoxide/RE-404- S (circle), Compound XVI of the '922 and '033 patents (square) , ERL 4221 (diamond) and RE-404-S (asterisk) , cured with an imidazole/dicyandiamide curing agent .
FIG. 7 depicts a TGA curve of cured reaction products of compositions based on gamma-terpinene diepoxide and RE-404-S at different ratios, and RE-404-S (asterisk) , cured with an imidazole/dicyandiamide curing agent .
FIG. 8 depicts a TGA curve of cured reaction products of compositions based on gamma-terpinene diepoxide/RE-404-S (circle), Compound XVI of the '922 and '033 patents (square), ERL 4221 (diamond) and RE-404-S, cured with an imidazole/dicyandiamide curing agent .
FIG. 9 depicts a TGA curve of cured reaction products of compositions based on methyl cyclopentadiene dimer diepoxide and RE-404-S at different ratios, and RE- 404-S (asterisk), cured with an anhydride curing agent. FIG. 10 depicts a TGA curve of cured reaction products of compositions based on methyl cyclopentadiene dimer diepoxide (circle), Compound XVI of the '922 and '033 patents (square) , ERL 4221 (diamond) and RE-404-S (asterisk), cured with an anhydride curing agent. FIG. 11 depicts a TGA curve of cured reaction products of compositions based on ethylidene norbornene diepoxide and RE-404-S at different ratios, and RE-404-S (asterisk), cured with an anhydride curing agent. FIG. 12 depicts a TGA curve of cured reaction products of compositions based on ethylidene norbornene diepoxide (circle), Compound XVI of the '922 and '033 patents (square) , ERL 4221 (diamond) and RE-404-S, cured with an anhydride curing agent .
FIG. 13 depicts a TGA curve of cured reaction products of compositions based on nopol epoxide glycidyl ether and RE-404-S at different ratios, and RE-404-S (asterisk), cured with an anhydride curing agent. FIG. 14 depicts a TGA curve of cured reaction products of compositions based on nopol epoxide glycdyl ether (circle), Compound XVI of the "922 and '033 patents (square) , ERL 4221 (diamond) and RE-404-S, cured with an anhydride curing agent . FIG. 15 depicts a 1H HMR spectra of nopol glycidyl ether.
FIG. 16 depicts a FT-IR spectra of nopol glycidyl ether.
FIG. 17 depicts a ^E HMR spectra of nopol epoxide glycidyl ether.
FIG. 18 depicts a FT-IR spectra of nopol epoxide glycidyl ether.
DETAILED DESCRIPTION OF THE INVENTION As noted above, the thermosetting resin compositions are useful for instance in microelectronic assembly applications, such as underfill sealants between a semiconductor device and a circuit board to which the semiconductor device is electrically connected. Of course, the compositions may also be used for other microelectronic assembly applications, such as the direct chip attach applications, including glob top, and dam and fill. In addition, the compositions may be used in far-flung applications, where thermosetting epoxies, or for that matter other thermosetting or thermoplastic adhesive, coating and sealant compositions, may be used.
For instance, the compositions may be used in the assembly of products, whose component parts have value as do the intermediate/finished products, to facilitate assembly and disassembly thereof where defective component parts are found. In that event, the defective component part(s) may¬ be readily removed from the intermediate/finished product (s) and be replaced without having to scrap the entire intermediate/finished product (s) . In addition, the speed with which the disassembly may proceed allows throughput to remain high. A non-microelectronic example of such a part is the assembly of prosthetic devices. The composition includes broadly (a) an epoxy resin component, at least a portion of which is a compound (I) having at least one linkage selected from oxiranes, thiiranes, and combinations thereof, substituted on at least three of the substitutable positions on the oxirane and/or thiirane carbons, respectively, with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interruption by one or more heteroatoms or halogens, as appropriate, provided that the compound I does not include as its sole component an epoxy compound within formula II:
Figure imgf000010_0001
wherein each R is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, Cι-4 alkoxy, halogen, cyano and nitro, Ri and R2 are each independently selected from the group consisting of hydrogen, methyl, ethyl, and propyl, provided that both Ri and R2 cannot be hydrogen, and R3 is indpendently selected from propyl, and isopropyl, provided at least one of R3a and R3b, and at least one of R3c and R3d is independently selected from the group consisting of methyl, ethyl, propyl, and isopropyl, and m is 0 or 1. and (b) a curing agent component selected from anhydride (- t o l_Λ o
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CQ 3 Ω Φ rr m 0 ø O ø* ii 1-* 0 rt CQ r t tr r tr TJ ø Φ 0 CQ X 0 rt SU s; P* 3 0 SD P* 3 iQ TJ rr Hi Φ ■S tr ^ ω r Φ -> ■S σi SD rt φ o rt CQ ii Hi TJ Hi tr 3
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TJ ii X rr ft ft ii 0 Φ μ- SD d 0 rr 3 TJ 0 ø rt μ- rt 3
Φ μ- • ; TS d *< ø ft tr ii 3 CQ Φ SD 0 CQ Hi TJ Φ d rt rt Φ μ- *< S tr 0 rt 0 Ω TJ
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weight percent, such as about 15 to about 75 weight percent, desirably about 25 to about 60 weight percent, of the total of the epoxy resin component. In the case of bisphenol-F- type epoxy resin, desirably the amount thereof should be in the range of from about 15 to about 60 weight percent, such as about 30 to about 50 weight percent, based on the weight of the curable resin component.
Examples of the multifunctional epoxy resin include bisphenol-A-type epoxy resin, bisphenol-F-type epoxy resin (diglycidyl ether of bisphenol-F-type epoxy resin, such as RE-404-S from Nippon Kayaku, Japan) , phenol novolac- type epoxy resin, and cresol novolac-type epoxy from resin (such as "ARALDITE" ECN 1871 from Ciba Specialty Chemicals, Hawthorne, New York) . Other suitable epoxy resins include polyepoxy compounds based on aromatic amines and epichlorohydrin, such as N,N,N' ,N' -tetraglycidyl-4,4 ' -diaminodiphenyl methane; N- diglycidyl-4-aminophenyl glycidyl ether; and N,N,N',N'- tetraglycidyl-l,3-propylene bis-4-aminobenzoate. Among the epoxy resins suitable for use herein also include polyglycidyl derivatives of phenolic compounds, such as those available commercially under the tradename "EPON", such as "EPON" 828, "EPON" 1001, "EPON" 1009, and "EPON" 1031 from Shell Chemical Co.; "DER" 331, "DER" 332, "DER" 334, and "DER" 542 from Dow Chemical Co.; and "BREN-S" from Nippon Kayaku. Other suitable epoxy resins include polyepoxides prepared from polyols and the like and polyglycidyl derivatives of phenol -formaldehyde novolacs, the latter of which are available commercially under the tradename "DEN", such as "DEN" 431, "DEN" 438, and "DEN" 439 from Dow Chemical. Cresol analogs are also available commercially under the tradename "ARALDITE", such as "ARALDITE" ECN 1235, "ARALDITE" ECN 1273, and "ARALDITE" ECN 1299 from Ciba Specialty Chemicals. SU-8 is a bisphenol-A- type epoxy novolac available from Interez, Inc.
Polyglycidyl adducts of amines, aminoalcohols and polycarboxylic acids are also useful in this invention, commercially available resins of which include "GLYAMINE" 135, "GLYAMINE" 125, and "GLYAMINE" 115 from F.I.C. Corporation; "ARALDITE" MY-720, "ARALDITE" 0500, and "ARALDITE" 0510 from Ciba Specialty Chemicals and PGA-X and PGA-C from the Sherwin-Williams Co.
Still other epoxy resins that are suitable for use herein include aliphatic epoxies with alkylene oxide residues, examples of which include, but are not limited to, mono-, di- or multi-functional epoxies containing ether linkages, such as primary, secondary and tertary alkylene diol diglycidyl ethers, and epoxies containing mono- or poly-alkylene oxide residues (such as ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, and hexylene oxide residues) .
For instance,
Figure imgf000013_0001
Figure imgf000013_0002
Figure imgf000013_0003
Figure imgf000013_0004
where n is an integer from 1 to about 18, are each appropriate, individually or in combination, for use as at least a portion of the epoxy resin component .
Examples of cycloaliphatic epoxies with alkylene oxide residues include mono-, di- or multi functional cyclohexyl epoxies; hydrated bisphenol A-type epoxies; and hydrated bisphenol F-type epoxies, containing alkylene ether residues. DME-100 (1, 4-cyclohexane dimethanol diglycidyl ether, available commercially from New Japan Chemical Co., Ltd.) as shown below is one such example.
Figure imgf000014_0001
Examples of aromatic epoxies with alkylene oxide residues include mono-, di- or multi-functional epoxies such as bisphenol A type epoxies; bisphenol F type epoxies; phenol novolac type epoxies; and cresol novolac type epoxies, containing alkylene ether residues.
Examples of such epoxies include BEO-60E (ethoxylated bisphenol A di-glycidyl ether, available
Figure imgf000014_0002
commercially from New Japan Chemical Co., Ltd.), and BPO-20E (propyloxylated bisphenol A di-glycidyl ether, available commercially from New Japan Chemical Co., Ltd.), which are shown below:
where n is an integer between and about 1 and 20, which for BPO-60E n is 1, and
Figure imgf000014_0003
where n is an integer between and about 1 and 20, which for BEO-60E n is 3.
And of course combinations of the different epoxy resins are also desirable for use herein. The inventive composition, which after cure lends itself to being "reworked" under appropriate conditions, includes a compound having at least one oxirane or thiirane linkage substituted on at least three of the substitutable positions on the oxirane or thiirane carbons, respectfully, with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interuption by one or more heteroatoms or halogens. When reacted with a curing agent it is believed that these oxirane or thiirane compounds form a tertiary ester (when the curing agent is anhydride based) or a tertiary ether (when the curing agent is nitrogen-based, such as with an imidazole) , which linkage is susceptible to controlled degradation under appropriate conditions, such as elevated temperature and/or acidic environment.
Particular examples of such compounds include di- or poly-oxirane and thiirane compounds prepared from 2,10- dimethyl-6-methylene-4, 8-bis (2-methyl-l-propenyl-2, 4,7,9- undecatetraene (CAS Reg. No. 249664-51-7), 4-[(4E or 4Z)- 1, 5-dimethyl-4-heptenylidene or octenylidene] -1-methyl- cyclohexene (CAS Reg. Nos. 221269-56-3, 221269-55-2, 209462- 40-8, 209462-39-5), 1,1'-[(1E or 1Z, 3E or 3Z)-5-(l,l- dimethyl-2-propenyl) -3- (3-methyl-2-butenyl) -1, 3-pentadiene- l,5-diyl]bis-benzene (CAS Reg. No. 207513-40-4), 4,6- dimethyl- [S or R- (E or Z, Z or E) ] -2, 5-octadiene (CAS Reg. No. 203515-58-6, 203515-52-0), 2, 6, 10, 14-tetramethyl-7- (3- methyl-4-pentenyl) -2, 5, 9, 13-pentadecatetraene (CAS Reg. No. 202134-68-7), 7-ethyl-3, 11-dimethyl- (3Z or 3E, 6E or 6Z, 10Z or 10E)-l,3,6,10-tridecatetraene (CAS Reg. No. 189387-61-9), 3,4,8-trimethyl-l,4,7-nonatriene (CAS Reg. No. 179981-39-6), 13-ethyl-9-methyl-l, 9, 12-pentadecatetraene (CAS Reg. No. 174189-19-6) , 1-methyl--4- (2-methyl-6-heptenylidene) - cyclohexene (CAS Reg. No. 170274-84-7), 2, 6, 11-trimethyl- (E or Z) -2,5,10-dodecatriene (CAS Reg. No. 169524-63-4), 2,6- dimethyl- (E or Z, E or Z) -2, 6, 9-tetradecatriene (CAS Reg.
No. 169265-90-1), 7- (3-methyl-2-butenyl- (E or Z) -6-dodecene (CAS Reg. No. 168141-30-8), 6- (3-methyl-2-butenyl) - (E or Z)- 6-dodecene (CAS Reg. No. 168141-25-1), 2,4,6,6,8- pentamethyl-2,4,7-nonatriene (CAS Reg. No. 164993-09-9), 3, 7-dimethyl-ll- (methyl) - (E or Z, E or Z) -1,3, 6,10- dodecatetraene (CAS Reg. No. 162189-16-4), 5- [3-methyl-1- (2- methyl-1-propenyl) -2-butenylidene] -1, 3-cyclopentadiene (CAS Reg. No. 162143-83-1), 4-[(4E or 4Z) -1, 5-dimethyl-4- heptenylidene] -1-methyl- (4Z or 4E) -cyclohexene (CAS Reg. No. 160359-81-9), 3, 7, 11-trimethyl-l, 3, 6, 10-docosatetraene (CAS Reg. No. 159085-88-8), 3, 1 , 11, 15-tetramethyl-l, 3, 6, 10- hexadecatetraene (CAS Reg. No. 158729-00-1), 9-ethyl-2, 6- dimethyl- (E or Z, E or Z) -2, 6, 9-dodecatriene (CAS Reg. No. 157337-30-9), 2-methyl-5-propyl- (E or Z) -2, 5-nonadiene (CAS Reg. No. 157337-25-2), 3, 7, 11-trimethyl- (Z or E, E or Z, E or Z ) -1 , 3 , 6 , 10-dodecatetraene (CAS Reg . Nos . 154579-52-9 ,
154579-50-7, 154579-49-4, 154579-40-5), 4 , 8 , 12-trimethyl- (Z or E, E or Z, E) -2, 4 , 7 , 11-tridecatetraene (CAS Reg. Nos. 154579-51-8, 154579-47-2), l-methyl-4- (2-methyl-6- heptenylidene) - (E or Z) -cyclohexene (CAS Reg. No. 152252-96- 5), 3-ethyl-7, 11-dimethyl- (E or Z, E or Z)-l,3, 6, 10- dodecatetraene (CAS Reg. No. 152195-83-0), 2,6,6,9- tetramethyl-7- (2-methyl-l-propenyl) -2,4, 8-decatriene (CAS Reg. No. 150280-97-0), 2, 7-dimethyl-4, 5-bis (2-methyl-l- propenyl) -2, 6-octadiene (CAS Reg. No. 150280-96-9), 3,7- dimethyl-1,3, 6-octatriene (CAS Reg. No. 147727-60-4), 2- methyl-5- (1-methylethylidene) -cyclohexene (CAS Reg. No. 147727-51-3) , 2, 6-dimethyl-5- (1-methylethylidene) -1,3- cyclohexadiene (CAS Reg. No. 138434-36-3), 2, 6-dimethyl-2, 5- decadiene or octadiene (CAS Reg. Nos. 134956-14-2, 128144- 73-0), 7-ethyl-3,ll-dimethyl-l, 3, 6,10-dodecatetraene (CAS
Reg. No. 134779-29-6), 2-methyl- (E or Z) -2, 5-octadiene (CAS Reg. No. 133797-14-5), 7-ethyl-3, 11-dimethyl- (E or Z, E or Z) -1,3, 6,10-dodecatetraene (CAS Reg. No. 127941-96-2), 2, 7, 11-trimethyl- (E or Z) -2, 5, 10-dodecatriene (CAS Reg. No. 124745-43-3), 6, 10-dimethyl- (Z or E, Z or E) -2,6,9- undecatrien-4-yne (CAS Reg. No. 122305-03-7), 2, 6-dimethyl- (Z or E)-2,5-dodecadiene (CAS Reg. No. 121403-30-3), 2,7- dimethyl-4, 5-bis (2-methyl-l-propenyl) -2, 4, 6-octatriene (CAS Reg. No. 117712-68-2), 2, 3, 6, 7-tetramethyl-l, 3, 6-octatriene (CAS Reg. No. 117527-68-1), 2-methyl-5-propyl- (Z or E)-2,5- dodecadiene (CAS Reg. No. 116893-95-9), 2-methyl-5- (1- methylethyl) - (E or Z) -2, 5-dodecadiene (CAS Reg. No. 116893- 93-7), 2-methyl-(Z or E) -2, 5-dodecadiene (CAS Reg. No. 116893-92-6), 2, 4, 4-trimethyl- (E or Z) -2, 5-heptadiene (CAS Reg. No. 116786-15-3), 2, 6-dimethyl-2, 5-octadiene (CAS Reg. No. 116668-48-5), 3, 4, 7, 11-tetramethyl- (E or Z, Z or E)-
1,3,6,10-dodecatraene (CAS Reg. Nos. 114091-33-7, 114091-32- 6), 3, 7, 11-trimethyl- (E or Z, E or Z)-l, 3, 6,10- dodecatetraene (CAS Reg. No. 113244-64-7), 4, 8-dimethyl- 1,4,7-nonatriene (CAS Reg. No. 110559-67-6), 3,7,11,15- tetramethyl-1, 3, 6, 10, 14-hexadecapentaene (CAS Reg. No.
110249-03-1), 2-methyl- (Z or E) -2, 5-pentadecadiene (CAS Reg. Nos. 108181-16-4, 108181-15-3), 2-methyl-5- (1- methylethylidene)-2-decene (CAS Reg. No. 107909-37-5), 2,6- dimethyl-2,5,7-decatriene (CAS Reg. No. 105694-90-4), 4,8- dimethyl-2, 4, 7-nonatriene (CAS Reg. No. 105694-88-0),
15, 19, 23-trimethyl-15, 18, 22-heptatriacontatriene (CAS Reg. No. 104519-12-2), 8- (2-methyl-l-propenyl) -6-tetradecene (CAS Reg. No. 10229-83-2), 3, 7 , 11-trimethyl- (E or Z)-l, 3, 6,10- dodecatetraene (CAS Reg. No. 97885-54-6), 3, 4-didehydro-2- (3-methyl-2-butenyl) -carotene (CAS Reg. No. 97231-43-1), 7- ethyl-3, 11-dimethyl-l, 3, 6, 10-dodecatetraene (CAS Reg. No. 96890-21-0), 1, 3-dimethyl-4-propylidene-cyclopentene (CAS Reg. No. 96095-54-4), 2, 7, 11-trimethyl- (E or Z, E or Z)- 1,3, 6,10-dodecatetraene (CAS Reg. No. 93517-88-5), 6,10- dimethyl-1, 4, 6, 9-undecatetraene (CAS Reg. No. 93308-70-4), 2- (1-methylethyl) -5- (1-methylethylidene) -1, 3-cyclohexadiene (CAS Reg. No. 92545-19-2), 2-ethyl-5-ethylidene- cyclohexadiene (CAS Reg. No. 92545-18-1), 2-methyl-5- (1- methylethylidene) -1, 3-cyclohexadiene (CAS Reg. No. 92545-16- 9), 3, 7, 10-trimethyl- (Z or E, E or Z) -1, 3, 6-undecatriene
(CAS Reg. No. 91203-72-4), 4- (1, 5-dimethyl-4-hexenylidene) - 1-methyl-cyclohexene (CAS Reg. No. 90458-95-0), l-methyl-4- ( 1-methylethylidene) -cyclohexene (CAS Reg. No. 83259-95-4), 2,5-dimethyl- (Z or E) -2, 5-heptadiene (CAS Reg. Nos. 83180- 40-9, 83180-39-6), 2-methyl-5- (1-methylethylidene) -1, 3- cyclohexadiene (CAS Reg. No. 81719-66-6), 2, 6, 10-trimethyl- (E or Z, Z or E) -2, 6, 9-tetradecatriene (CAS Reg. No. 80873- 82-1), 6-methyl-(Z or E, E or Z) -2, 5-dodecadiene (CAS Reg. Nos. 80873-79-6, 80873-78-5), 2, 3, 6-trimethyl- (E or Z, E or Z) -1,3, 6-octatriene (CAS Reg. No. 80651-22-5), tetrahydro- 3, 7, 11-trimethyl-l, 3, 6, 10-dodecatetraene (CAS Reg. No.
80338-47-2) , 3, 4 , 7, 11-tetramethyl-l, 3, 6, 10-dodecatetraene (CAS Reg. No. 7983-34-9), 3, 4 , 7 , 11-tetramethyl- (Z or E, Z or E) -1,3, 6, 10-dodecatetraene (CAS Reg. No. 79383-33-8), 2,6- dimethyl-4-methylene-2, 5-heptadiene (CAS Reg. No. 77832-43- 6), 5-ethyl-2-methyl-2, 5-heptadiene (CAS Reg. No. 78811-91- 3), 2, 5-dimethyl-2, 5-heptadiene or octadiene (CAS Reg. Nos. 78811-90-2, 78811-89-9), 3, 7, 11-trimethyl-dodecatriene (CAS Reg. No. 78339-48-7), 2, 4 , 6, 6, 8-pentamethyl- (E or Z)-2,4,7- nonatriene (CAS Reg. No. 78310-14-2), 3, 7-diethyl-ll-methyl- 1,3, 6,10-tridecatetraene (CAS Reg. No. 78216-57-6), 7-ethyl- 3,ll-dimethyl-l,3, 6, 10-tridecatetraene (CAS Reg. No. 78183- 46-7), 2, 6-dimethyl- (E or Z) -2, 5-dodecadiene (CAS Reg. No. 77958-38-4), 2, 6, 10-trimethyl- (E or Z, E or Z)-2,6,9- tetradecatriene (CAS Reg. No. 77958-36-2), 3,7,11,15- tetramethyl- (Z or E, E or Z, E or Z) -1, 3, 6, 10, 14- hexadecapentaene (CAS Reg. No. 77898-98-7), 3,7,11,15- tetramethyl-(3E or 3Z, 6E or 6Z, 10E or 10Z) -1, 3, 6, 10, 14- hexadecapentaene (CAS Reg. No. 77898-97-6), l-ethenyl-4- (1- methylethylidene) -cyclohexene (CAS Reg. No. 77142-28-0), 1- methyl-6-methylene-4- (1- methylethylidene) -cyclohexene (CAS Reg. No. 77142-23-5), 3, 7, 11-trimethyl-l, 3, 6-dodecatriene (CAS Reg. No. 74253-06-8), 4- (1, 5-dimethylhexylidene) -1- methyl-cyclohexene (CAS Reg. No. 74253-05-7), 7-ethyl-3, 11- dimethyl- (3Z or 3E, 6E or 6Z) -1, 3, 6, 10-dodecatetraene (CAS Reg. No. 73690-00-3), 1, 3, 3 ' , 4, 4 ' , 16-hexadehydro-l, 2- dihydro-2,2'-bis (3-carotene (CAS Reg. No. 77365-74-9), 7- methyl- (Z or E, Z or E) -3, 6-dodecadiene (CAS Reg. Nos. 72858-64-1, 72858-63-0), 6-ethylidene-2, 3, 10-trimethyl- (E or Z, E or Z)-l,3,9-undecatriene (CAS Reg. No. 72564-39-7), 2,3, 6,7,10,ll-hexamethyl-(E or Z, E or Z)-l,3,6,10- dodecatetraene (CAS Reg. No. 72564-36-4), 2,3,6,7- tetramethyl- (E or Z) -1, 3, 6-octatriene (CAS Reg. No. 72564- 35-3), 2, 7, 11-trimethyl-l, 3, 6, 11-dodecatetraene (CAS Reg. No. 71803-35-5), 3, 7 , 11, 15, 19, 23, 27, 31, 35-nonamethyl- 1,3, 6, 10, 14, 18,22,26,30,34-hexatriacontadecaene (CAS Reg. No. 71278-21-2), 2, 6-dimethyl-9-propyl-2, 6, 9-tridecatriene (CAS Reg. No. 70602-78-7), 3, 6-dimethyl- (E or Z, E or Z)- 1,3, 6-octatriene (CAS Reg. No. 70569-76-5), 3, 7-diethyl-ll- methyl-(3Z or 3E, 6E or 6Z) 1, 3, 6, 10-tridecatetraene (CAS Reg. No. 70239-70-2), 7-ethyl-3, 11-dimethyl- (3Z or 3E, 6E or 6Z) -1,3, 6, 10-tridecatetraene (CAS Reg. No. 70234-77-4), 1- methyl-4- (5-methyl-4-hexenylidene) - (4E or 4Z) -cyclohexene (CAS Reg. No. 66916-06-9), 2, 6, 10-trimethyl- (Z or E)-2,5,9- undecatriene (CAS Reg. Nos. 68974-97-0, 68974-96-9), 2, 6, 7, 7-tetramethyl- (Z or E) -2, 5-octadiene (CAS Reg. Nos. 68974-95-8, 68974-94-7), 2, 6, 10, 11, ll-pentamethyl-2, 6, 9- dodecatriene (CAS Reg. No. 68965-68-4), 2, 6, 10-trimethyl- 2,6,9-tetradecatriene (CAS Reg. No .68965-67-3) , 2,6- dimethyl- (Z or E) -2, 5-decadiene (CAS Reg. Nos. 68965-66-2, 68965-65-1), 6, 10-dimethyl-l, 6, 9-undecatrien-4-yne (CAS Reg. No. 68483-39-6), 2, 3, 6-trimethyl-2, 5-heptadiene (CAS Reg. No. 67796-57-0), 2, 4-dimethyl- (E or Z) -2, 5-heptadiene (CAS Reg. No. 67796-55-8), 2, 7, 11-trimethyl- (E or Z, E or Z)- 1,3, 6, 11-dodecatetraene (CAS Reg. No. 67023-83-0), 6-ethyl- 3-methyl-2, 5-decadiene (CAS Reg. No. 65668-94-2), 2,6,10- trimethyl-(Z or E) -2, 5-undecadiene (CAS Reg. Nos. 64583-07- 9, 64583-04-6), 3, 7-dimethyl-3, 6-octadien-l-yne (CAS Reg. No. 64547-65-5), 2, 7, 10-trimethyl-l, 6, 9-undecatriene (CAS Reg. No. 61058-91-1), 4 , 5-dimethyl- (E or Z, E or Z, E or Z)- 3,5,8-undecatriene (CAS Reg. No. 59681-86-6), 4, 5-dimethyl- 2,5,8-undecatriene (CAS Reg. No. 59681-84-4), 1 ' - [4-methyl- 2- (2-methyl-l-propenyl) -1, 3-pentadienylidene] bis-benzene, 1 (CAS Reg. No. 55861-06-8), 4- (1, 5-dimethyl-4-hexenylidene) - 1-methyl- (4E or 4Z) -cyclohexene (CAS Reg. No. 53585-13-0), 2, 6, 11, 15-tetramethyl- (Z or E) -2, 6, 9, 14-hexadecatetraene (CAS Reg. Nos. 53254-62-9, 53254-61-8), [3-methyl-l- (2- methyl-1-propenyl) -2-butenyl] -benzene (CAS Reg. No. 53210- 24-5), 2, 6, 11-trimethyl- (E or Z, E or Z) -2, 6, 9-dodecatriene (CAS Reg. No. 51795-79-0), 2, 6-dimethyl- (E or Z, E or Z)- 2, 6, 9-dodecatriene (CAS Reg. No. 51795-74-5), 2,3,6,7,10,11- hexamethyl-1, 3, 6, 11-dodecatetraene (CAS Reg. No. 45214-38- 8), 19-methyl-l-(2-methyl-l-2,4,6,8,10,12,14,16,18- eicosanonaenylium (CAS Reg. No. 40544-26-1), 17-methyl-l- (2- methyl-1-propenyl) -2,4,6,8, 10, 12, 14, 16-octadecaoctaenylium (CAS Reg. No. 40544-25-0), 15-methyl-l- (2-methyl-l- propenyl) -2, 4, 6, 8, 10, 12, 14-hexadecaheptaenylium (CAS Reg. No. 40544-24-9), 13-methyl-l- (2- methyl-1-propenyl) -
2, 4, 6, 8, 10, 12-tetradecahexaenylium (CAS Reg. No. 40544-23- 8) , 11-methyl-l- (2-methyl-l-propenyl) -2,4, 6,8,10- dodecapentaenylium (CAS Reg. No. 40544-22-7), 9-methyl-l- (2- methyl-1-propenyl) -2, 4, 6, 8-decatetraenylium (CAS Reg. No. 40544-21-6), 7-methyl-l- (2-methyl-l-propenyl) -2, 4, 6- octatrienylium (CAS Reg. No. 40544-20-5), 4 , ethylidene-2, 6- dimethyl-2, 5-heptadiene (CAS Reg. No. 39117-23-2), 3, 7, 11- trimethyl- (E or Z) -3, 6, 11-dodecatrien-l-yne (CAS Reg. No. 36629-58-0), 3, 7-dimethyl- (3E or 3Z) -3, 6-octadien-l-yne (CAS Reg. Nos. 36602-32-1, 36602-31-0), 3, 7-dimethyl- (E or Z)- 3, 6-nonadien-l-yne (CAS Reg. Nos. 36597-67-8, 36597-66-7), 3, 6, 7-trimethyl- (E or Z) -3, 6-octadien-l-yne (CAS Reg. Nos. 36597-64-5, 36957-63-4), 7-ethyl-3-methyl- (E or Z)-3,6- nonadien-1-yne (CAS Reg. Nos. 36597-61-2, 36597-60-1), 3, 7, 11-trimethyl- (Z or E) -3, 6, 11-dodecatrien-l-yne (CAS Reg. Nos. 36597-58-7, 36597-56-5, 36597-56-4), 2,3,6,7,10,11- hexamethyl-1, 3, 6, 11-dodecatetraene (CAS Reg. No. 34888-55- 6), 2, 6-dimethyl-2, 5-heptadiene (CAS Reg. No. 34484-31-6), 2-methyl-2, 5-heptadiene (CAS Reg. No. 34484-29-2), 3,6,10- trimethyl-2, 5, 7, 10-dodecatetraene (CAS Reg. No. 32945-35-0), 2, 7, 10-trimethyl-l, 3, 7, 10-dodecatetraene (CAS Reg. No. 32925-31-8), 3, 6-dimethyl-l, 3, 6-octatriene (CAS Reg. No. 32778-25-9) , 12- (2, 2-dimethyl-6-methylenecyclohexyl) -3, 8 , 8- trimethyl-11-methylene- (E or Z) - (S) -1, 3, 6-dodecatriene (CAS Reg. No. 29738-44-1), ocimene (CAS Reg. No. 29223-32-3), 3, 7, 11-trimethyl-, (3Z or 3E, 6Z or 6E) -1, 3, 6, 10- dodecatetraene (CAS Reg. Nos. 28973-99-1, 28973-98-0, 26560- 14-5), 2-methyl-4-methylene-2, 5-heptadiene (CAS Reg. No. 24498-9-5), 3, 8, 8, 14, 18-pentamethyl-ll-methylene- (E or Z)- 1,3, 6, 13,17-nonadecapentaene (CAS Reg. No. 23192-59-8), 2,7- dimethyl-2,5-octadiene (CAS Reg. No. 20733-73-7),
3, 8, 8, 14, 18-pentamethyl-ll-methylene- (E or Z, E or Z, E or Z) -1,3, 6, 13,17-nonadecapentaene (CAS Reg. No. 19953-95-8), 6, 10-dimethyl-2,4, 6, 9-undecatetraene (CAS Reg. No. 19048-50- 1), 2-methyl-(Z or E) -2, 5-heptadiene (CAS Reg. No. 18316-09- 1), 2-methyl-(E or Z) -2, 5-heptadiene (CAS Reg. No.18316-08- 0), 3, 7-dimethyl-l, 3, 6-octatriene (CAS Reg. No. 13877-91-3), 4- (1, 5-dimethyl-4-hexenylidene) -1-methyl- (4Z or 4E)- cyclohexene (CAS Reg. No. 13062-00-5), 2, 6,10,14,19,22,27,31-octamethyl-2,6,10,14,16,18,22,26,30- dotriacontanonaene (CAS Reg. No. 13050-81-2), 2, 6-dimethyl- 2, 5-heptadiene (CAS Reg. No. 6090-16-0), 4- (1, 5-dimethyl-4- hexenylidene) -1-methyl-cyclohexene (CAS Reg. No .5957-36-8 ) , 3, 7-dimethyl- (3E or 3Z) -1, 3, 6-octatriene (CAS Reg. No. 3779- 61-1) , 2,6, 10, 14, 19,23, 31-heptamethyl- 2,5,10,14, 16, 18, 22,26, 29-dotriacontanonaene (CAS Reg. No. 3625-51-2), 3, 7, dimethyl- (3Z or 3E) -1, 3, 6-octatriene (CAS Reg. No. 3338-55-4), 3-methyl-l- (2-methyl-l-propenyl- (E or Z) -2-pentenyl (CAS Reg. No. 3229-66-1), 2, 6-dimethyl-4- (2- methylpropenyl) -1, 3, 5-heptatriene (CAS Reg. No. 1606-44-6), 2, 6-dimethyl-4-methylene-2, 5-heptadiene (CAS Reg. No. 927-
02-6), l-methyl-4- (1-methylethylidene) -cyclohexene (CAS Reg. No. 586-62-9), 3, 7 , 11-trimethyl- (3E or 3Z, 6E or 6Z)- 1,3, 6, 10-dodecatetraene (CAS Reg. No. 502-61-4), 4-(l,5- dimethyl-4-hexenylidene) -1-methyl-cyclohexene (CAS Reg. No. 495-62-5) , isoprene, yrcene, dihydromyrene, linalool, terpinenes (α, β, and γ) , limonene, terpinolene, menthadiene (p-3,8 or p-2,4), geraniol, nerol, geranylacetate, neryl acetate, nerolidol (CAS Reg. No. 7212-44-4), farnesol (CAS Reg. No. 4602-14-0), dehydronerolidol (CAS Reg. No. 2387-68- 0) , α-bisabolol, valancene, nookatene, nootkatone, dimethyl- 2, 4, 6-octratriene, ?-phellandrences (CAS Reg. No. 6153-17- 9), piperitols (-, cis and +, trans) (CAS Reg. Nos. 65733- 28-0, 65733-2-9), 1-methyl-l, 4-cyclohexadiene, methyl cyclopentadiene dimer, ethylidene norbornene, dipentene, carvestrene, carvone (- or +) , alloocimenes [4-trans-6-cis (CAS Reg. No. 7216-56-0) and 4-trans-6-trans (CAS Reg. No. 3016-19-1)], alloocimenols (CAS Reg. No. 18479-54-4), iono ers (CAS Reg. Nos. 127-41-3, 14901-07-6), guaiazulene, lanosterol (CAS Reg. No. 76-63-0), squalene (CAS Reg. No. 111-02-4), lycopene (CAS Reg. No. 502-65-8), and carotenes [β and γ (CAS Reg. Nos. 7235-40-7, 472-94-5)].
Of course, combinations of these compounds, with or without conventional epoxy compounds, may be used, provided that excluded as the sole component from these compounds are those within the teachings of U.S. Patent Nos. 5,948,922 (Ober) and 5,973,033 (Ober). That is, excluded as the sole component from these compounds are epoxy compounds within the following formula:
Figure imgf000022_0001
where each R is independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert- butyl, C1-4 alkoxy, halogen, cyano and nitro, Rx and R2 are each independently selected from hydrogen, methyl, ethyl and propyl, provided that both Ri and R2 cannot be hydrogen, R3 is independently selected from hydrogen, methyl, ethyl, propyl, and isopropyl, provided at least one of R3a and R3b, and at least one of R3c and R3cj is independently selected from methyl, ethyl, propyl, and isopropyl, and m is 0 or 1. Particularly desirable epoxy or oxirane compounds within formula I_ include limonene diepoxide and gamma- terpinene diepoxide. Limonene diepoxide may be obtained commercially from Daicel Chem. Co., Ltd., Japan under the tradename "CELLOXIDE" 3000.
Other particularly desirable epoxy or oxirane compounds include methyl cyclopentadiene diepoxide dimer ("MCPD dimer"), ethylidene norbornene diepoxide ("ENB diepoxide"), and nopol epoxide glycidyl ether ("NEGE").
The presence in the curable resin component of one or more epoxy compounds having at least one oxirane or thiirane linkage substituted on at least three of the substitutable positions on the oxirane or thiirane carbons, respectfully, with an alkyl, alkenyl or aryl substituent having a carbon content of one to about twelve carbon atoms, with or without substitution or interuption by one or more heteroatoms or halogens allows for repair, replacement, recovery and/or recycling of operative electronic components from assemblies that have become at least in part inoperative .
The compounds with the oxirane linkage (s) can be prepared from olefinically unsaturated compounds, many of which havine at least two olefinic linkages, with at least one of the olefinic linkages being substituted on at least three of the substitutable positions on the epoxy carbons with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interuption by one or more heteroatoms or halogens. This olefinically unsaturated compound may 'then be contacted with an epoxidation agent in an amount and under conditions appropriate to react with the olefinic linkages to form an inventive compound having an oxirane linkage.
Appropriate epoxidation agents useful in forming oxirane rings include peracids (such as peracetic acid, . t
KΛ o o
3 Ti Ti rt rt Ω SU Hi 03 su 0 ^—^ Ω •i SU HI Ω su Q Ω o rt Φ tϋ 3 tr S rt ^-^ su TJ
0 Φ Φ tr tr o H μ- O < •i CD 0 Φ I-* d 0 ii H li tr 0 φ su μ- μ- tr < Ω Φ ri ■i ■i Φ Φ su d H l SU ft • ø μ- rt CQ 3 φ ■- Ω μ- £ Ti . rt < rt 0 Φ φ μ- ii
CD Ω Ω ii rt 3 m μ- Φ P Ω ø φ Φ TJ Ω -- rt μ- ii tr μ- tr ?* 0 ft tr
Φ φ μ- Φ Φ μ- Φ LΠ h-1 ii Φ Hi ii ft 0 TJ μ- O tr H φ ω 0 ø μ- SU ii rt ^\ Φ
Ti ø ø ø 0 ft ø ii SU 0 0 0 0 ft Ti μ- su 03 •> ft ιp ø cp Φ d ø- ø
SU rt rt <! Hi d tr 0 rt ii rt 03 Φ rt • Φ μ- ø 03 ω 03 φ SU ii ^ N ii φ SU 3 Ω Hi μ- ii Ω tr μ- 0 Φ 0 li Φ I-* $u su CQ Ω φ ft 0 rt ø μ** 0 Φ ø SU μ- Φ l-J rt ø rr SU ■^ oo 3 rt rt ii μ- μ- TJ CQ rt d 0 3 SU rt ø μ- rt Φ SU 0 Ω - SU Ti μ- μ- H 0 Ω
Ω SU d μ- H-3 3 X TS O Hi tr rr μ- TJ IP Ω Ω 3 μ- > rt ft φ o i-E μ- LΠ ■<: l-1 > Φ 03 0 0 •P d i Ω <! tr μ- μ- 0 rt ii 0 tr 0 SU tr su SU SU 03 tr μ- co 3 0 ø t φ CQ ii 0 — Φ su
H r tr φ Φ ø ft 0 tr o d φ 0 ii Hi Φ 03 ■<! φ φ Ti Ω to tr Su μ- su ø Ω
SU μ- d φ φ Φ 3 rt rt d 3 - h-1 SU n ø 0 o rt 0 Φ Q ii 0 rt Ω SU μ- ri Ω u Ω μ- 3 - 0 ■i ii SU μ- 03 μ- 0 *< 0 • φ Hi d tr ii ,-, rt Φ ft SU 0 Ti ft r-> d CQ 0 ø rt > to su 0 Ω Φ Ω SU Hi ø su TJ S d ιp H ii ft Φ -
> H- 3 o ø 03 ft ft ø ft d ft su ø rt d μ- ft I-* ft rt O SU 03 O su O φ ii ii
SU μ- TJ ii μ- μ- μ- Φ 3 3 ■P ft Φ 03 ø μ- μ- ω H ii Φ ø ii Hi SU μ- LΠ 0 3
SU ii ø 0 IP rt H ø 03 SU μ- φ Su SU 03 ø φ 0 3 3 Φ SU rt ft Φ ft 03 Φ - X Φ tr (-■ CQ SU ii μ- Ω μ- rt Ω ii ii μ- 0 3 Hi ii Φ o s: 0 rt μ- 03 rt rt ft to μ- rt
0 ^ r μ- 0 μ- Ω H ■i Φ ii 0 Φ H H SU Su μ- d ιp li ø μ- ft Φ ø_ rt μ- 1 ft SU d tr rt μ- ft 0 d SU Ω O Hi * μ- rt ø SU * Φ rt ft CQ tr Ti 3 03 O ►P-. Φ 1 rt SU φ μ- Ω φ ø ft tr tr ø •i Ω d Ω • ø ø 0" •*> d μ- ii φ d d •• Ω tr 0 - Φ H 03 03 SU Φ ft U i tr μ- Φ Φ μ- TJ tr Ω μ- Φ tr rr H tr
H 0 ii ø Hi ø Φ - tr H Φ Φ Φ Ω rt ø SU φ rt tr ii TS 0 03 lP» 03
171 d u μ- tr μ- rt «. 0 SU 03 3 ft •T] tr li ii tr SU SU Hi rt d o Φ 0 r ø μ- 0 rt tr 3 -l d rr μ- su 0 d φ 0 Hi •- id Hi rt Φ Φ su ø ii Su ø Φ ii rt ιp ø ii ii 0 Su SU 03 rt μ- •i > Hi ø ii μ- H su o μ- μ- Q φ SU Hi ø rt . — ^ 0
0 H φ φ 0 μ- CQ rt TJ d <! SU rt ϋ μ- g H Ω ø ft rt ii rt μ- < su α TJ o ii 0 ft Φ Φ SU Ω CO φ tr tr rt •i φ μ- ft § 3 d μ- rt I-1 μ- O μ- φ φ
SU 0 ø φ ii ø tr H -> Φ tr Φ μ- ø φ Φ SU d tr CQ tr μ- 0 3 SU 0 ω ii tr rt Hi Ω 0 - Ω μ- I-1 *< φ φ SU ø CQ ii ø 1 -1 SU *<. Ω 0 ø 0 H φ rt • tr
0 0 su 0 μ- 0 SU d su o
SU c μ- rt Hi rt Φ rt PJ li H CQ ? t h-1 TJ d Φ d su 3 3 rt ø H ø 03 03 0 03 ii Φ 0 SU Ω Φ H" ii 0 Φ SU 0 *< O ii TJ ø rt SU tr 0 TJ ii I-1 03 ω ft 3 3 0 φ ft ϋ ø 0 ø li I H φ 03 IP Hi rt X Φ SU N tr 0 d 0 μ- d rt Φ rt μ- Su φ ft ω Ω Ω 3 o Ti Hi d ft Φ O Ω μ- H rt 0 φ> 0 d ø ø ft 3 ii Hi ii tr Ω CQ d 0 μ- φ TJ li μ- μ- ft φ ii Φ •> μ- O ft H Φ μ- o d rt rr Φ φ μ- d 0 φ ii H ii •i ø - 0 tr ø ø Φ ii φ 03 ø H 3 μ- 0 ø Ω rt ø ø Ω ii r 0 tr Hi ιp 0 o Φ Ω O Φ Ω Ω < 00 TJ N — rt
2 ui d rt SD d rr tr 03 ø μ- u Su r rt (D H 0 I-* μ- ø 0 i 0 φ su SU
Φ σi TJ ø 3 Φ d Φ μ- 03 ø < Ω ii CQ t 0 0 Φ d ϋ Ω Hi μ- 0 ø tr Φ rt SU ≥! Ω μ- o rt 3 ft ft 03 h-1 Φ φ Φ μ- Φ rt φ *«!« ft su φ tr <J rr 0 rr μ- 0 0 μ- ιp 0 r SU ø Φ rt μ- TJ • SU H •» 0 Φ tr . 3 Φ Φ μ- d Φ 0 ft 03 ft tr S 0 ^ Ω μ- 0 ii Ω 03 SU SU r μ- μ- φ 3 H tr ft 0 ! ri - ø • rt Φ Su 0 rt Hi SU SU SU d ii Φ Ω ø 3 "^ φ rt Φ μ- rt Φ 03 rt μ- tr -J tr 3 ii CQ ft Ω rt < ft SU 0 SU rt tr Ω μ- μ- • rt 0 tr tf-» rt
Ti (P 0 o Φ tr μ- 0 Φ Ω tr μ- 0 μ- 03 ii ø SU tr Φ Φ tr ø O Ω a Hi Φ d
Φ tr d μ- ft i rt 0 Ω s >i 03 - ιp *< 0 "< Ti ø O σi ø
•i r rr 3 Ti ø φ tr ft 3 su rt 0 SU ft Φ μ- μ- α SU 3 μ- ft μ-1 en ιp
Ω Φ ii su •*- Ω Φ Φ 3 03 φ μ- d CQ ø 3 Ti ω 03 l-* Ti Ω 0* μ- t 03
Φ Ti en μ- Φ r O CQ φ o su Su d μ- SU 0 μ- d to O SU Φ rt ø Φ o ιp 03 μ- 03 0 μ- μ- ii 0 ω ø I-1 03 Ω Ω rt 0 Cfl tr . CQ d φ to μ- rt ii tr Φ 0 μ- rt ø •X! Ω ø μ- tr Φ T5 d Hi Φ >< ø h-1 O 1 Ω
- Ω rr ø 0 H" SU 0 ø μ- N *< rt Hi ii o H μ- ii TJ 0 ft *< H *• en
Φ Φ rt CQ μ- μ- ii $u su rt φ 0 su μ- μ- (-• Hi ft φ SU rt 03 Φ
SU ø μ- Ω ø ιp rt μ-* tr SU 03 Su μ- φ tr rt tr Hi ■S
0 r ιp μ- su μ- su μ- Φ 0 H ft * Φ Φ μ- μ- ft tr ø 1 ø ø 0 ^ . φ CQ φ o 0 rt 0 rt rt ιp μ- ø ii O Hi rt μ- tr
Ω Ω
even more particularly about 20 to about 35 weight percent, such as about 30 weight percent.
The curing agent component should include materials capable of catalyzing the polymerization of the epoxy resin component of the inventive compositions.
Desirable curing agents for use with the present invention include an anhydride component, a nitrogen-containing component, such as an amine compound, an amide compound, and an imidazole compound, or combinations thereof. Appropriate anhydride compounds for use herein include mono- and poly-anhydrides, such as hexahydrophthalic anhydride ("HHPA") and methyl hexahydrophthalic anhydride ("MHHPA") (commercially available from Lindau Chemicals, Inc., Columbia, South Carolina, used individually or as a combination, which combination is available under the trade designation "LINDRIDE" 62C) and 5- (2 , 5-dioxotetrahydrol) -3- methyl-3-cyclohexene-l, 2-dicarboxylic anhydride (commercially available from ChrisKev Co., Leewood, Kansas under the trade designation B-4400) . Of course, combinations of these anhydride compounds are also desirable for use in the compositions of the present invention.
The nitrogen-containing compound includes amine compounds such as polyamines and di-and tri-aza compounds, modified amine compounds, amide compounds, imidazole compounds, and combinations thereof.
Examples of the amine compounds include the following alkyl poly amines: diethylenetriamine, triethylenetetraamine, diethylaminopropylamine, and quinoxaline.
Examples of the di-or tri-aza compounds include:
Figure imgf000025_0001
1, 5-diazabicyclo [4.3.0] non-5-ene
Figure imgf000026_0001
1, 8-diazabicyclo [5.4.0] undec-7-ene ("DBU") ;
Figure imgf000026_0002
1,5, 7-triazabicyclo [4.4.0] dec-5-ene; and
the bicyclo mono- and di-aza compounds
Figure imgf000026_0003
quinuclidine; and
Figure imgf000026_0004
1 , 4 -diazabicyclo [2.2.2.] octane ,
Examples of modified amine compounds include epoxy amine additives formed by the addition of an amine compound to an epoxy compound. Of course, combinations of these amine compounds are also desirable for use in the compositions of the present invention.
Examples of amide compounds include cyano- functionalized amides, such as dicyandiamide . The imidazole compounds may be chosen from imidazole, isoimidazole, and substituted imidazoles -- such as alkyl-substituted imidazoles (e.g. , 2 -methyl imidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, butylimidazole, 2-heptadecenyl-4-methylimidazole, 2- undecenylimidazole, 1-vinyl-2 -methylimidazole, 2-n- heptadecylimidazole, 2-undecylimidazole, 2- heptadecylimidazole, l-benzyl-2-methylimidazole, l-propyl-^2- methylimidazole, l-cyanoethyl-2-methylimidazole, 1- cyanoethyl-2-ethyl-4-methylimidazole , 1-cyanoethyl-2- undecylimidazole, l-cyanoethyl-2-phenylimidazole, 1- guanaminoethyl-2-methylimidazole and addition products of an imidazole and trimellitic acid, 2-n-heptadecyl-4~ methylimidazole and the like, generally where each alkyl substituent contains up to about 17 carbon atoms and desirably up to about 6 carbon atoms) , and aryl-substituted imidazoles [e.g. , phenylimidazole, benzylimidazole, 2- methyl-4, 5-diphenylimidazole, 2 , 3 , 5-triphenylimidazole, 2- styrylimidazole, 1- (dodecyl benzyl) -2-methylimidazole, 2- (2- hydroxyl-4-t-butylphenyl) -4, 5-diphenylimidazole, 2- (2- methoxyphenyl) -4, 5-diphenylimidazole, 2- (3-hydroxyphenyl) - 4 , 5-diphenylimidazole, 2- (p-dimethylaminophenyl) -4,5- diphenylimidazole, 2- (2-hydroxyphenyl) -4, 5- diphenylimidazole, di (4 , 5-diphenyl-2 -imidazole) -benzene-1, 4 , 2-naphthyl-4 , 5-diphenylimidazole, l-benzyl-2- methylimidazole, 2-p-methoxystyrylimidazole, and the like, generally where each aryl substituent contains up to about 10 carbon atoms and desirably up to about 8 carbon atoms] .
Examples of commercial imidazole compounds are available from Air Products, Allentown, Pennsylvania under the trade designation "CUREZOL" 1B2MZ and from Synthron, Inc., Morganton, North Carolina under the trade designation "ACTIRON" NXJ-60.
Examples of the modified imidazole compounds include imidazole adducts formed by the addition of an imidazole compound to an epoxy compound. For instance, "AJICURE" PN-23, commercially available from Ajinomoto Co., Inc., Tokyo, Japan, is believed to be an adduct of EPON 828 (bisphenol-A-type epoxy resin, epoxy equivalent 184-194, commercially available from Shell Chemical Co.), 2-ethyl-4-methylimidazole and phthalic anhydride. Others
Figure imgf000028_0001
d T! Hi CQ rt o 3 SU Cd ^__. tr r ft 03 ft m r Hi SU rt SU su rt Ω SU ω SU SU S Ω ø ii ii μ- tr • φ 3 v Ω d μ- Φ μ- Φ Ti ii ø tr tr 3 tr 0 I-1 • i ft ft o ft 0 o Φ μ> μ- 0 ■<: 0 rt rt 03 CQ φ μ- O ft Φ 0 0 Φ 3 W t ft ft 1 3
Φ Ti 3 su ιp d 0 3 Su Su μ- Su μ- Ω 3 ■t d d T5 o d μ- IV) § ii *< ø Ω rt tr ø ø 3 ø 0 ιp 0 ιp μ- Φ SU μ- Ω rt ø TJ 0 Ω rt JS.
O φ 0 O rt r ø φ 0 μ- ø φ ø u rt tr ft d rt ii d tr tn rt μ- "^ Φ s li rt to 03 3 Φ ii (-■ d $u SU tr μ- Φ ii ω Φ ø Φ a o Ω tr rt H - Ti SU Ti d - Ω SU 3 rt -— , rt rt 0 ø su 0 03 ft - ft ø 3 μ- φ •i 0 tr Φ TJ μ- rt μ- Ω μ- μ- X μ- rt tr rt l-h Φ CQ d μ- > > su μ- d IP 03 0 li a su 0 H 0 0 0 Φ ^ rr μ- H 0 ø ω Ω CQ S H rt Φ ø (-■ H μ- d Ω rt ■S Φ μ-* 1 < ø 3 ø 03 • ! H rt Φ Hi 1-3 rt su o . Φ 0 Ti s H H ii rt ft • ; 0 rt rt Φ 0 tr s; μ-1 o TJ 3 CQ TJ 0 • : $u ri tr ii Hi ft 3 Φ a o
SU tr Φ Ω μ- 0 Φ *< rt TJ > Φ > O μ- Ti SU ii tr 0 Φ μ- Φ • 3 ii o c! ft 0 ii μ- SU 0 H rt SU ø . Φ ii 1 ii 1 0 l-1 ii ιp SU 0 φ 0 3 0 Ω Φ 03 < pa SU
Φ X ft ft ø tr φ su rt 0 M Ω H . SU 0 φ ft Hi 03 d Ω < Su 0 i φ > M <!
■ ! rt ^ ft • S rt 0 d ii <i tr ii TJ -J μ- W - ø Ti ø ft μ- rt Su d φ h-1 d Ω ft o 3 su ft 03 tr h-1 μ- φ 0 d 03 03 su μ- Su ii ■4^ SU O Φ ri rt μ- rt ø tr ii ø 03 li μ- μ-
Φ μ- Φ rt μ- rt Φ φ μ- 03 >r μ- — -~ * — - α μ- - rt tr σi 0 μ- rt 0 CQ su μ- a CD
03 ι-j rt μ- cp SU ft ^ ^-_. μ- su . -. su . — . Su μ- φ Ω o d ø μ- Φ H ø t Q su μ- u rt ii 0 tr tr σi su ft 03 rt •<; ø Ω rt 03 0 0 rt (P 0 ft - = 1 tr tP ø ii μ- ø rt 0 d tr μ- Φ SU tr 0 Φ d 0 Ω 3 t 0 φ ^ tr t I-*
0 Φ SU 3 d S ft ø μ-* rt , — , su 0 d 3 Ω d TS Φ H su . 03 Ω μ- M I-1 φ
SU ft φ TJ rr Φ tr ft Φ ii to rt < ft ii
- 3 03 tr ii 0 μ- ■-P μ- 0 SU 03 X CT) rt , — Φ rt SU Φ μ- Φ φ μ- μ- su μ-
^ Φ rt μ- 0 ιp rt Φ ■i |3 < TJ 1 o μ- Ω tr ft ii t tp ii Hi ft t r μ- 3 ϋ H su tr ø φ tr 0 ø SD o" SU tr ω SU 0
0 0 ft 0 tr Ω tr Hi ii φ 1 SU φ Ω SU 03 Φ ιp 0 rt rt tr μ- μ- Φ I 0 φ ø 3 Φ X φ φ s rt rt 0 Ω CT ø su rt o μ- ø ft U H1 ø ø t ft CO
3 03 ^ CQ ø Φ 0 tr 3 >< μ- SU tr tr 0 u Φ su Ω SU -> TJ tr Ω φ su su 0 t
Φ μ- ω μ- rt μ- Ti s; Φ CQ rt su ø 03 0 ιp Φ 0 0 rt tr H 3 Hi
1 ii ιp μ- 0 - ιp Φ SU « TJ φ Φ Ω ø 1-* 03 3 φ ft ii d 3 Hi μ- \-> . — . > li
H Ω ø ø tr ii tr rt φ 0" . — , 03 ii Φ *<! Hi μ- Ti ø φ Ω rt TJ 0 0 Φ SU 3 o
H μ- $u su tr rt Ω μ- ii ø 0 to Hi ^ Ω o μ-* 0 rt T5 Φ 0 ii ø ø H 3
O u rt ø Ti SU Φ H SU ii 03 1 Hi ii I-* rt su ii su 03 Φ 0 μ> 0 CQ Hi Φ n
O l-1 μ- φ ■i CQ Ti ø μ- ft μ- TJ TJ O 0 o μ- < ø μ- Ω 0 rt o Φ d ii TJ μ-
- — >
0 0 Φ Φ rt rt Φ Ω tr ii ■i 3 X Ω SU d φ rt 0 ft -> o 0 03 0 0 0 3 pa LJ.
*-. *< ø _— _ 3 ft ii - ^ tr μ- 0 > d μ- CQ μ- 3 μ- rt Φ Hi 3 X μ- IS μ-
Ω 0 Ω ft rt TJ d O rt Φ su 0 Ti ø tr ^ ^ ft s ø
3 SU > 0 rt 0 Φ 03 SU Φ T. 0 Φ CQ to Ti su ø ø 0 ιp su Φ 3 μ- r > su o
Su < 1 3 Φ ø 0 d ιp 03 Φ 1 0 Φ H ii d tr tr ft 0 03 μ- SU ø tr 03 N > 3
■ ! SU 1 3 ii rt Ω Φ μ- rt o > 0 ø I-1 Φ \ 3 Φ 0 Φ ιp ■ ! Φ SU SU 0 H o μ- oo φ CQ rt - tr ø <P ■i tr d Ti ft Φ H 0 su 0 Hi ft tr rr CQ tr 0 H α rt tr -j ii - - rt 0 0 - 0 Φ ø ^ Φ φ ii *< rt rt tr tr Φ μ- ft Φ 0 φ su Ω Φ ft su SU Ω X ii ft H ii Hi μ- • Ω o Φ φ 1 ^^ n tr μ- CQ Φ 03 3 rt tr ft ^ Φ Φ ϋ ø rt SU 0 ø TJ μ- Ω -3 tr μ- d 0 su d rt CQ Su μ- Φ μ- μ- ii rt rt 0 μ- d Φ d Ω 3 μ- 2 μ- pa ø
CQ φ ■i H Ω 0 μ- SU *< 0 3 tr 3 ø ii tr 3 μ- rt 03 ii rt ii CQ 0 μ- tr o 03 w Ω
Φ tr rt ii tr ø μ- * Φ rt μ- Φ ø u 0 CQ tr Ω Φ 3 ft su < Ti > ft Hi ιp ^ su u 0 tr Ω ft rt μ- tr 3 O Ω ø φ Φ Φ ft TJ SU - > \rr S d ii Su su M tr d Φ « su ii - ø Φ φ rt to μ-1 Su μ- 0 0 N o φ > ft
0 3 SU 03 rt 0 "< Ω rt ii H d rt ø 0 S rt μ- CQ 0 tr1 α 0 1-3 Φ
3 3 S < d 1 cp !_, μ*1 rt tr SU ft Φ Ω 0 Φ - ø μ- rt ta 0 a
Su SU rt Φ o 03 U1 H φ d i 0 ft Φ • H μ- rt Φ ft M • *s
O 1 μ- tr μ- SU • Φ σi 0 ø 1 tr o ft — - ft SU X Φ d rt ιp 03 su μ- 3 > to SU Φ ιp Ω • — ■ H φ o ft * 0 ft tr tr d ø 0 - 3
H 3 SU tr 0 (Jl • t 1 Φ Ω φ Φ rt Ω 0 H H μ- tr rt d μ- _. rt tr 03 3 X Φ 0 O ø rr ø *< SU rt 0 0J 1 TJ
0 Φ 0 r-1 s Hi su 0 • 0 pa
Hi su CQ Hi X M ø φ s
When used, the adhesion promoters may be used in an amount of about 1 to about 20 weight percent, such as about 5 to about 15 weight percent, desirably about 8 to about 12 weight percent, based on the total weight of the composition.
Cyanate esters may also be used in the inventive compositions . The cyanate esters useful as a component in the inventive compositions may be chosen from dicyanatobenzenes , tricyanatobenzenes , dicyanatonaphthalenes, tricyanatonaphthalenes, dicyanato- biphenyl, bis (cyanatophenyl) methanes and alkyl derivatives thereof, bis (dihalocyanatophenyl) propanes, bis (cyanatophenyl) ethers, bis (cyanatophenyl) sulfides, bis (cyanatophenyl) propanes, tris (cyanatophenyl) phosphites, tris (cyanatophenyl ) phosphates , bis (halocyanatophenyl) methanes, cyanated novolac, bis [cyanatophenyl (methylethylidene) ] benzene, cyanated bisphenol-terminated thermoplastic oligomers, and combinations thereof. More specifically, aryl compounds having at least one cyanate ester group on each molecule and may be generally represented by the formula Ar(OCN)m, where Ar is an aromatic radical and m is an integer from 2 to 5. The aromatic radical Ar should contain at least 6 carbon atoms, and may be derived, for example, from aromatic hydrocarbons, such as benzene, biphenyl, naphthalene, anthracene, pyrene or the like. The aromatic radical Ar may also be derived from a polynuclear aromatic hydrocarbon in which at least two aromatic rings are attached to each other through a bridging group. Also included are aromatic radicals derived from novolac-type phenolic resins -- i.e., cyanate esters of these phenolic resins. The aromatic radical Ar may also contain further ring-attached, non-reactive substituents . Examples of such cyanate esters include, for instance, 1, 3-dicyanatobenzene; 1, 4-dicyanatobenzene; 1,3,5- tricyanatobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7- dicyanatonaphthalene ; 1,3, 6-tricyanatonaphthalene ; 4,4'- dicyanato-biphenyl; bis (4 -cyanatophenyl) methane and 3, 3 ' , 5, 5 ' -tetramethyl bis (4 -cyanatophenyl) methane; 2,2- to to *-Λ
μ- ii Ω Ω ft tr ø φ *< •<: μ- μ-
Ω u (U su tr Q
H Ω 0 ø ii ,—, d rr SD (U 0 ω ft μ- rt rt 3 -
Φ <! 0 o 0 σi φ Ti TJ 1 1
3 tr tr tf-» ft
0 ft Φ Φ 1 μ-
0 & μ- 0 ø ft Ω
0 TJ ■ : μ- tr
Hi TJ d H H Ω d ii φ — ^ 0 ø 0 0 Ti Φ SU ii
Ω TS rt ii rt 0 o rt ii • 0 tr SU 1 μ- μ- Ti Φ rt rf^
0 su SU ii 0 1 ø rt 0 -. TS Ω
SU φ Φ tr *< μ-* tr φ SU ii μ- 0 0
0 Φ rt 03 ^ SU ii U ii . — . I-* rt
Ω μ- * > 0
Ω rt 03 1 TJ Ti
Φ μ- _— , Ω ii tr ii <! 1^ *< 0 Φ rt φ 1 SU TJ ø
SU Ω 0 SU *< μ- ft *< SU 0 H1 ø μ- SU rt φ - —
0 0 *»• TJ
3 d SU Ti ii d φ rt tr tr 0 ø 0 φ μ- TJ rt rt TJ 0 03 SU μ- 03 tr ^ . — . 0
Hl φ M φ> Φ d Hi 0 — ' 1 -. ø 0 *< CQ
Ω ii h-1 d t rt — *- μ- d 1 Hi to
0 CQ Ti μ- 1 ø Φ tr ft tr
Su 0 φ μ- μ*1 tr 03 ω φ Ti ^-_.
Φ ii tr to ω
Ti φ μ- -
0 μ- rt to un
X ø Φ 1 1
K. ~. tr
3 μ-
(U CQ
• ;
Figure imgf000030_0001
1
resins and episulfides. The reactive diluent should have a viscosity which is lower than that of the curable resin component. Ordinarily, the reactive diluent should have a viscosity less than about 250 cps . In the event such a monofunctional epoxy resin is included as a reactive diluent, such resin should be employed in an amount of up to about 50 weight percent, based on weight of the curable resin component.
The monofunctional epoxy resin should have an epoxy group with an alkyl group of about 6 to about 28 carbon atoms, examples of which include C6.28 alkyl glycidyl ethers, C6_28 fatty acid glycidyl esters and C6.28 alkylphenol glycidyl ethers.
Commercially available monofunctional epoxy resin reactive diluents include those from Pacific Epoxy Polymers, Richmond, Michigan, under the trade designations PEP- 6770 (glycidyl ester of neodecandoic acid) , PEP- 6740 (phenyl glycidyl ether) and PEP- 6741 (butyl glycidyl ether) .
Commercially available multifunctional epoxy resin reactive diluents include those from Pacific Epoxy Polymers, under the trade designations PEP-6752 (trimethylolpropane triglycidyl ether) and PEP-6760 (diglycidyl aniline) .
The compositions of the present invention may further include other additives, such as defoaming agents, leveling agents, dyes, and pigments. Moreover, photopolymerization initiators may also be incorporated therein, provided that such initiators do not adversely affect the properties of the composition or reaction products formed therefrom. The present invention also includes novel diepoxide-containing compounds, set forth in detail below.
Figure imgf000031_0001
Figure imgf000032_0001
where R4, R5, R6, R7, R8, and R9 are individually selected from the group consisting of hydrogen, alkyl from one to eight carbon atoms, alkenyl from two to eight carbon atoms and combinations thereof, and X and X1 are individually selected from O and S.
More specific examples of such novel diepoxide- containing compounds include :
Figure imgf000032_0002
Figure imgf000032_0003
t t o
SU ø ft
Hi
O
S μ- ø ιp φ u
03 μ-
^
•
Figure imgf000033_0001
Generally, it is desirable to prepare thermosetting resin compositions, of this invention by selecting the types and proportions of various components to reach a viscosity at a temperature of 25°C in the range of 500 to 70,000 cps, such as 800 to 20,000 cps, depending on the amount present (if any) of an inorganic filler component, so as to improve its ability to penetrate into the space (e.g. , of 10 to 500 μxa) between the circuit board and the semiconductor device. At this viscosity, the gel times of the compositions will also be tailored to a specified period of time (such as 15 seconds, or 1 or 2 minutes) at a temperature of about 150°C. In such case, the inventive compositions should show no or substantially no increase of viscosity after a period of time of about six hours. With such a gel time, the compositions penetrate into the space (e.g. , of 10 to 500 μ ) between the circuit board and the semiconductor device relatively rapidly, and allow for a greater number of assemblies to be filled without observing a viscosity increase in the composition thereby rendering it less effective for application.
Reference to FIG. 1 shows a mounted structure (i.e. , a FC package) in which a thermosetting resin composition of the present invention has been applied and cured. The FC package 4 is formed by connecting a semiconductor chip (a bare chip) 2 to a carrier substrate 1 (e.g. , a circuit board) and sealing the space therebetween suitably with a thermosetting resin composition 3.
More specifically, for example, in the assembly of FC semiconductor devices using SBB technology, the semiconductor chip 2 may be passed over a substrate bearing a conductive adhesive paste (such as a metal-filled epoxy) to form a layer thereof on the semiconductor chip 2. The layer is ordinarily formed by a printing mechanism. The conductive adhesive paste may be applied on either the carrier substrate or the semiconductor chip . One way to do this is with the stencil claimed and described in International Patent Publication No. PCT/FR95/00898. Alternatively, this connection may also be made by an t t o
ft Ω 03 tr rt μ- Ω 3 Ω Ω 3 Ω φ SU ιp 0 03 ø Ξ Ω TJ 03 rt φ <J su TJ SU 03 O TJ SU μ- SU Φ Φ tr Hi 03 0 Su 0 0 Φ SU μ* H I-* ii 0 μ- μ- 0 ii Φ tr 3 su ø su ø φ < Su ø
03 ii 3 μ- Φ rt ø • : 0 0 I-* ii φ φ SU tr rt rt 3 o SU Φ TJ ri ft rt ft 3 φ rt μ-
Ti ii μ- 0 ii Φ 0 ø 0 ft rt ii Ω 03 rt 03 ii tr TJ ft 1-* μ- rt μ- ii Φ 03 φ μ- Ω £ φ ii ii Φ tr Φ d μ- μ- rt SU 03 Su rt μ- H d Φ 03 0 φ CO Φ σi Ω ø O ø φ 0 rt ft Ω Φ Ω Ω ø φ li 1 TJ ii ft su Φ Ω ft φ ; rt • ii 0 rt rt rt
03 ii ø 0 TS μ- rt rt rt IP ii μ- 03 ii Φ Si) φ rt rt 3 Φ < ø 0 0 tr ri
Φ ft SU ø Φ Hi μ- μ- Ω 0 Φ 03 rt 1 Ti Φ μ- ft Φ ø tf Φ TJ 0 ii CQ d H S 03 su ft o 0 <! 03 01 SU μ- Φ tr 0 H1 0 μ- Ω 0 ι-3 ft d d Ti
- d Ω 0 μ- 03 ii ii ø Φ 0 d M d ø 0 03 su * Hi rt 0 Hi tr rt Ω Ω tr μ- a tr rt rt μ- μ- rt 3 03 tr 03 Hi Hi π 03 ^ 1-3 tr ø H φ tr rt Su >-3 I-1 Ω
Su 03 03 0 rt tr 0 H> 0 Hi Φ - su ft 01 Ω φ 0 0 su Φ μ- tr Hi rt ft ø S SU Φ 0 ii tr μ- SU μ- rt ii tr ιp • ; rt ft ft φ rt 0 ft ii tr Hi ii ft 3 Φ μ- tr su d SU Ω •<; ii ii Φ Ω l-1 rt ø ii μ- su rt Φ TJ tr H ii 0 Ω φ ii μ- (-■ φ Ω o • ! O Φ Ω μ- ϋ u h-1 tr IP Su Ω Q CQ 03 tr i SU Su φ SU 0 Ω Φ (U μ- 3 ft 03 H rr rt ii 03 ø ii Su Ω φ Φ rt <:
Φ rt tr rt d d Φ 03 ii 03 0 rt Φ 0 ft rr H φ SU φ φ rt tr 0 ft - ft ii tr ii Su μ- ii su Φ μ- £ tr Ω tr rt rt μ- H Φ Ω 3 1 o Hi rt 1 3 rt tr φ ii φ d O ii μ- Hi O Ω
3 TJ su φ tr Ω tr 3 μ- <! rt 3 Φ ii Φ - μ- tr φ ii ii rt Ω Hi μ- TJ 03 rr ø O
0 03 ≤ ϋ Φ SU φ μ- Ω Φ Φ 3 μ- 0 Ti Φ 03 ii Ω su ii 3 Ω tr rt Φ d Φ 0
03 d μ- 3 3 rt Ω ii ii d H- SU 0 0 0 03 d μ- Ti 0 rt 3 0 tr rt 0 μ- Ω ti CO tr ii ≥! ft φ μ- rr Su 0 φ rt ii 03 φ SU Φ ^ ø X μ- to tr su 0 0 0 03 μ- 0 d <! O 03 - O d rt rt tr ^ μ- 03 03 Φ μ- Φ SU ø Ω •• 03 03 I-*
^ μ- ft 03 03 Φ TJ ιp φ 0 CQ μ- rt • Ω rt su ø Φ rt ft Φ 3 tr M ft rt tr 0 rt a rt ; d Ti φ rt μ- tr ft d 03 ii rr rr μ- tr rt tr rt - ii μ- 0 H ri Φ Hi SU u d ii rt 1 Ω SU rt rt CO 3 u d tr SU tr ) μ- ø l-1 tr Φ rt rt rt Ω ø *< rt μ- 03 e ø su SU 0 tr rt Ω rt μ- Ti 0 ft Ω CQ μ- rt Φ o <J ιp φ Φ tr μ- rt 0 03 0 ft tr Ω d rt rt ø rt Φ 0 Φ μ- ø SU ii ii tr rt rt ø Φ 1-3 Φ ii φ ø tr d ø μ- Φ SU CQ tr Ω to ft Φ Ti ø ii • ø ιp ø O ft Φ μ- ii 03 ^__ ii SU rt Φ <P φ SU tr ft tr ø μ*1 Φ φ μ- ■i 03 SU N ιp ft <! μ- 03 <! SU su H φ su
Φ TS tr 3 Φ 03 d d ft •i $u Φ
CQ 3 CQ 0 Ω i Φ ø μ- Φ rt 3 ω ft
CQ Ti Φ 0 < ii CQ Ω rt Ω 3 to μ- >< 03 Ω ø d 3 03 Ω tr ii Φ rt su < Φ μ- μ- μ- u. tr μ- μ*1 ii <! Φ Φ φ 0 ii rt Ti ω pr Φ d ft μ- SU μ- ^ μ- Φ 03 tr ii ii φ S3 ιp ø Ω -J Φ ø μ- 3 Φ ø 03 3 0 SU 0 CQ ω φ ,— _ 03 3 μ- ø 1— I >< < Ω Ti 03 μ- φ Φ μ- ft H ø 0 ~---. 03
Ω 0 ft rt μ- μ- rt rt ii . . 0 d μ- rt Ti 03 μ- su I-1 μ- ø TJ ø" 3 03 ø H μ-
Ω SU 03 ø Ω μ- Φ rt ii Ω Ω tr tr rt 0 0 ø Ω μ- << su Φ Φ d & ) <!
0 rt Φ tr 0 0 0 - Ω Φ tr 0 tr Φ Φ φ φ tr ii Ω su su 03 CQ 0 ø Ω d σi Φ
3 μ- rt Φ Hi Ω ø d tr Ω μ. SU ø 0 ø 01 d ft Ω 0 ii tr su rt μ- o rt tr Ω ι »
Ti O rt Hi O ft μ- rt μ- tr ø 0 su ft SU o d Ω φ rt μ- 0 3 ii μ- Φ < s rt
0 ø μ- 0 SU d rr tr Ti ø μ- CQ d ii I-* Ω 0 ø SU ø 3 Ti μ- t-1 tr φ S su 0 •
CQ ø li Ti Ω ^ Φ 0 0 01 Ω ft μ- tr > J-l 0 < 0 $u TJ 0 φ μ- φ 3 Ω μ- ti to μ- 3 ιp Φ Hi 0 rt μ- ii 0 Ω rt 03 Ω 03 μ- Φ ii 0 03 ii rt su SU Ti O rt 3 φ rt φ SU 03 O rt ii 03 O ft rt 0 0 -. su o rt ■i I μ- 03 μ- rt i 0 ii CQ CQ ii 0 μ- rt 03 ^ i su SU tr U Ω Φ μ- Su ii μ- μ- μ- ii Φ Φ IP Φ l CQ rt ø tr
0 ø Φ rt 1-" rt 03 03 φ ii 0 0 Su d 3 d μ- Ω rr d ^ TJ φ Ω 0 tr Ti to d 0 0 >< rt μ- d Ω tr rt Φ rt ø μ- H
0 03 0 μ- Ω 3 i μ- 0 tr rt d Φ Φ ft tr Φ TS 0
- μ- μ- ii 0 tr i-* φ rt μ- Ω tr ft CQ 0 rt Φ 3 0 ø 03 tr ii Φ ii rt μ- ø CQ φ ø μ- O rt Ω ft O Ω rt μ- rt O φ 0 03 SU ø rt Φ Φ Ω O 3 t Φ ø CQ - Ti ii μ- rt tr SU μ- J rt ii ^ ft rt μ- •< ω ii d ii μ- Φ CQ ii d Ω Hi 0 ii Φ Hi M 0 tr Su μ- -.. Su H 03 • Su 03 3 ii rt I-1 0 μ- 0 su Ω 0 μ- rt SU 3 rt IP μ- SU I-1 0 rt φ rt 3 Hi μ- tr tr rt Ti Φ Φ 03 tr Φ 03 SU
Ω tr 3 X tr CQ SU tr Ω Φ Ω "i 0 Φ μ- CQ H Ω Φ o Φ SU Ω ft O Ω rt rt
Ω Ti φ Φ ^ φ 03 SU μ- tr I-* 03 ft d 0 Ω 0 d ι-3 Ω tr (-■ su rt tr TJ μ-
0 su 0 ft ft rt H Φ μ- rt μ- φ tr 3 0 0 Ω I-* tr H φ su tr ft ■i su 0 O ii 03 CQ Φ tr H ii Ω μ- tr W 03 03 ii φ 0 ft φ ø Φ 0 rt 03 ø ft μ- rt CQ Φ μ- d ^ rt rt SU φ φ tr -.. rt Ω ii su μ- tr μ- ii ft μ- Su su su rt 0 Ω ?*r Ω ii su • μ- ii Φ 0 rt Ω 03 Φ 03 su - Φ rt rt H ø μ- ii Hi φ rt 0 rt tr Ω su ii CQ Φ d rt 3 03 ø' μ-
Ω 0 rt μ- μ- . d ft Φ μ- tr rr Su μ- ft ii -j Φ 0
Φ ø tr tr X Φ ιp Φ 3 0 φ φ μ- i ø φ Φ φ Φ 03 tr & 03 μ- ø ft φ 03 φ ft ft 1 • ; Ω • 0 ft
t t o o
03 ii r-> ii SU U Ω ft 03 Ω SU $u rt rt Su Ω Ω tp TJ rt μ- 03 TJ 03 rt Ti tr Ω Φ rt tr Ω φ $
Φ Φ μ- Φ Ω ft O φ Φ 0 Ti Ω Φ tr rt 0 d φ φ Φ ø d φ d tr Φ Φ 0 SU tr Φ 0 μ-
3 CQ >V CQ Ω tr 3 Ti 3 3 TS tr 3 Φ 3 ii 0 ii 3 <! tr 0 tr φ ø ø 3 ii Φ rt Φ rt μ- μ- φ μ- Φ φ TJ Φ μ- Ti H* μ- TJ SU TJ Φ φ μ- TJ Φ CQ φ 03 Φ Ω Ti I-* ii s TJ Ω tr
Ω ø - 03 TS 03 0 ø Ω H μ- φ Φ TJ ii 0 Φ ø rt rt rt 03 rt Φ 0 *< 3 φ 0 rt
0 rt rt μ- 03 ft 0 Φ Φ < ri ii rt Φ rt SU ft ii rt H ii ii Φ ii 03 Su φ 03 ii rt ø Ω Hi SU SU <! μ- μ- 0 rt ft φ SU Φ Φ rt μ- μ-* su μ- SU SU SU 3 Su SU μ- 03 0 μ- 0 tr ft 0 0 ø tr Φ rt ø ft Φ rt 03 3 Φ 3 μ-" 0 rt 0 rt rt rt μ- rt 0 rt rt rt ø μ- d 3 ii Ω H μ- t d ω < C Φ TJ φ • Hi d 0 Φ Φ Φ Ω Φ H- Su *< rt μ- μ- 03
Ω Ti Φ φ Hi 0 Ω *• tr Φ ii 0 Φ Ω ii "* 0 01 μ- 0 IP tr 0 Ω rt 0 H rt - 0 ø O 0 rt 0 1-3 ii Φ rt ii d 0 SU rt Φ 3 1-3 SU Hi ø ø 0 Φ Ω ι-3 φ 0 SU μ-
0 CQ 0 tr 3 ii CQ d ø 0 rt d tr CQ SU i Hi Hi μ- SU tr ø d rt ft μ- Ω d tr ø ii μ- φ Ω Φ Ω ii i tr φ μ- rt Φ rt 3 μ- ^ φ ft M tr d ø ii 03 0 ii Φ Ω TJ < rt rt tr Ω φ 0 Φ SU Φ ft ιp SU 0 d SU Φ Φ 0 ii φ Ω rt Φ ø- Hi φ Su Φ *< Φ ft μ- tr su Φ tr - Hi ft Ti Ω Su 0 ø < μ- tr ii 0 3 rt * rt 0 Su 0 ft rt ii ø ø
Φ 0 Φ Ti 3 su Ti tr 03 tr 3 0 ft φ Φ 03 0 0 rt ii 0 tr rt 0 03 S rt tr ii Φ Ω rt
<! ø TJ μ- ø tr rt ii I-* μ- Ti Φ . 0 ft 0 d u Hi tr ft 03 φ μ- tr ii rt φ CQ tr tr φ μ- rt 0 μ- μ- 3 M Ω μ- φ tr Φ μ- T3 Su d 03 rt 0 0 rt TJ φ μ- φ ø Φ tr μ- *< ii Φ ii 0 0
Ω 0 0 μ- su Ω su Φ SU Ω - Ω CQ 0 TJ tr μ- Hi tr TJ Su ø rr 03 rt ii Ω φ μ- SU 03 3 ii SU 0 ø
Φ Hi d Ω u rt Ω SU Φ d rt ii 0 0 CQ M tr ii SU rt Φ 0 3 tr ø rt 0 rt Φ ø su M TJ rt rt s; μ- O ii ø SU Φ μ- 0 su ii μ- 3 0 μ- 03 03 tr tr 03 03 Φ Ω μ- μ- rt rt rt ii r ii μ- μ- tr tr rt 0 ft rt tr ii 3 Ω d ø μ- ø μ- rt CQ S Ti Hi μ- Φ Φ Φ d CQ rt CQ
03 tr μ- μ- Φ T5 Φ Φ 0 O μ- Φ su Hi d 1 Ω 0 < μ- SU rt cp tp Ω tr Φ • SU H* ιp su rt tr Φ
Φ ø 0 03 i 03 CQ 0 ø Ω rt tr Ω rt Su d Φ ø rt Φ ^ 0 Φ rt Ω d ø rt su rt 03 tr ft su
3 ιp ø μ- 0 μ- Φ tr ■ rr rt μ- ø rt ft d μ- o ii ø rt Φ μ- μ- μ- TJ μ- rt *< TJ
0 Ti CQ 03 TJ 03 ø TJ Φ •^ tr μ- 3 rt 0 • 0 tr φ ft Φ μ- 3 ft Hi ø TJ ø ii 03 TJ d ii Ti rt Φ rt rt ii su Φ Φ < φ tr H SU Φ 0 σi Hi φ 03 d ø ø 0 tr μ- μ- ιp IP SU Ω φ μ-1 ø Φ ii Hi su ii SU 0 3 ø SU ii μ- Φ σ. Hi μ- Ω rt ιp ri Φ rt Ω - μ- rt SU 3 μ- rt 03 0 0 ø rt 0 μ- ft 0 ft 3 rt Ω U1 rt 03 0 rt SU Ω ø rt μ- Φ rt >< SU Ω ii Φ T! μ- φ
Φ Φ Ω ii Ω μ- Ω ø d d rt l_J. 0 ^ d d Φ Φ Hi 0 tr d 0 ■i ii 0 ■S 0 rt su Φ μ- Ω ft ft ø Φ φ Φ Φ < Ω ø tr d 03 ii 03 O ii rt o ii Ω ii Φ Φ < Φ rt tr rt 03 SU 0 rt 03 S - 03 Φ rt rt Φ 03 Φ μ- Φ . 03 rt ω d φ 0 03 Φ Φ CQ Φ μ- μ- ø H 0 rt
0 03 tr - SU ø 03 rt rt ø ft SU tr o rt ft 3 Ω 03 μ- ■i 0 0 ri 0 ø ft su ft 0 ø μ- μ- 3 ø rr 0 Ω Φ rt ιp tr φ TJ tr Ti ø ^ Φ rt ø ii d ø tr Ω 0 03 ft μ- 0 Hi su ft μ- SU i-3 0 Ti 3 H tr 0 μ- SU rt rt ft tr Ω rt ^ Ω rt rt <! • ; tr μ- d O Hi ii ø Ω rt tr d Ω μ- to *<: 03 TJ Ω Ω tr tr tr d Φ 0 0 tr rr tr tr Φ 03 Ω Φ ø Ω ti CQ ιp 0 d rt rt 0 ø o μ- • Φ 0 *<; φ su Ω ii Hi 3 φ SU 0 Φ
Φ ø d rt rt tr f-1 rt 0 μ- 0 ø ii 03 tr 3 d tr rr 3 rt rt 3 Ti Ω i rt 03 tr d Φ ft tr d φ ii ft Φ - σi φ TJ rt rt Φ μ- tr TJ TS Ω μ- 0 tr 0 03 ft TJ
Ω μ- μ- φ ii su Ω Φ Φ ii ■i SU Φ μ- r-> 0 Φ 0 su 0 Φ 0 ii SU μ- 0 03 φ 03 φ μ- Ω φ μ- 0 ø • ; Φ 03 rt 3 03 03 03 rt SU rt rt Ω 01 03 rt 0 rr CQ Φ ii rt 0 Φ su μ- 3 0 - ii
•i 0 <P i 0 rt φ CQ μ- μ- rt tr 0 0 μ- • SU μ- 03 $ μ- tr ii rt rt rt μ- 0 μ- μ-
Ω -• su i Hi μ- ø tr d rt ø 0 μ- Φ 3 rt tr ø Φ rt Φ μ- 3 μ- rt μ- Ω TS TS d rt ii Φ Ω 03 φ 3 tr 0 ø < SU TJ μ- 0 cp 0 Φ μ- su φ 0 ø μ- 0 0 μ- • tr μ- su tr φ 03 Φ rt ii su 03 Ω 03 φ Ω tr 0 0 ϋ. d Hi ø 0 rr ii ii ø ø ø ø Φ rt Hi φ μ- X TJ ii 3 ^ ft Hi 0 - H 0 0 03 ø 0 rt rt ø μ- Φ < cp α ft rt ii rt d CQ 1 ii su 0 i μ- 3 3 d μ- ■s 0 rr rt ø 03 μ- d μ- d 0 ι-3 ^ tr Φ rr 01 rt Ω 0 rt CQ <! SU TJ SU TJ rt rt φ H tr tr μ- ιp d Φ 03 ii ii CQ Ω tr
0 ii tr φ Su ii TJ Φ Φ SU rt H 0 ø 3 0 μ- u < 00 SU Φ Φ CQ tr SU Ω Φ μ- rt rt φ 0 su φ ft ø SU Φ rt ii Φ 03 ft 0 03 H 0 ø φ o rt 03 03 0 03 rt ii Φ rt •<. SU μ- ft μ- σi ø ii Ti Ω rt ø 0 tr Hi rt ri Ω Ω ii su tr μ- 03 H- ιp tr ii Φ ft tr 3 tr φ ? rt X μ- SU (-■ rt tr Φ rt μ- O ii su μ-1 φ ii μ- ø Φ ft
Φ 0 Φ μ- μ- Ω ø ø 3 μ- φ ii μ- 3 ø Φ ii SU ^ rt rt ø Ω CQ tr
PJ CQ ii SU ø Φ Φ ιp ft 0 0 ø SU 0 μ- SU μ- Hi 03 ii 0 Ω rt *< tr tr Ti Φ
03 φ φ ø ιp 03 μ-* 03 ø Ω rt ø ø ø rt 0 φ H- ≤ su Φ φ μ- SU rt μ- ft - -~ ii rr rt Φ Φ d ft μ- li 0 Φ φ ii SU TJ Ω rt ø φ Φ tr 0 rr su rt ii ft ii SU ø • φ μ- • rt Su ø 03 φ Hi Φ 1 Su μ- ø ft ø tr 0 rt μ- 03 rt Φ ft ιp Φ ft ø 0 ii
described above, the resulting structure is tested with respect to characteristics of the semiconductor device, connection between the semiconductor device and the circuit board, other electrical characteristics, and the state of sealing. In the event a failure is found, repair can be made in the following manner and as shown in the flow diagram depicted in FIG. 2.
The area around the semiconductor device which has failed is heated at a temperature of about 190 to about 260°C for a period of time ranging from about 10 seconds to about 2 minutes. (See FIG. 2, step 1.) Desirably, the temperature should be maintained in the range of about 210 to about 220°C and the period of time should be within the 30 seconds to 2 minute range. Localized heating is particularly desirable, such as the application of hot air to the failure site by a heating gun.
As soon as the solder is melted and the resin is softened by partial decomposition to cause a reduction in bond strength, the semiconductor device may be pulled apart and removed from the substrate, such as with tweezers or pliers, or through automated processes.
After the semiconductor device 4 is removed, a residue of the cured reaction product of the thermosetting resin composition and a residue of the solder are left on the circuit board 5. The residue of the cured product of the thermosetting resin composition can be removed, for example, by scraping it off after the residue has been softened by heating it to a predetermined temperature. The residue of the solder can be removed, for example, by use of a solder-absorbing braided wire. (See FIG. 2, step 2.)
Alternatively, use of a dremel at about 25,000 rpm or more, followed by application of a flat-end horse hair brush, will achieve the desired result.
Finally, a new semiconductor chip may be mounted azain onto the circuit board (which has been cleaned, with fluxing, as described above) in the manner as described above. (See FIG. 2, step 3.) Following mounting, a thermosetting resin composition in accordance with this invention may be dispensed in the area between the semiconductor device and the circuit board, and cured. (See FIG. 2, step 4.) Repair of the failure site is thus completed.
Where a failure site is found in the circuit board, the semiconductor device can be reused by removing the residue of the cured reaction product of the thermosetting resin composition and the residue of the solder left on the bottom of the semiconductor device in the same manner as described above . The present invention will be more readily appreciated with reference to the examples which follow.
EXAMPLES Synthesis of Epoxides Limonene [125 grams (477 mmoles)] and methylene chloride (1000 ml) were added to a reaction flask, and the resulting solution cooled with an ice bath to a temperature in the range of about 0 to about 10°C. Then, 70% m- chloroperbenzoic acid [259.5 grams (1050 mmoles)] was added with stirring in small increments over a period of time of about 110 minutes, while maintaining the temperature of the reaction mixture below about 15°C. The reaction mixture was stirred overnight, while maintaining the temperature below about 15°C. m-Chlorobenzoic acid was formed as a precipitate, and filtered off, with the organic filtrate - washed twice with 500 ml portions of 10% aqueous Na2S03, twice with 500 ml portions of saturated aqueous Na2C03 solution, and twice with 500 ml portions of water. The organic layer was separated, dried over anhydrous MgS04, and then filtered. Basic alumina (50 grams) was then added to the organic filtrate, with the mixture stirred for a period of time of about 45 minutes, and then filtered. The organic solvent was removed under reduced pressure, and the resulting product vacuum distilled. Limonene diepoxide was obtained in an amount of 120.7 grams (86% yield) . 1H NMR (CDC13) S 3.0 (m, 1, C2C-H) , 2.5 (m, 2, C-C-H) , 1.0-2.2 ( , 7, CH, CH2) , 1.3 (s, 3, ring CH3) , 1.2 (m, 3, side-chain CH3) ; IR (neat) 2932, 1436, 1381, 853, 763 cm"1.
Gamma-terpinene diepoxide, methyl cyclopentadiene dimer diepoxide and ethylidene norbornene diepoxide were prepared in the same manner. Their spectral data are given as follows: lE NMR (CDC13) δ 2.5-3.0 (m, 2, C2C-H) , 2.1 ( , 4, CH2) , 1.6 ( , 1, CH) , 1.3 (s, 3, CH3) , 1.0 (m, 6, side- chain CH3) ; IR (neat) 2963, 1467, 1107, 834, 709 cm-1; XH NMR
(CDCI3) δ 3.0-3.5 (m, 1, C-C-H), 2.5-2.7 (m, 1.5, C2C-H) , 1.2-1.9 (m, 8, CH, CH2) , 1.4-1.5 (m, 6, CH3) ; IR (neat) 2956, 1448, 1078, 829, 759 cm"1; and XH NMR (CDCI3) δ 3.0-3.5
(m, 2, C-C-H), δ 3.0-3.5 (br s, 1, C-C-H), 1.1-2.3 (m, 6, CH, CH2) , 1.3 (d, 3, CH3) ; IR (neat) 2979, 1449, 1376, 1008, 852, 757 cm-1, respectively.
The yields and boiling points of these diene diepoxides are given below in Table 1.
Table 1 Yields and Boiling Points of Certain Diene Diepoxides
Figure imgf000039_0001
Nopol epoxide glycidyl ether was prepared as follows „
To a four-necked 1000 ml reaction flask, equipped with a mechanical stirrer, thermometer, and condenser, was added 200 ml of 50 weight percent aq. NaOH, epibro ohydrin (144.3 g, 1.03 mol), and tetrabutylammonium hydrogen sulfate (4.2 g, 12 mol) . The mixture was stirred vigorously at room temperature for a period of time of about 20 minutes to a pale yellow color. The mixture was then cooled to a temperature of about 10°C in an ice/water bath. To the mixture was added (IR) -(-) -nopol (50 g, 295 mmol) dropwise over a period of time of about 30 minutes. The reaction temperature was maintained at or near about 10°C during the addition. The ice/water bath was removed, and the mixture was allowed to warm to ambient temperature, while it stirred overnight. The reaction mixture was then quenched with 500 ml of ice cold water, which was added over a period of time of about 15 minutes, with stirring for an adiitional period of time of about 20 minutes. The mixture was transferred to a 2 liter separatory funnel, where it was twice extracted with 200 ml of diethyl ether. The organic portion was then washed twice with 200 ml of sat. aq. NaCl, separated, dried over anhydrous MgS04/ and then filtered. After filtration, the solvent was removed under reduced pressure. The crude product was vacuum distilled to yield about 48.1 g (74%) yield of nopol glycidyl ether, with a boiling point of about 94-96°C at atmospheric pressure. The spectral data are given as follows: XH NMR (CDC13) δ 5.25 (br s, 1, =CH) , 2.8 - 3.7 (m, 7, OCH, OCH2) , 2.0 - 2.4 (m, 6, CH, CH2) , 1.6 (s, 1, CH) , 1.3 (s, 3, CH3) , 1.1 (d, 1, CH) , 0.8 (s, 3, CH3) (see FIG. 15); FT-IR 2927, 2908, 1468, 1364, 1108, 910, 849 cm-1 (see FIG. 16) .
To a four-necked 500 ml flask equipped with a mechanical stirrer, thermometer, and condenser, was added nopol glycidyl ether (48.2 g, 205.4 mmol), and methylene chloride (250 ml) . To the solution was added 70% m- chloroperoxybenzoic acid (53 g, 215 mmol) over a period of time of about 2 hours . The reaction temperature was maintained below about 15°C with an ice/water bath during the addition. After the addition was complete, the reaction mixture was stirred overnight and maintained at a temperature below about 20°C with an ice water bath. m- Chlorobenzoic acid was formed as a precipitate, and filtered the organic filtrate washed off, twice with 200 ml portions of 10% aq. Na2Sθ3, twice with 200 ml portions sat. aq. NaHC03, and twice with 200 ml portions of water. The organic layer was separated, dried over anhydrous MgS04, and filtered. Solvent was removed under reduced pressure, and the crude product was vacuum distilled. Nopol epoxide glycidyl ether was obtained in a yield of about 46.5 g (91 %) , with a boiling point of about 110-113°C at 800 mTorr. XH NMR (CDC13) δ 2.8-3.7 (m, 8, OCH, 0CH2) , 2.0-2.4 ( , 8,
CH, CH2), 1.3 (s, 3, CH3) (see FIG. 17), 0.9 (s, 3, CH3) ; FT- IR 2917, 1470, 1110, 911, 855, 761 cm"1 (see FIG. 18) .
Thermosetting Resin Compositions Preparation
A thermosetting resin composition (Sample No. 1) was prepared by mixing together for a period of time of about 10 minutes at room temperature in an open vessel the following components: 1. an epoxy resin component including
51.7 weight percent of limonene diepoxide prepared as above, and
2. a curing agent component including 46.5 weight percent of MHHPA, 0.8 weight percent of benzyldimethyl amine, and
1 weight percent of ethylene glycol . Four additional compositions (Samples Nos. 2-5) were prepared in this manner, substituting for the limonene diepoxide, the same amounts of gamma-terpinene diepoxide, Compound XVI of the '922 patent, and the commercially available epoxy resins, ERL-4221 and RE-404-S. [See Table 2(a) .]
A further thermosetting resin composition (Sample No. 6) was prepared as described above by mixing together the following components:
1. an epoxy resin component including 51.7 weight percent of limonene diepoxide, and
2. a curing agent component including
4.7 weight percent of dicyandiamide, and 1.9 weight percent of an imidazole (commercially available from Synthron, Inc. under the trade designation "ACTIRON" NXJ-60) .
Four additional compositions (Samples Nos. 7-10) were prepared as Sample No. 6, substituting for the limonene diepoxide, the same amounts of gamma-terpinene diepoxide, Compound XVI of the '922 patent, and the commercially available epoxy resins ERL-4221 and RE-404-S. [See Table 2(a) .]
Table 2 fa)
Figure imgf000042_0001
A further thermosetting resin composition (Sample No. 11) was prepared with a limonene diepoxide/RE-404-S combination, designed with an imidazole/dicyandiamide cure, as described above by mixing together the following components :
1. an epoxy resin component including
74.7 weight percent of limonene diepoxide, and
18.7 weight percent of RE-404-S, and 2. a curing agent component including
4.7 weight percent of dicyandiamide, and 1.9 weight percent of the imidazole, NXJ-60. Two additional compositions (Samples Nos. 12-13) were prepared as Sample No. 11, except that the weight percent of the limonene diepoxide was decreased and the weight percent of the RE-404-S was increased. [See Table 2(b) .]
A still further thermosetting resin composition (Sample No. 14) was prepared with a terpinene diepoxide/RE- 404-S combination, designed with an imidazole/dicyandiamide cure, as described above by mixing together the following components :
1. an epoxy resin component including 74.7 weight percent of terpinene diepoxide, and
18.7 weight percent of RE-404-S, and
2. a curing agent component including
4.7 weight percent of dicyandiamide, and 1.9 weight percent of the imidazole, NXJ-60.
Two additional compositions (Samples Nos. 15-16) were prepared as Sample No. 14, except that the weight percent of the terpinene diepoxide was decreased and the weight percent of the RE-404-S was increased. [See Table 2(b) .]
/An additional thermosetting resin composition (Sample No. 17) was prepared based on a limonene diepoxide/RE-404-S combination, designed with an imidazole/dicyandiamide cure, as described above by mixing together the following components :
1. an epoxy resin component including
39.17 weight percent of limonene diepoxide, and
26.11 weight percent of RE-404-S; 2. a curing agent component including
1.4 weight percent of the imidazole, NXJ-60, and
3.14 weight percent of dicyandiamide; 3. 30 weight percent of an inorganic filler component, SO-E5 silica; and
4. a flowability agent including the silanes, octyl (A-137, 0.06 weight percent) and glycidyl (A-187, 0.06 weight percent), and titanate (KR-55, 0.06 weight percent). Five additional compositions (Sample Nos. 18-21 and 25) were prepared along these lines, except that the limonene diepoxide/RE-404-S ratio was varied, and as to Sample Nos. 21 and 25, the weight percents of the components of the flowability agent were also varied. [See Tables 2 (b) and 2 (c) .]
Table 2(b)
Figure imgf000044_0001
A further additional thermosetting resin composition (Sample No. 22) was prepared based on a limonene diepoxide/RE-404-S combination, designed with an anhydride cure, as described above by mixing together the following components :
1. an epoxy resin component including
10.83 weight percent of limonene diepoxide, and
16.24 weight percent of RE-404-S; a curing agent component including 24.36 weight percent of LINDRIDE 62C,
2.71 weight percent of B-4400, and
0.11 weight percent of the imidazole, NXJ-60;
3. 45 weight percent of an inorganic filler component, SO-E5 silica;
4. a flowability agent including the silanes (A-137, 0.09 weight percent) and (A-187, 0.12 weight percent), and titanate (KR-55, 0.45 weight percent); and
5. 0.1 weight percent of red pigment.
Two additional compositions (Sample Nos. 23-24) were prepared along these lines, except that the limonene diepoxide/RE-404-S ratio was varied, the weight percents of the components of the anhydride cure agent were also varied, and the weight percent of the inorganic filler component were varied as well. [See Table 2(c).]
Table 2 (c)
Figure imgf000045_0001
Yet a further additional thermosetting resin composition (Sample No. 26) was prepared based on a limonene diepoxide (commercially available from Daicel Chem. Co., Ltd., Japan under the tradename "CELLOXIDE" 3000), designed to cure with a latent hardener (commercially available from Asahi-Ciba, Ltd., Japan under the tradename "NOVACURE" HX- 3921 HP) , and without a second epoxy resin, as described above by mixing together the following components:
1. an epoxy resin component including
40 weight percent of limonene diepoxide; and
2. a curing agent component including
60 weight percent of "NOVACURE" HX-3921 HP. Four additional compositions (Sample Nos. 27-30) were prepared along these lines, except that the limonene diepoxide/latent hardener ratio was varied, and an inorganic filler component was included in various weight percents, and a second epoxy resin was included in Sample No. 30. [See Table 2(c) .]
Table 2 (d)
Figure imgf000046_0001
Sample Nos. 31 and 32 show thermosetting resin compositions prepared from ethylidene norbornene diepoxide and methyl cyclopentadiene dimer diepoxide, respectively, designed to cure with an anhydride curing agent . Sample Nos. 33-35 show thermosetting resin compositions, based on limonene diepoxide/RE-404-S in combination at various ratios (like Sample Nos. 21-25) designed to cure with an anhydride curing agent, an imidizole curing agent, or both. Sample Nos. 36-40 show thermosetting resin compositions based on limonene diepoxide designed to cure with a latent hardener (commercially available for Asahi-Ciba, Ltd., Japan under the tradename "NOVACURE" HX03921 HP) , with and without an inorganic filler. [See Table 2(d).]
Yet a further additional thermosetting resin composition (Sample No. 41) was prepared based on a limonene diepoxide (commercially available from Daicel Chem. Co., Ltd., Japan under the tradename "CELLOXIDE" 3000), designed to cure with a latent hardener (commercially available from Asahi-Ciba, Ltd., Japan under the tradename "NOVACURE" HX- 3921 HP) , without a second epoxy resin, as described above by mixing together the following components:
1. an epoxy resin component including
40 weight percent of limonene diepoxide; and
2. a curing agent component including 60 weight percent of "NOVACURE" HX-3921 HP.
Nine additional compositions (Sample Nos. 42-49) were prepared along these lines, except that the type and amount of the epoxy resin was varied as noted, and an inorganic filler component was included in various weight percents, and a second epoxy resin was included in Sample
Nos. 43 and 46-49, with a third epoxy resin being including in Sample Nos. 47 and 48. [See Table 2(e) .] Table (β)
Figure imgf000048_0001
In Table 2(f) below, combinations of RE-404-S together with either methyl cyclopentadiene dimer diepoxide, ethylidene norbornene diepoxide or nopol epoxide dylycidyl ether, at different ratios are presented as Sample Nos. 50- 58, designed to cure with anhydride curing agents, and Sample No. 59, which is nopol epoxy glycidyl ether cured with an anhydride curing agent .
Table 2(f)
Figure imgf000049_0001
Shelf-Stability
While the compositions were used upon formation (see below) , they may be stored for a period of time of up to about 3 to about 6 months at a temperature of about -40°C without experiencing viscosity increase.
After formation, the composition was transferred to a 10 ml syringe made of non-reactive plastic. Mounting/Underfill Process
Using cream solder (PS10R-350A-F92C; manufactured by Harima Chemicals, Inc.), a CSP having a package of 20mm square, an electrode diameter of 0.5mm, an electrode pitch of 1.0mm, and a carrier substrate made of alumina was mounted on a 1.6mm thick glass-reinforced epoxy board having a circuit formed thereon.
Certain of the samples (Sample Nos. 17-25) were dispensed through a 12G needle connected to the syringe into the junction between the carrier substrate and semiconductor device an assembly previously formed as above.
After such dispensing, the assembly was transferred to an oven while the temperature was maintained at about 165°C. The composition cured initially after about 1 minute, and thereafter cured completely after about 15 minutes at that temperature .
Rather than using all the samples as underfill sealants, certain of them (Sample Nos. 1-16) were dispensed onto an aluminum dish, and cured in a step-wise manner by exposure to an elevated temperature of about 100°C for a period of time of about 2 hours, followed by exposure to an elevated temperature of about 140°C for a period of time of about 6 hours, at the end of which time the compositions were observed to have cured.
Physical Properties
The compositions have a variety of properties in both the uncured and cured state which are measurable and useful parameters for the end user in choosing a particular formulation for a desired need.
For instance, in the uncured state, the flow rate is of interest; in reaching the cured state, the cure schedule is of interest .
The flow time allows the end user to determine the rapidity with which the adhesive may be applied during a fabrication process, such as a circuit assembly operation. It may be measured by passing the composition through a 25 μm gap between glass slides aligned perpendicular to one another, using metal shims as spacers. The time required for the composition to flow between the slides is then measured at a length of about one inch, "at 0.25 inch intervals. Values in seconds for the flow times of the compositions set forth above are presented as an average of three measurements below in Table 3.
The cure schedule refers to the time required for the onset of cure to occur at a certain temperatrue, in a specified period of time. This may be seen in more detail with regard to certain of the samples prepared in accordance with the present invention below in Table 3.
Table 3
Figure imgf000051_0001
As the composition progresses through its cure schedule, the reaction exotherm, or enthalpy, assists in determining the effectiveness of a (co) polymerization reaction. The reaction exotherm here is measured by differential scanning calorimetry ("DSC") . The peak temperature ("TPEAK") and onset temperature ("T0NSET") may be determined from the DSC measurement . These values provide information for minimum reasonable curing temperatures, the curing temperature range, maximum reaction temperatures, and relative curing time at each temperature. See Tables 4a, 4(b) and 4(c) .
Table 4(a)
Figure imgf000052_0001
In the cured state, a variety of properties are useful depending on the end use for which the composition is destined.
For instance, adhesion provides information on the strength of the bond formed by the cured reaction product, data for which is set forth in Table 5. In this adhesion evaluation, die shear adhesion is measured by a Sebastion 5 die shear measurement instrument, which measures the amount of shear strength (in Kgf) required to pull apart a die attached to a circuit board by the cured reaction product as an underfill sealant (without a solder mask, or chipbonding adhesive) .
Table 5
Figure imgf000053_0001
Reworkability determines the ease with which a cured reaction product may be controllably degraded. The extent to which the cured reaction product loses mass over time at an increase in temperature may be measured by thermal gravimetric analysis ("TGA"), and provides information on the temperature (or range) at which the cured reaction product degrades.
Reference to FIGs . 3-4 show TGA data for cured reaction products of Sample Nos. 1-5 using an anhydride curing agent, compared with TGA data for cured reaction products of compositions based on the commercially available epoxies ERL-4221 (Sample No. 4) and RE-404-S (Sample No. 5), and Compound XVI of the '922 and '033 patents (Sample No. 3) .
Reference to FIGs. 5-6 show TGA data for cured reaction products of Sample Nos. 7-10 using an imidazole/dicyandiamide curing agent, compared with TGA data for cured reaction products of compositions based on the commercially available epoxies ERL-4221 (Sample No. 9) and RE-404-S (Sample No. 10), and Compound XVI of the '922 and '033 patents (Sample No. 8). Reference to FIGs. 7-8 show TGA data for cured reaction products of Sample Nos. 10 and 11-16 using an imidazole/dicyandiamide curing agent, comparing TGA data for cured reaction products of compositions based on the commercially available RE-404-S, and cured reaction products of 80:20, 70:30, and 60:40 combinations of limonene diepoxide/RE-404-S (Sample Nos. 11-13) and of terpinene diepoxide (Sample Nos. 14-16).
Reference to FIGs. 9-10 show TGA data for anhydride cured reaction products of Sample Nos. 5 (RE-404- S) , 32 (methyl cyclopentadiene dimer diepoxide), and 50-52, having 80:20, 60:40 and 40:60 combinations of methyl cyclopentadiene dimer diepoxide/RE-404-S and RE-404-S, and for anhydride cured reaction products of methyl cyclopentadiene dimer diepoxide (Sample No. 32), the commercially available epoxies ERL-4221 (Sample No. 4) and RE-404-S (Sample No. 5), and Compound XVI of the '922 and '033 patents (Sample No. 3).
Reference to FIGs. 11-12 show TGA data for anhydride cured reaction products of Sample Nos. 5, 31 (ethylidene norbornene diepoxide), 53-55, having 80:20, 60:40 and 40:60 combinations of ethylidene norbornene diepoxide/RE-404-S, and RE-404-S, and anhydride cured reaction products of ethylidene norbornene diepoxide (Sample No. 31), the commercially available epoxies ERL-4221 (Sample No. 4) and RE-404-S (Sample No. 5), and Compound XVI of the '922 and '033 patents (Sample No. 3).
Reference to FIGs. 13-14 show TGA data for anhydride cured reaction products of Sample Nos. 5, 55-58 and 59 (nopol epoxide glycidyl ether), having 80:20, 60:40, and 40:60 combinations of nopol epoxide glycidyl ether/RE- 404-S, and RE-404-S, and anhydride cured reaction products of nopol epoxide glycidyl ether (Sample No. 59), commercially available epoxies ERL-4221 (Sample No. 4), and RE-404-S (Sample No. 5), and Compound XVI of the '922 and '033 patents (Sample Nos. 3) . The TGA data indicate that cured reaction products of the inventive compositions (e.g., Sample Nos. 1-2, and 7- 8) degrade and lose mass at a temperature lower than cured reaction products of the compositions based on either of the commercially available epoxies, to which reference is made above .
Practical reworkability was demonstrated using a hot air generator to heat the area around the die, fixed to the circuit board with the compositions of Sample Nos. 17- 25, 42-46 and 49, to an air temperature of about 280°C, with a die temperature of about 215-220°C for a period of time of about 1 to about 2 minutes. Then, the die may be easily removed by pulling or twisting the die from the circuit board using tweezers in a period of time of about 20 to about 30 seconds. The circuit board may then be cleaned using a dremel at about 25,000 rpm, followed by application of a flat-end horse hair brush. The circuit board cleaning ordinarily occurs within a period of time of about 2 to about 3 minutes . In addition, Sample Nos. 26-30 were reworked by localized heating to a temperature of about 100°C for a period of time of about 60 minutes. Although reworkability data for these samples was observed, an increased temperature for a shortened time perod would likely improve the data observed.
Thermosetting resin compositions prepared without limonene diepoxide, with the balance of the epoxy resin component from the RE-404-S epoxy resin (e.g. , Sample Nos. 5 or 10) , which was dispensed and cured as above, do not allow for die removal in the manner so described.
The site of the failed semiconductor chip should then be fluxed and a new semiconductor chip may be attached using conventional flip chip technology. Then, the thermosetting resin composition of this invention may be applied around the periphary of the newly-replaced semiconductor chip and cured by heating to an appropriate temperature, as described herein. The samples described above are presented as illustrative, rather than limiting, examples of the inventive compositions. Many additional embodiments thereof are included in the spirit and scope of the invention, which is defined by the claims .

Claims

What Is Claimed Is;
1. A thermosetting resin composition, said composition comprising:
(a) a curable resin component, at least a portion of which is a compound having at least one linkage selected from the group consisting of oxiranes and thiiranes, substituted on at least three of the substitutable positions on the oxirane or thiirane carbons, respectively, with an alkyl,* alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interruption by one or more heteroatoms or halogens (I) ; and
(b) a curing agent component selected from the group consisting of anhydride compounds, amine compounds, amide compounds, imidazole compounds, and combinations thereof, provided that the compound I does not include as its sole component an epoxy compound within formula II:
Figure imgf000057_0001
wherein each R is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, Cι_4 alkoxy, halogen, cyano and nitro, Ri and R2 are each independently selected from 'the 'group consisting of hydrogen, methyl, ethyl, and propyl, provided that both Rx and R2 cannot be hydrogen, and R3 is indpendently selected from propyl, and isopropyl, provided at least one of R3a and Rb, and at least one of R3c and R3d is independently selected from the group consisting of methyl, ethyl, propyl, and isopropyl, and m is 0 or 1.
2. The composition according to Claim 1, wherein reaction products of which are capable of softening and losing their adhesiveness under exposure to temperature conditions in excess of those used to cure the composition
3. The composition according to Claim 1, wherein the curable resin component includes a compound having at least one oxirane linkage substituted on at least three of the substitutable positions on the oxirane carbons with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interuption by one or more heteroatoms or halogens .
4. The composition according to Claim 3, wherein the compound having at least one oxirane linkage is a member selected from the group consisting of oxiranes prepared from 2, 10-dimethyl-6-methylene-4, 8-bis (2-methyl-l-propenyl
2, 4,7, 9-undecatetraene, 4-[(4E or 4Z) -1, 5-dimethyl-4- heptenylidene or octenylidene] -1-methyl-cyclohexene, 1,1'- [(1E or 1Z, 3E or 3Z) -5- (1, l-dimethyl-2-propenyl) -3- (3- methyl-2-butenyl) -1, 3-pentadiene-l, 5-diyl] bis-benzene, 4, 6- dimethyl-[S or R- (E or Z, Z or E) ] -2, 5-octadiene, 2,6,10,14- tetramethyl-7- (3-methyl-4-pentenyl) -2, 5, 9, 13- pentadecatetraene, 7-ethyl-3, 11-dimethyl- (3Z or 3E, 6E or 6Z, 10Z or 10E) -1,3, 6, 10-tridecatetraene, 3, 4, 8-trimethyl- 1,4, 7-nonatriene, 13-ethyl-9-methyl-l, 9, 12- pentadecatetraene, l-methyl-4- (2-methyl-6-heptenylidene) - cyclohexene, 2, 6, 11-trimethyl- (E or Z) -2, 5, 10-dodecatriene, 2, 6-dimethyl- (E or Z, E or Z) -2, 6, 9-tetradecatriene, 7- (3- methyl-2-butenyl- (E or Z) -6-dodecene, 6- (3-methyl-2- butenyl)-(E or Z) -6-dodecene, 2, 4, 6, 6, 8-pentamethyl-2, 4, 7- nonatriene, 3, 7-dimethyl-ll- (methyl) - (E or Z, E or Z)- 1,3, 6, 10-dodecatetraene, 5- [3-methyl-l- (2-methyl-l- propenyl) -2-butenylidene] -1, 3-cyclopentadiene, 4-[(4E or 4Z) -l,5-dimethyl-4-heptenylidene] -1-methyl- (4Z or 4E)- cyclohexene, 3,7, 11-trimethyl-l, 3,6, 10-docosatetraene, 3,7,11, 15-tetramethyl-l, 3,6, 10-hexadecatetraene, 9-ethyl- 2, 6-dimethyl- (E or Z, E or Z) -2, 6, 9-dodecatriene, 2-methyl- 5-propyl- (E or Z) -2, 5-nonadiene, 3, 7, 11-trimethyl- (Z or E, E or Z, E or Z) -1, 3, 6, 10-dodecatetraene, 4 , 8 , 12-trimethyl- (Z or E, E or Z, E) -2, 4, 1 , 11-tridecatetraene, 1-methyl- - (2- methyl-6-heptenylidene) - (E or Z) -cyclohexene, 3-ethyl-7, 11- dimethyl- (E or Z, E or Z)-l,3, 6, 10-dodecatetraene, 2, 6, 6, 9-tetramethyl-7- (2-methyl-l-propenyl) -2,4,8- decatriene, 2, 7-dimethyl-4, 5-bis (2-methyl-l-propenyl) -2, 6- octadiene, 3, 7-dimethyl-l, 3, 6-octatriene, 2-methyl-5- (1- ethylethylidene) -cyclohexene, 2, 6-dimethyl-5- (1- methylethylidene) -1, 3-cyclohexadiene, 2, 6-dimethyl-2, 5- decadiene or octadiene, 7-ethyl-3, 11-dimethyl-l, 3, 6, 10- dodecatetraene, 2-methyl-(E or Z) -2, 5-octadiene, 7-ethyl- 3, 11-dimethyl- (E or Z, E or Z) -1, 3, 6, 10-dodecatetraene, 2, 7, 11-trimethyl- (E or Z) -2, 5, 10-dodecatriene, 6,10- dimethyl-(Z or E, Z or E) -2, 6, 9-undecatrien-4-yne, 2,6- dimethyl-(Z or E) -2, 5-dodecadiene, 2, 7-dimethyl-4 , 5-bis (2- methyl-1-propenyl) -2,4, 6-octatriene, 2,3,6, 7-tetramethyl- 1, 3, 6-octatriene, 2-methyl-5-propyl- (Z or E)-2,5- dodecadiene, 2-methyl-5- (1-methylethyl) - (E or Z)-2,5- dodecadiene, 2-methyl-(Z or E) -2 , 5-dodecadiene, 2,4,4- tri ethyl- (E or Z) -2, 5-heptadiene, 2, 6-dimethyl-2, 5- octadiene, 3, 4 , 7 , 11-tetramethyl- (E or Z, Z or E) -1,3, 6,10- dodecatraene, 3, 7 , 11-trimethyl- (E or Z, E or Z)-l, 3, 6, 10- dodecatetraene, 4, 8-dimethyl-l, 4, 7-nonatriene, 3,7,11,15- tetramethyl-1, 3, 6, 10, 14-hexadecapentaene, 2-methyl-(Z or E)- 2 , 5-pentadecadiene, 2-methyl-5- ( 1-methylethylidene) -2- deceηe, 2, 6-dimethyl-2, 5, 7-decatriene, 4, 8-dimethyl-2, 4, 7- nonatriene, 15,19, 23-trimethyl-15, 18,22- heptatriacontatriene, 8- (2-methyl-l-propenyl) -6-tetradecene, 3, 7, 11-trimethyl- (E or Z) -1, 3, 6, 10-dodecatetraene, 3,4- didehydro-2- (3-methyl-2-butenyl) -carotene, 7-ethyl-3, 11- dimethyl-l, 3, 6, 10-dodecatetraene, 1, 3-dimethyl-4- propylidene-cyclopentene, 2, 7, 11-trimethyl- (E or Z, E or Z)- 1,3,6, 10-dodecatetraene, 6, 10-dimethyl-l, 4,6,9- undecatetraene, 2- (1-methylethyl) -5- (1-methylethylidene) - 1, 3-cyclohexadiene, 2-ethyl-5-ethylidene-cyclohexadiene, 2- methyl-5- (1-methylethylidene) -1, 3-cyclohexadiene, 3, 7, 10- trimethyl- (Z or E, E or Z) -1, 3, 6-undecatriene, 4- (1,5- dimethyl-4-hexenylidene) -1-methyl-cyclohexene, l-methyl-4- (1-methylethylidene) -cyclohexene, 2, 5-dimethyl- (Z or E)-2,5- heptadiene, 2-methyl-5- (1-methylethylidene) -1, 3- cyclohexadiene, 2, 6, 10-trimethyl- (E or Z, Z or E) -2,6,9- tetradecatriene, 6-methyl-(Z or E, E or Z) -2 , 5-dodecadiene, 2, 3, 6-trimethyl- (E or Z, E or Z) -1, 3, 6-octatriene, tetrahydro-3, 7 , 11-trimethyl-l, 3,6, 10-dodecatetraene, 3,4,7, 11-tetramethyl-l, 3,6, 10-dodecatetraene, 3, 4 , 7, 11- tetramethyl- (Z or E, Z or E) -1, 3, 6, 10-dodecatetraene, 2,6- dimethyl-4-methylene-2, 5-heptadiene, 5-ethyl-2-methyl-2, 5- heptadiene, 2, 5-dimethyl-2, 5-heptadiene or octadiene, 3, 7, 11-trimethyl-dodecatriene, 2, , 6, 6, 8-pentamethyl- (E or Z) -2, 4, 7-nonatriene, 3, 7-diethyl-ll-methyl-l, 3, 6, 10- tridecatetraene, 7-ethyl-3, 11-dimethyl-l, 3, 6, 10- tridecatetraene, 2, 6-dimethyl- (E or Z) -2 , 5-dodecadiene, 2, 6, 10-trimethyl- (E or Z, E or Z) -2, 6, 9-tetradecatriene, 3,7, 11, 15-tetramethyl- (Z or E, E or Z, E or Z) -1, 3, 6, 10, 14- hexadecapentaene, 3, 7, 11, 15-tetramethyl- (3E or 3Z, 6E or 6Z, 10E or 10Z) -1, 3, 6, 10, 14-hexadecapentaene, l-ethenyl-4- (1- methylethylidene) -cyclohexene, l-methyl-6-methylene-4- (1- methylethylidene) -cyclohexene, 3, 7, 11-trimethyl-l, 3, 6- dodecatriene, 4- (1, 5-dimethylhexylidene) -1-methyl- cyclohexene, 7-ethyl-3, 11-dimethyl- (3Z or 3E, 6E or 6Z)- 1,3,6, 10-dodecatetraene, 1,3, 3', 4, ', 16-hexadehydro-l, 2- dihydro-2, 2 ' -bis-3-carotene, 7-methyl-(Z or E, Z or E)-3,6- dodecadiene, 6-ethylidene-2, 3, 10-trimethyl- (E or Z, E or Z)- 1, 3, 9-undecatriene, 2, 3, 6, 7', 10, 11-hexamethyl- (E or Z, E or Z) -1, 3, 6, 10-dodecatetraene, 2, 3, 6, 7-tetramethyl- (E or Z)- 1,3, 6-octatriene, 2,7, 11-trimethyl-l, 3, 6, 11-dodecatetraene, 3,7,11,15,19,23,27,31,35-nonamethyl-
1,3, 6, 10, 14, 18, 22, 26, 30, 34-hexatriacontadecaene, 2,6- dimethyl-9-propyl-2, 6, 9-tridecatriene, 3, 6-dimethyl- (E or Z, E or Z) -1, 3, 6-octatriene, 3, 7-diethyl-ll-methyl- (3Z or 3E, 6E or 6Z) 1, 3, 6, 10-tridecatetraene, 7-ethyl-3, 11-dimethyl- (3Z or 3E, 6E or 6Z) -1, 3, 6, 10-tridecatetraene, l-methyl-4- (5-methyl-4-hexenylidene) - (4E or 4Z) -cyclohexene, 2,6,10- trimethyl-(Z or E) -2, 5, 9-undecatriene, 2 , 6, 1 , 7-tetramethyl- (Z or E) -2, 5-octadiene, 2, 6, 10, 11, ll-pentamethyl-2, 6, 9- dodecatriene, 2, 6, 10-trimethyl-2, 6, 9-tetradecatriene, 2,6- dimethyl- (Z or E) -2, 5-decadiene, 6, 10-dimethyl-l, 6, 9- undecatrien-4-yne, 2, 3, 6-trimethyl-2, 5-heptadiene, 2,4- dimethyl- (E or Z) -2, 5-heptadiene, 2, 7 , 11-trimethyl- (E or Z, E or Z) -1, 3, 6, 11-dodecatetraene, 6-ethyl-3-methyl-2, 5- decadiene, 2, 6, 10-trimethyl- (Z or E) -2, 5-undecadiene, 3,7- dimethyl-3, 6-octadien-l-yne, 2,7, 10-trimethyl-l, 6, 9- undecatriene, 4, 5-dimethyl- (E or Z, E or Z, E or Z)-3,5,8- undecatriene, 4, 5-dimethyl-2, 5, 8-undecatriene, 1 ' - [4-methyl- 2- (2-methyl-l-propenyl) -1 , 3-pentadienylidene] bis-benzene, 1, 4- (l,5-dimethyl-4-hexenylidene) -1-methyl- (4E or 4Z)- cyclohexene, 2, 6, 11, 15-tetramethyl- (Z or E) -2, 6, 9,14- hexadecatetraene, [3-methyl-l- (2-methyl-l-propenyl) -2- butenyl] -benzene, 2, 6, 11-trimethyl- (E or Z, E or Z) -2,6,9- dodecatriene, 2, 6-dimethyl- (E or Z, E or Z) -2,6,9- dodecatriene, 2, 3, 6, 7, 10, 11-hexamethyl-l, 3, 6, 11- dodecatetraene, 19-methyl-l- (2-methyl-l-
2,4,6,8, 10, 12, 14, 16, 18-eicosanonaenylium, 17-methyl-l- (2- methyl-1-propenyl) -2, 4, 6, 8, 10, 12, 14, 16-octadecaoctaenylium, 15-methyl-l- (2-methyl-l-propenyl) -2, 4, 6, 8, 10, 12, 14- hexadecaheptaenylium, 13-methyl-l- (2- methyl-1-proρenyl) - 2, 4, 6, 8, 10, 12-tetradecahexaenylium, 11-methyl-1- (2-methyl-l- propenyl) -2,4,6,8, 10-dodecapentaenylium, 9-methyl-l- (2- methyl-1-propenyl) -2,4,6, 8-decatetraenylium, 7-methyl-1- (2- methyl-1-propenyl) -2,4, 6-octatrienylium, 4, ethylidene-2, 6- dimethyl-2, 5-heptadiene, 3, 7, 11-trimethyl- (E or Z) -3, 6, 11- dodecatrien-l-yne, 3, 7-dimethyl- (3E or 3Z) -3, 6-octadien-l- yne, 3, 7-dimethyl- (E or Z) -3, 6-nonadien-l-yne, 3,6,7- trimethyl- (E or Z) -3, 6-octadien-l-yne, 7-ethyl-3-methyl- (E or Z) -3, 6-nonadien-l-yne, 3, 7 , 11-trimethyl- (Z or E) -3, 6, 11- dodecatrien-l-yne, 2,3,6,7, 10, 11-hexamethyl-l, 3, 6, 11- dodecatetraene, 2, 6-dimethyl-2, 5-heptadiene, 2-methyl-2, 5- heptadiene, 3,6, 10-trimethyl-2, 5,7, 10-dodecatetraene, 2,7, 10-trimethyl-l, 3,7, 10-dodecatetraene, 3, 6-dimethyl- 1,3, 6-octatriene, 12- (2, 2-dimethyl-6-methylenecyclohexyl) - 3,8,8-trimethyl-ll-methylene-(E or Z) - (S) -1, 3, 6- dodecatriene, ocimene, 3, 7, 11-trimethyl- (3Z or 3E, 6Z or 6E) -1, 3, 6, 10-dodecatetraene, 2-methyl-4-methylene-2, 5- heptadiene, 3, 8, 8, 14, 18-pentamethyl-ll-methylene- (E or Z)- 1, 3, 6, 13, 17-nonadecapentaene, 2, 7-dimethy1-2, 5-octadiene, 3, 8, 8, 14, 18-pentamethyl-ll-methylene- (E or Z, E or Z, E or Z) -1, 3, 6, 13, 17-nonadecapentaene, 6, 10-dimethyl-2, 4 , 6, 9- undecatetraene, 2-methyl- (Z or E) -2, 5-heptadiene, 2-methyl- (E or Z) -2, 5-heptadiene, 3, 7-dimethyl-l, 3, 6-octatriene, 4- (1, 5-dimethyl-4-hexenylidene) -1-methyl- (4Z or 4E)~ cyclohexene, 2, 6, 10, 14, 19, 22, 27, 31-octamethyl- 2, 6, 10, 14, 16, 18, 22, 26, 30-dotriacontanonaene, 2, 6-dimethyl- 2, 5-heptadiene, 4- (1, 5-dimethyl-4-hexenylidene) -1-methyl- cyclohexene, 3, 7-dimethyl- (3E or 3Z) -1, 3, 6-octatriene, 2,6,10,14,19,23,31-heptamethyl-2,5,10,14,16,18,22,26,29- dotriacontanonaene, 3, 7, dimethyl- (3Z or 3E) -1,3,6- octatriene, 3-methyl-l- (2-methyl-l-propenyl- (E or Z)-2- pentenyl, 2, 6-dimethyl-4- (2-methylpropenyl) -1,3,5- heptatriene, 2, 6-dimethyl-4-methylene-2, 5-heptadiene, 1- methyl-4- (1-methylethylidene) -cyclohexene, 3,7, 11-trimethyl- (3E or 3Z, 6E or 6Z) -1, 3, 6, 10-dodecatetraene, 4-(l,5- dimethyl-4-hexenylidene) -1-methyl-cyclohexene, isoprene, myrcene, dihydromyrene, linalool, terpinenes (o., β, and y) , limonene, terpinolene, menthadiene (p-3,8 or p-2,4), geraniol, nerol, geranylacetate, neryl acetate, nerolidol, farnesol, dehydronerolidol, -bisabolol, valancene, nookatene, nootkatone, dimethyl-2, 4, 6-octratriene, β- phellandrences, piperitols (-, cis and +, trans), 1-methyl- 1, 4-cyclohexadiene, methyl cyclopentadiene dimer, ethylidene norbornene, dipentene, carvestrene, carvone (- or +) , alloocimenes (4-trans-6-cis and 4-trans-6-trans) , alloocimenols, ionomers, guaiazulene, lanosterol, squalene, lycopene, carotenes [β and γ) , nopol glycidyl ether, and combinations thereof.
5. The composition according to Claim 3, wherein the compound having at least one oxirane linkage is a member selected from the group consisting of limonene diepoxide, gamma-terpinene diepoxide, methyl cyclopentadiene diepoxide dimer, ethylidene norbornene diepoxide, nopol epoxide glycidyl ether and combinations thereof.
6. The composition according to Claim 1, wherein the anhydride component of the curing agent component may be selected from the group consisting of hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, 5- (2, 5- dioxotetrahydrol) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, and combinations thereof.
7. The composition according to Claim 1, wherein the amine compounds of the curing agent component may be selected from the group consisting of 1, 5-diazabiyclo
[4.3.0]non-5-ene; 1, 8-diazabiylo [5.4.0] undec-7-ene; 1,5,7- triazabicyclo [4.4.0] dec-5-ene; quinuclidine; 1,4- diazabicyclo [2.2.2. ] octane; and combinations thereof.
8. The composition according to Claim 1, wherein the amide compounds of the curing agent component may be dicyandiamide .
9. The composition according to Claim 1, wherein the imidazole compounds of the curing agent component may be selected from the group consisting of imidazole, isoimidazole, 2-methyl imidazole, 2-ethyl-4-methylimidazole, 2, 4-dimethylimidazole, butylimidazole, 2-heptadecenyl-4- methylimidazole, 2-undecenylimidazole, l-vinyl-2- methylimidazole, 2-n-heptadecylimidazole, 2- undecylimidazole, 2-heptadecylimidazole, l-benzyl-2- methylimidazole, 1-propyl-2-methylimidazole, l-cyanoethyl-2- methylimidazole, l-cyanoethyl-2-ethyl-4-methylimidazole, 1- cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- phenylimidazole, 1-guanaminoethyl-2-methylimidazole, addition products of an imidazole and trimellitic acid, addition products of an imidazole and 2-n-heptadecyl-4- methylimidazole, phenylimidazole, benzylimidazole, 2-methyl- 4, 5-diphenylimidazole, 2, 3, 5-triphenylimidazole, 2- styrylimidazole, 1- (dodecyl benzyl) -2-methylimidazole, 2- (2- hydroxyl-4-t-butylphenyl) -4, 5-diphenylimidazole, 2- (2- methoxyphenyl) -4, 5-diphenylimidazole, 2- (3-hydroxyphenyl) - 4, 5-diphenylimidazole, 2- (p-dimethylaminophenyl) -4,5- diphenylimidazole, 2- (2-hydroxyphenyl) -4, 5- diphenylimidazole, di (4, 5-diphenyl-2-imidazole) -benzene-1, 4, 2-naphthyl-4, 5-diphenylimidazole, l-benzyl-2- methylimidazole, 2-p-methoxystyrylimidazole, and combinations thereof.
10. The composition according to Claim 1, wherein the curing agent component is used in an amount of from about 1 to about 100 weight percent, based on the weight of the epoxy resin component.
11. The composition according to Claim 1, further comprising an inorganic filler component.
12. The composition according to Claim 11, wherein the inorganic filler component may be selected from the group consisting of materials constructed of or containing reinforcing silicas, aluminum oxide, silicon nitride, aluminum nitride, silica-coated aluminum nitride, boron nitride, and combinations thereof.
13. The composition according to Claim 11, wherein the inorganic filler component has a low ion concentration and a particle size in the range of about 2-10 microns .
14. The composition according to Claim 1, further comprising a flowability agent.
15. The composition according to Claim 14, wherein the flowability agent is a member selected from the group consisting of silanes, titanates and combinations thereof .
16.- The composition according to Claim 14, wherein the flowability agent is a member selected from the group consisting of octyl trimethoxy silane, methacryloxy propyl trimethoxy silane, titanium IV tetrakis [2,2-bis[(2- propenyloxy) methyl] -l-butanolato-0]
[bis (ditridecylphosphito-0) , dihydrogen] 2, and combinations thereof .
17. The composition according to Claim 1, further comprising an adhesion promtor.
18. The composition according to Claim 19, wherein the adhesion promoter is a member selected from the group consisting of glycidyl trimethoxysilane, gamma-amino propyl triethoxysilane, and combinations thereof.
19. The composition according to Claim 1, further comprising a cyanate ester.
20. The composition according to Claim 19, wherein the cyanate ester is a member selected from the group consisting of dicyanatobenzenes, tricyanatobenzenes, dicyanatonaphthalenes, tricyanatonaphthalenes, dicyanato- biphenyl, bis (cyanatophenyl) methanes and alkyl derivatives thereof, bis (dihalocyanatophenyl) propanes, bis (cyanatophenyl) ethers, bis (cyanatophenyl) sulfides, bis (cyanatophenyl) propanes, tris (cyanatophenyl) phosphites, tris (cyanatophenyl) phosphates, bis (halocyanatophenyl) methanes, cyanated novolac, bis [cyanatophenyl (methylethylidene) ] benzene, cyanated bisphenol-terminated thermoplastic oligomers, and combinations thereof.
21. The composition according to Claim 1, which is capable of sealing underfilling between a semiconductor device including a semiconductor chip mounted on a carrier substrate and a circuit board to which the semiconductor device is electrically connected.
22. The composition according to Claim 1, which is capable of sealing underfilling between a semiconductor device including a semiconductor chip mounted on a carrier substrate and a circuit board to which the semiconductor device is electrically connected, wherein the curable resin component is present in an amount within the range of about 10 to 70 weight percent, based on the total weight of the composition; the curing agent component is present in an amount within the range of 1 to about 100 weight percent, based on the weight of the curable resin component; and further comprising an inorganic filler component in an amount up to about 70 weight percent, based on the total weight of the composition; and a flowability agent in an amount up to about 2 weight percent, based on the weight of the composition.
23. The composition according to Claim 1, wherein the curable resin component includes a compound having at least one thiirane linkage substituted on at least three of the substitutable positions on the thiirane carbons with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interuption by one or more heteroatoms or halogens.
24. The composition according to Claim 23, wherein the compound having at least one thiirane linkage is a member selected from the group consisting of thiiranes prepared from 2, 10-dimethyl-6-methylene-4, 8-bis (2-methyl-l- propenyl 2, 4, 7, 9-undecatetraene, 4-[(4E or 4Z) -1, 5-dimethyl- 4-heptenylidene or octenylidene] -1-methyl-cyclohexene, 1,1'- [(1E or 1Z, 3E or 3Z) -5- (1, l-dimethyl-2-propenyl) -3- (3- methyl-2-butenyl) -1, 3-pentadiene-l, 5-diyl] bis-benzene, 4,6- dimethyl-[S or R- (E or Z, Z or E) ] -2, 5-octadiene, 2,6,10,14- tetramethyl-7- (3-methyl-4-pentenyl) -2,5,9,13- pentadecatetraene, 7-ethyl-3, 11-dimethyl- (3Z or 3E, 6E or 6Z, 10Z or 10E) -1, 3, 6, 10-tridecatetraene, 3, 4 , 8-trimethyl- 1,4, 7-nonatriene, 13-ethyl-9-methyl-l, 9, 12- pentadecatetraene, l-methyl-4- (2-methyl-6-heptenylidene) - cyclohexene, 2, 6, 11-trimethyl- (E or Z) -2, 5, 10-dodecatriene, 2, 6-dimethyl- (E or Z, E or Z) -2, 6, 9-tetradecatriene, 7- (3- methyl-2-butenyl- (E or Z) -6-dodecene, 6- (3-methyl-2- butenyl)-(E or Z) -6-dodecene, 2, 4, 6, 6, 8-pentamethyl-2, 4, 7- nonatriene, 3, 7-dimethyl-ll- (methyl) - (E or Z, E or Z)- 1,3,6, 10-dodecatetraene, 5- [3-methyl-l- (2-methyl-l- propenyl) -2-butenylidene] -1, 3-cyclopentadiene, 4-[(4E or 4Z) -l,5-dimethyl-4-heρtenylidene] -1-methyl- (4Z or 4E)- cyclohexene, 3,7, 11-trimethyl-l, 3, 6, 10-docosatetraene, 3,7,11, 15-tetramethyl-l, 3,6, 10-hexadecatetraene, 9-ethyl- 2, 6-dimethyl- (E or Z, E or Z) -2, 6, 9-dodecatriene, 2-methyl- 5-propyl- (E or Z) -2, 5-nonadiene, 3, 7 , 11-trimethyl- (Z or E, E or Z, E or Z) -1, 3, 6, 10-dodecatetraene, 4, 8, 12-trimethyl- (Z or E, E or Z, E) -2, , 7, 11-tridecatetraene, l-methyl-4- (2- methyl-6-heptenylidene) - (E or Z) -cyclohexene, 3-ethyl-7 , 11- dimethyl- (E or Z, E or Z)-l,3, 6, 10-dodecatetraene, 2,6,6, 9-tetramethyl-7- (2-methyl-l-propenyl) -2,4,8- decatriene, 2 , 7-dimethyl-4 , 5-bis (2-methyl-l-propenyl) -2 , 6- octadiene, 3, 7-dimethy-l-l, 3, 6-octatriene, 2-methyl-5- (1- methylethylidene) -cyclohexene, 2, 6-dimethyl-5- (1- methylethylidene) -1, 3-cyclohexadiene, 2, 6-dimethyl-2, 5- decadiene or octadiene, 7-ethyl-3, 11-dimethyl-l, 3, 6, 10- dodecatetraene, 2-methyl- (E or Z) -2, 5-octadiene, 7-ethyl- 3, 11-dimethyl- (E or Z, E or Z) -1, 3, 6, 10-dodecatetraene, 2, 7, 11-trimethyl- (E or Z) -2, 5, 10-dodecatriene, 6,10- dimethyl-(Z or E, Z or E) -2, 6, 9-undecatrien-4-yne, 2,6- dimethyl-(Z or E) -2, 5-dodecadiene, 2, 7-dimethyl-4, 5-bis (2- methyl-1-propenyl) -2,4, 6-octatriene, 2,3,6, 7-tetramethyl- 1, 3, 6-octatriene, 2-methyl-5-propyl- (Z or E)-2,5- dodecadiene, 2-methyl-5- (1-methylethyl) - (E or Z)-2,5- dodecadiene, 2-methyl- (Z or E) -2, 5-dodecadiene, 2,4,4- trimethyl-(E or Z) -2, 5-heptadiene, 2, 6-dimethyl-2, 5- octadiene, 3, 4, 7, 11-tetramethyl- (E or Z, Z or E)-l,3,6,10- dodecatraene, 3, 7, 11-trimethyl- (E or Z, E or Z) -1,3, 6, 10- dodecatetraene, 4, 8-dimethyl-l, 4, 7-nonatriene, 3,7,11,15- tetramethyl-1, 3, 6, 10, 14-hexadecapentaene, 2-methyl- (Z or E)- 2 , 5-pentadecadiene, 2-methyl-5- (1-methylethylidene) -2- decene, 2, 6-dimethyl-2, 5, 7-decatriene, 4, 8-dimethyl-2, 4, 7- nonatriene, 15,19, 23-trimethyl-15, 18, 22- heptatriacontatriene, 8- (2-methyl-l-propenyl) -6-tetradecene, 3, 7, 11-trimethyl- (E or Z) -1, 3, 6, 10-dodecatetraene, 3,4- didehydro-2- (3-methyl-2-butenyl) -carotene, 7-ethyl-3, 11- dimethyl-l, 3,6, 10-dodecatetraene, 1, 3-dimethyl-4- propylidene-cyclopentene, 2, 7, 11-trimethyl- (E or Z, E or Z)- 1,3,6, 10-dodecatetraene, 6, 10-dimethyl-l, ,6,9- undecatetraene, 2- (1-methylethyl) -5- (1-methylethylidene) - 1, 3-cyclohexadiene, 2-ethyl-5-ethylidene-cyclohexadiene, 2- methyl-5- (1-methylethylidene) -1, 3-cyclohexadiene, 3,7, 10- trimethyl- (Z or E, E or Z) -1, 3, 6-undecatriene, 4-(l,5- dimethyl-4-hexenylidene) -1-methyl-cyclohexene, l-methyl-4- (1-methylethylidene) -cyclohexene, 2, 5-dimethyl- (Z or E)-2,5- heptadiene, 2-methyl-5- (1-methylethylidene) -1, 3- cyclohexadiene, 2, 6, 10-trimethyl- (E or Z, Z or E) -2,6,9- tetradecatriene, 6-methyl-(Z or E, E or Z) -2, 5-dodecadiene, • 2, 3, 6-trimethyl- (E or Z, E or Z) -1, 3, 6-octatriene, tetrahydro-3, 7, 11-trimethyl-l, 3,6, 10-dodecatetraene, 3,4,7, 11-tetramethyl-l, 3,6, 10-dodecatetraene, 3, 4, 7, 11- tetramethyl- (Z or E, Z or E) -1, 3, 6, 10-dodecatetraene, 2,6- dimethyl-4-methylene-2, 5-heptadiene, 5-ethyl-2-methyl-2, 5- heptadiene, 2, 5-dimethyl-2, 5-heptadiene or octadiene, 3, 7, 11-trimethyl-dodecatriene, 2 , 4, 6, 6, 8-pentamethyl- (E or Z) -2, 4, 7-nonatriene, 3, 7-diethyl-ll-methyl-l, 3,6, 10- tridecatetraene, 7-ethyl-3, 11-dimethyl-l, 3,6, 10- tridecatetraene, 2, 6-dimethyl- (E or Z) -2, 5-dodecadiene, 2, 6, 10-trimethyl- (E or Z, E or Z) -2, 6, 9-tetradecatriene, 3, 7, 11, 15-tetramethyl- (Z or E, E or Z, E or Z) -1, 3, 6, 10, 14- hexadecapentaene, 3, 7, 11, 15-tetramethyl- (3E or 3Z, 6E or 6Z, 10E or 10Z) -1, 3, 6, 10, 14-hexadecapentaene, l-ethenyl-4- (1- ethylethylidene) -cyclohexene, l-methyl-6-methylene-4- (1- methylethylidene) -cyclohexene, 3,7, 11-trimethyl-l, 3, 6- dodecatriene, 4- (1, 5-dimethylhexylidene) -1-methyl- cyclohexene, 7-ethyl-3, 11-dimethyl- (3Z or 3E, 6E or 6Z)- 1,3,6, 10-dodecatetraene, 1,3, 3', 4, 4', 16-hexadehydro-l, 2- dihydro-2, 2 ' -bis-3-carotene, 7-methyl-(Z or E, Z or E)-3,6- dodecadiene, 6-ethylidene-2, 3, 10-trimethyl- (E or Z, E or Z)- 1, 3, 9-undecatriene, 2, 3, 6, 7, 10, 11-hexamethyl- (E or Z, E or Z) -1, 3, 6, 10-dodecatetraene, 2, 3, 6, 7-tetramethyl- (E or Z)- 1,3, 6-octatriene, 2,7, 11-trimethyl-l, 3,6, 11-dodecatetraene, 3,7,11,15,19,23,27,31,35-nonamethyl-
1,3,6,10,14,18,22,26,30, 34-hexatriacontadecaene, 2,6- dimethyl-9-propyl-2, 6, 9-tridecatriene, 3, 6-dimethyl- (E or Z, E or Z) -1, 3, 6-octatriene, 3, 7-diethyl-ll-methyl- (3Z or 3E, 6E or 6Z) 1, 3, 6, 10-tridecatetraene, 7-ethyl-3, 11-dimethyl- (3Z or 3E, 6E or 6Z) -1, 3, 6, 10-tridecatetraene, l-methyl-4- (5-methyl-4-hexenylidene) - (4E or 4Z) -cyclohexene, 2, 6, 10- trimethyl- (Z or E) -2, 5, 9-undecatriene, 2 , 6, 7 , 7-tetramethyl- (Z or E) -2, 5-octadiene, 2, 6, 10, 11, ll-pentamethyl-2, 6, 9- dodecatriene, 2, 6, 10-trimethyl-2, 6, 9-tetradecatriene, 2,6- dimethyl-(Z or E) -2, 5-decadiene, 6, 10-dimethyl-l, 6, 9- undecatrien-4-yne, 2, 3, 6-trimethyl-2, 5-heptadiene, 2,4- dimethyl- (E or Z) -2, 5-heptadiene, 2, 7, 11-trimethyl- (E or Z, E or Z) -1, 3, 6, 11-dodecatetraene, 6-ethyl-3-methyl-2, 5- decadiene, 2, 6, 10-trimethyl- (Z or E) -2, 5-undecadiene, 3,7- dimethyl-3, 6-octadien-l-yne, 2,7, 10-trimethyl-l, 6,9- undecatriene, 4, 5-dimethyl- (E or Z, E or Z, E or Z) -3,5,8- undecatriene, 4, 5-dimethyl-2, 5, 8-undecatriene, 1 ' - [4-methyl- 2- (2-methyl-l-propenyl) -1, 3-pentadienylidene] bis-benzene, 1, 4- (l,5-dimethyl-4-hexenylidene) -1-methyl- (4E or 4Z)- cyclohexene, 2, 6, 11, 15-tetramethyl- (Z or E) -2, 6, 9,14- hexadecatetraene, [3-methyl-l- (2-methyl-l-propenyl) -2- butenyl] -benzene, 2, 6, 11-trimethyl- (E or Z, E or Z) -2,6,9- dodecatriene, 2, 6-dimethyl- (E or Z, E or Z)-2,6,9- dodecatriene, 2,3,6,7,10, 11-hexamethyl-l, 3, 6, 11- dodecatetraene, 19-methyl-l- (2-methyl-l-
2, 4, 6, 8, 10, 12, 14, 16, 18-eicosanonaenylium, 17-methyl-l- (2- methyl-1-propenyl) -2, , 6, 8, 10, 12, 14, 16-octadecaoctaenylium, 15-methyl-l- (2-methyl-l-propenyl) -2,4,6,8,10,12,14- hexadecaheptaenylium, 13-methyl-l- (2- methyl-1-propenyl) - 2,4,6,8,10, 12-tetradecahexaenylium, 11-methyl-1- (2-methyl-l- propenyl) -2,4,6,8, 10-dodecapentaenylium, 9-methyl-l- (2- methyl-1-propenyl) -2,4,6, 8-decatetraenylium, 7-methyl-l- (2- methyl-1-propenyl) -2,4, 6-octatrienylium, 4, ethylidene-2, 6- dimethyl-2, 5-heptadiene, 3, 7 , 11-trimethyl- (E or Z) -3, 6, 11- dodecatrien-l-yne, 3, 7-dimethyl- (3E or 3Z) -3, 6-octadien-l- yne, 3, 7-dimethyl- (E or Z) -3, 6-nonadien-l-yne, 3,6,7- trimethyl- (E or Z) -3, 6-octadien-l-yne, 7-ethyl-3-methyl- (E or Z) -3, 6-nonadien-l-yne, 3, 7 , 11-trimethyl- (Z or E) -3, 6, 11- dodecatrien-l-yne, 2,3,6,7, 10, 11-hexamethyl-l, 3, 6, 11- dodecatetraene, 2, 6-dimethyl-2, 5-heptadiene, 2-methyl-2, 5- heptadiene, 3,6, 10-trimethyl-2, 5,7, 10-dodecatetraene, 2,7, 10-trimethyl-l, 3,7, 10-dodecatetraene, 3, 6-dimethyl- 1,3, 6-octatriene, 12- (2, 2-dimethyl-6-methylenecyclohexyl) - 3,8,8-trimethyl-ll-methylene-(E or Z) - (S) -1, 3, 6- dodecatriene, ocimene, 3, 7, 11-trimethyl- (3Z or 3E, 6Z or 6E) -1,3,6, 10-dodecatetraene, 2-methyl-4-methylene-2, 5- heptadiene, • 3, 8, 8, 14, 18-pentamethyl-ll-methylene- (E or Z)- 1, 3, 6, 13, 17-nonadecapentaene, 2, 7-dimethyl-2, 5-octadiene, 3, 8, 8, 14, 18-pentamethyl-ll-methylene- (E or Z, E or Z, E or Z)-l,3,6,13, 17-nonadecapentaene, 6, 10-dimethyl-2, 4 , 6, 9- undecatetraene, 2-methyl- (Z or E) -2, 5-heptadiene, 2-methyl- (E or Z) -2, 5-heptadiene, 3, 7-dimethyl-l, 3, 6-octatriene, 4- (l,5-dimethyl-4-hexenylidene) -1-methyl- (4Z or 4E)- cyclohexene, 2 , 6, 10, 14, 19, 22 , 21 , 31-octamethyl- 2,6,10,14,16,18,22,26, 30-dotriacontanonaene, 2, 6-dimethyl- 2, 5-heptadiene, 4- (1, 5-dinnethyl-4-hexenylidene) -1-methyl- cyclohexene, 3, 7-dimethyl- (3E or 3Z) -1, 3, 6-octatriene, 2,6,10,14,19,23,31-heptamethyl-2,5,10,14,16,18,22,26,29- dotriacontanonaene, 3, 7, dimethyl- (3Z or 3E) -1,3,6- octatriene, 3-methyl-l- (2-methyl-l-propenyl- (E or Z)-2- pentenyl, 2, 6-dimethyl-4- (2-methylpropenyl) -1,3,5- heptatriene, 2, 6-dimethyl-4-methylene-2, 5-heptadiene, 1- methyl-4- (1-methylethylidene) -cyclohexene, 3,7, 11-trimethyl- (3E or 3Z, 6E or 6Z) -1, 3, 6, 10-dodecatetraene, 4-(l,5- dimethyl-4-hexenylidene) -1-methyl-cyclohexene, isoprene, myrcene, dihydromyrene, linalool, terpinenes (α, β, and y) , limonene, terpinolene, menthadiene (p-3,8 or p-2,4), geraniol, nerol, geranylacetate, neryl acetate, nerolidol, farnesol, dehydronerolidol, α-bisabolol, valancene, nookatene, nootkatone, dimethyl-2, 4, 6-octratriene, β- phellandrences, piperitols (-, cis and +, trans) , 1-methyl- 1, 4-cyclohexadiene, methyl cyclopentadiene dimer, ethylidene norbornene, dipentene, carvestrene, carvone (- or +) , alloocimenes (4-trans-6-cis and 4-trans-6-trans) , alloocimenols, ionomers, guaiazulene, lanosterol, squalene, lycopene, carotenes {β and γ) , nopol glycidyl ether, and combinations thereof.
25. The compositions according to Claim 1, wherein the thiirane compound is a member selected from the group consisting of thiiranes prepared from limonene, terpinene, nopol, ethylidene norbornene, methyl cyclopentadiene dimer, and combinations thereof.
26. A method of sealing underfilling between a semiconductor device including a semiconductor chip mounted on a carrier substrate and a circuit board to which said semiconductor device is electrically connected or a semiconductor chip and a circuit board to which said semiconductor chip is electrically connected, the steps of which comprise:
(a) dispensing into the underfilling between the semiconductor device and the circuit board or the semiconductor chip and the circuit board a composition according to any one of Claims 1-25;. and
(b) exposing the composition as so dispensed to conditions appropriate to cause the composition to form a reaction product.
27. A method of reworking a reaction product of a composition according to any one of Claims 1-25 which forms underfill sealing between a semiconductor device including a semiconductor chip mounted on a carrier substrate and a circuit board to which said semiconductor device is electrically connected or a semiconductor chip and a circuit board to which said semiconductor chip is electrically connected, a step of which comprise:
(a) exposing the reaction product to conditions appropriate to cause the reaction product to ■ soften and lose adhesiveness .
28. The method according to Claim 27, further comprising the steps of:
(b) removing the semiconductor chip or semiconductor device from the circuit board; and
(c) optionbally, cleaning the surface of the circuit board to remove any cured reaction product that remains .
29. A method of preparing an epoxy compound for use in a composition according to any one of Claims 1-25, the steps of which comprise : (a) providing an olefinically unsaturated compound having at least two olefinic linkages, at least one of which olefinic linkages being substituted on at least three of the substitutable positions on the olefin carbons with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interruption by one or more heteroatoms or halogens ; and
(b) providing an epoxidation agent in an amount and under conditions appropriate to react with the olefinic linkages to form the epoxide compound.
30. A method of preparing an episulfide compound for use in a composition according to any one of Claims 1- 25, the steps of which comprise:
(a) providing an olefinically unsaturated compound having at least two olefinic linkages, at least one of which olefinic linkages being substituted on at least three of the substitutable positions on the olefin carbons with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interruption by one or more heteroatoms or halogens ;
(b) providing an epoxidation agent in an amount and under conditions appropriate to react with the olefinic linkages to form an epoxide compound; and
(c) providing an episulfidizing agent in an amount and under conditions appropriate to react with the epoxide compound to form an episulfide compound.
31. Reaction products formed from the compositions according to any one of Claims 1-25.
32. An electronic device comprising a semiconductor device and a circuit board to which said semiconductor device is electrically connected assembled using a thermosetting resin composition according to any one of Claims 1-26 as an underfill sealant between the semiconductor device and the circuit board, wherein reaction products of the composition are capable of softening and losing their adhesiveness under exposure to temperature conditions in excess of those used to cure the composition.
33. A compound within the following structure:
Figure imgf000073_0001
wherein R4, R5, R6, R7, R8, and R9 are individually selected from the group consisting of hydrogen, alkyl from one to eight carbon atoms, alkenyl from two to eight carbon atoms and combinations thereof, and X and X1 may be selected from the group consisting of O and S.
34. A compound within the structure:
Figure imgf000073_0002
wherein R4, R5, R6, R7, R8, and R9 are individually selected from the group consisting of hydrogen, alkyl from one to eight carbon atoms, alkenyl from two to eight carbon atoms and combinations thereof, and X and X1 may be selected from the group consisting of O and S.
35. A compound within the structure:
Figure imgf000073_0003
wherein R4, R5, R6, R7, R8, and R9 are individually selected from the group consisting of hydrogen, alkyl from one to eight carbon atoms, alkenyl from two to eight carbon atoms and combinations thereof, and X and X1 may be selected from the group consisting of 0 and S.
36. A compound represented by:
Figure imgf000074_0001
37. A compound represented by:
Figure imgf000074_0002
38. A compound selected from the group consisting of:
Figure imgf000074_0003
39. A compound represented by:
Figure imgf000074_0004
AMENDED CLAIMS
[received by the International Bureau on 21 August 2001 (21.08.01); original claims 18 and 32 amended; remaining claims unchanged (2 pages)]
18. The composition according to Claim 17, wherein the adhesion promoter is a member selected from the group consisting of glycidyl trimethoxysilane, gamma-amino propyl triethoxysilane, and combinations thereof.
19. The composition according to Claim 1, further comprising a cyanate ester.
20. The composition according to Claim 19, wherein the cyanate ester is a member selected from the group consisting of dicyanatobenzenes, tricyanatobenzenes, dicyanatonaphthalenes, tricyanatonaphthalenes, dicyanato- biphenyl, bis (cyanatophenyl) ethanes and alkyl derivatives thereof, bis (dihalocyanatophenyl) ropanes, bis (cyanatophenyl) ethers, bis (cyanatophenyl) sulfides, bis (cyanatophenyl) ropanes, tris (cyanatophenyl) phosphites, tris (cyanatophenyl) phosphates, bis (halocyanatophenyl) methanes, cyanated novolac, bis [cyanatophenyl (methylethylidene) ] benzene, cyanated bisphenol-terminated thermoplastic oligomers, and combinations thereof .
21. The composition according to Claim 1, which is capable of sealing underfilling between a semiconductor device including a semiconductor chip mounted on a carrier substrate and a circuit board to which the semiconductor device is electrically connected.
22. The composition according to Claim 1, which is capable of sealing underfilling between a semiconductor device including a semiconductor chip mounted on a carrier substrate and a circuit board to which the semiconductor device is electrically connected, wherein the curable resin component is present in an amount within the range of about 10 to 70 weight percent, based on the total weight of the composition; the curing agent component is present in an amount within the range of 1 to about 100 weight percent, based on the weight of the curable resin component; and further comprising an inorganic filler component in an amount up to about 70 weight percent, based on the total weight of the composition; and a flowability agent in an amount up to about 2 weight percent, based on the weight of the composition. (a) providing an olefinically unsaturated compound having at least two olefinic linkages, at least one of which olefinic linkages being substituted on at least three of the substitutable positions on the olefin carbons with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interruption by one or more heteroatoms or halogens; and
(b) providing an epoxidation agent in an amount and under conditions appropriate to react with the olefinic linkages to form the epoxide compound.
30. A method of preparing an episulfide compound for use in a composition according to any one of Claims 1- 25, the steps of which comprise:
(a) providing an olefinically unsaturated compound having at least two olefinic linkages, at least one of which olefinic linkages being substituted on at least three of the substitutable positions on the olefin carbons with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interruption by one or more heteroatoms or halogens ;
(b) providing an epoxidation agent in an amount and under conditions appropriate to react with the olefinic linkages to form an epoxide compound; and
(c) providing an episulfidizing agent in an amount and under conditions appropriate to react with the epoxide compound to form an episulfide compound.
31. Reaction products formed from the compositions according to any one of Claims 1-25.
32. An electronic device comprising a semiconductor device and a circuit board to which said semiconductor device is electrically connected assembled using a thermosetting resin composition according to any one of Claims 1-25 as an underfill sealant between the semiconductor device and the circuit board, wherein reaction products of the composition are capable of softening and losing their adhesiveness under exposure to temperature conditions in excess of those used to cure the composition.
PCT/US2001/008624 2000-03-31 2001-03-27 Reworkable composition of oxirane(s) or thiirane(s)-containing resin and curing agent WO2001074798A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US10/182,450 US7012120B2 (en) 2000-03-31 2001-03-27 Reworkable compositions of oxirane(s) or thirane(s)-containing resin and curing agent
MXPA02009639A MXPA02009639A (en) 2000-03-31 2001-03-27 Reworkable composition of oxirane(s) or thiirane(s) containing resin and curing agent.
CA002403595A CA2403595A1 (en) 2000-03-31 2001-03-27 Reworkable composition of oxirane(s) or thiirane(s)-containing resin and curing agent
JP2001572491A JP2003529643A (en) 2000-03-31 2001-03-27 Reworkable composition of oxirane or thiirane containing resin and hardener
AU2001247541A AU2001247541A1 (en) 2000-03-31 2001-03-27 Reworkable composition of oxirane(s) or thiirane(s)-containing resin and curing agent
EP01920494A EP1268457A4 (en) 2000-03-31 2001-03-27 Reworkable composition of oxirane(s) or thiirane(s)-containing resin and curing agent
US12/004,343 US8053587B2 (en) 2000-03-31 2007-12-20 Reworkable thermosetting resin composition

Applications Claiming Priority (2)

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US19354200P 2000-03-31 2000-03-31
US60/193,542 2000-03-31

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US10182450 A-371-Of-International 2001-03-27
US11/007,754 Division US20050288458A1 (en) 2000-03-31 2004-12-08 Reworkable thermosetting resin composition

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JP (1) JP2003529643A (en)
KR (1) KR100790081B1 (en)
CN (1) CN1232515C (en)
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CA (1) CA2403595A1 (en)
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EP1803758A1 (en) * 2004-10-20 2007-07-04 Kansai Paint Co., Ltd. Polyepoxy compound, method for producing same, thermosetting resin composition containing same, cured product of such composition, and method for removing such cured product
US8969577B2 (en) 2008-11-24 2015-03-03 Basf Se Curable composition comprising a thermolatent base

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JP4816333B2 (en) * 2006-08-28 2011-11-16 パナソニック電工株式会社 Manufacturing method of semiconductor device
JP5767540B2 (en) * 2011-09-14 2015-08-19 積水化学工業株式会社 B-stage film, multilayer substrate and laminated film which are episulfide resin materials
BR112015007871B1 (en) * 2012-10-11 2021-12-14 Prc-Desoto International, Inc METHOD FOR PREPARING A NEUTRALIZED BASED AQUEOUS RESIN DISPERSION
JP2016029152A (en) * 2014-07-24 2016-03-03 日本合成化学工業株式会社 Curing agent for anion curable compound, curable composition, and cured product
JP2020063343A (en) * 2018-10-16 2020-04-23 日東シンコー株式会社 Resin composition
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EP1268457A4 (en) 2005-07-20
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CN1427831A (en) 2003-07-02
JP2003529643A (en) 2003-10-07
KR100790081B1 (en) 2007-12-31
KR20020087442A (en) 2002-11-22
CA2403595A1 (en) 2001-10-11
CN1232515C (en) 2005-12-21
AU2001247541A1 (en) 2001-10-15

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