WO2014123849A1 - Résine époxy mono-constituant comprenant un copolymère séquencé acrylique - Google Patents

Résine époxy mono-constituant comprenant un copolymère séquencé acrylique Download PDF

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Publication number
WO2014123849A1
WO2014123849A1 PCT/US2014/014581 US2014014581W WO2014123849A1 WO 2014123849 A1 WO2014123849 A1 WO 2014123849A1 US 2014014581 W US2014014581 W US 2014014581W WO 2014123849 A1 WO2014123849 A1 WO 2014123849A1
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block
phenoxy resin
composition
block copolymer
poly
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PCT/US2014/014581
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English (en)
Inventor
Rong-Chang Liang
Yuhao Sun
Chin-Jen Tseng
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Trillion Science, Inc.
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Priority claimed from US13/761,703 external-priority patent/US20130146816A1/en
Application filed by Trillion Science, Inc. filed Critical Trillion Science, Inc.
Priority to CN201480007640.3A priority Critical patent/CN105143376A/zh
Publication of WO2014123849A1 publication Critical patent/WO2014123849A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • 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
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00—Presence of block copolymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2461/00—Presence of condensation polymers of aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0783—Using solvent, e.g. for cleaning; Regulating solvent content of pastes or coatings for adjusting the viscosity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads

Definitions

  • the invention relates to epoxy adhesive or molding compound compositions suitable for connecting, assembling, encapsulating or packaging electronic devices particularly for display, circuit board, flip chip and other semiconductor devices containing a low profile additive.
  • This invention particularly relates to one-part epoxy compositions containing an acrylic block copolymer, that can be used as a dispersant to provide a stable dispersion of phenoxy resin in weak solvents which have a solubility parameter less than 9.5 and, more particularly less than about 9.0 and which are compatible with microencapsulated latent hardeners (i.e., they do not attack or soften the shell wall).
  • ACF anisotropic conductive film
  • the acrylic block copolymer may also provide the function of a low profile additive.
  • Epoxy systems one part epoxy systems in particular, have the advantages of convenient applications as adhesives or molding compounds for connecting, assembling, encapsulating or packaging electronic devices, for adhesive or molding compound applications, epoxies are considered to be superior to the thermoplastic adhesives because of the process-ability of the uncured composition and the heat resistance of the cured products. Furthermore, among the epoxy applications, the one-part epoxy systems are in general more preferred than the two-part systems for most of the molding compounds and pre-coated products including anisotropic conductive adhesive films (ACFs or ACAFs). This is because the one-part systems are much more user friendly between these two systems. [0003] Although epoxy adhesive compositions exhibit a number of advantages including good strength and high adhesion, they suffer certain drawbacks.
  • polar solvents having a solubility parameter in the range of greater than 9.5 to 11.5 to dissolve the high molecular weight phenoxy resins, thermoplastic polyethers based on bisphenol-A and epichlorohydrin with bisphenol-A terminal groups, which are often used as the binder particularly in the ACF applications.
  • these solvents have a tendency to attack the latent hardener shell wall and reduce the stability or shelf life of the adhesive composition.
  • Epoxy adhesives also shrink upon curing and this shrinkage causes internal stress that can cause the formation of micro- voids or micro-cracks.
  • This shrinkage is associated with two occurrences: (1) thermal contraction when the heated bonding element is removed and the compound cools, and (2) volume shrinkage resulting from the tight network that is developed upon physical and chemical crosslinking of the compound. These cracks and voids reduce the mechanical strength of the adhesive bond and they also make the compound susceptible to moisture such that the bonded electronic component may fail when subjected to high temperature and high humidity aging (HHHT).
  • HHHT high temperature and high humidity aging
  • the one-part epoxy coating fluid typically includes an uncured phenoxy resin component, a latent hardener, a multifunctional epoxide, an acrylic block copolymer dispersant and a weak solvent having a solubility parameter less than 9.5 and, more particularly, less than about 9.0.
  • the acrylic block copolymer includes at least one flexible mid block and, more particularly, an elastomeric mid block; and at least one rigid block that renders the copolymer compatible with the uncured epoxy resin.
  • the latent hardener is a microencapsulated hardener, e.g., a latent hardener of the Novacure variety, for example, Novacure HXA-3922, 3932, 3641 and 3742 available from Asahi Kasei K .
  • Novacure latent hardeners from Asahi Kasei are microcapsules of highly reactive curing agents such as imidazoles and their epoxide adducts encapsulated by e.g. a polyurethane or polyurea shell or matrix, and dispersed in multifunctional epoxides such as bisphenol F diglycidyl ether, or mixtures thereof with other epoxides.
  • the improved epoxy composition as will be further described below in one embodiment may be implemented in an exemplary embodiment as conductive coating or adhesive for an anisotropic conductive film (ACF) and, in a particular embodiment in the ACF described in U.S. Published Application 2006/0280912 to Liang et al.
  • the ACF includes a plurality of conductive particles disposed at predetermined locations in or on an adhesive layer on a release substrate.
  • the improved epoxy composition may further be employed as a conductive coating or adhesive for connecting, packaging or encapsulating electronic components in another exemplary embodiment similar to the application of the adhesive described in U.S. Published Application 2008/0090943.
  • the film without the conductive particles may be used in various applications such as in semiconductor packaging or in LED assemble.
  • the use of the block copolymers, as disclosed herein, as dispersants enables a uniform coating process and results in a stable, long shelf life coated films containing a latent hardener such as imidazole microcapsules.
  • the block copolymers act as dispersants for the phenoxy resins in weak solvents (e.g., solvents having a solubility parameter less than 9.5 and more particularly less than about 9.0). These weak solvents have reduced tendency to attack the latent hardeners during the compounding and coating processes and thereby provide a more shelf stable adhesive composition both before and after the coating is dried.
  • the epoxy resin component includes at least one epoxy resin that has two or more epoxy groups in a single molecule.
  • a multifunctional epoxide is a di-, tri-, terra-, penta-, hexa- or other polyfunctional epoxide. Multifunctional epoxides having three or more epoxide groups are useful as cross-linkers in the composition. Improved
  • thermomechanical properties of cured epoxy adhesives or coatings may be achieved by incorporating small amounts of about 1 to 10% of a crosslinking epoxide into the composition. However, too high a concentration of a crosslinker may provide a product that is too brittle.
  • the latent hardener containing the curing agent initiates and/or accelerates the reaction by either catalyzing and/or taking part in the reaction.
  • Typical examples of multifunctional epoxides or epoxy resins used in adhesives or molding compounds include polyglycidyl ethers of polyhydric phenols such as bisphenol epoxy resins derived from epichlorohydrin and bisphenol A or bisphenol F, and epoxy novolak resins derived from epichlorohydrin and phenol novolak or cresol novolak resins (e.g., Epon 161 and Epon 165 available from available from Hexion Specialty Chemicals).
  • mulifunctional epoxides or epoxy resins include polyglycidyl esters of polycarboxylic acids, alicyclic epoxy compounds, polyglycidyl ethers of polyhydric alcohols, and polyglycidyl compounds of polyvalent amines.
  • bisphenol F epoxy resin such as EPOTOHTO YDF-8170 from Tohto Kasei Co., Ltd. and YL 983U from JAPAN EPOXY RESINS Co., Ltd ; ,and bisphenol A epoxy resins such as DER-332 from The Dow Chemical Company, and YL 980.from JAPAN EPOXY RESINS Co., Ltd.; and alicyclic epoxy resin such as
  • the adhesive may also contain a binder or thickener to improve the melt flow charateristics and the structure integrity during high speed ACF bonding processes.
  • Linear polymers or copolymers of bisphenol A and diglycidyl ether and other phenoxy resins are often employed as the binder in ACF applications.
  • Paphen phenoxy resin (PKHH) from Phenoxy Specialties or PKFE from Inchem Corp. is used as the binder or thickener.
  • This resin series typically has a solubility parameter of about 10.68 and is available from companies such as InChem Corp, Rock Hill , SC.
  • the cured adhesives are also of high modulus and better reliability at high temperature applications.
  • the binder may be used in amounts of about 10 to 50 wt. % and more particularly about 20 to 40 wt. %.
  • the epoxy composition comprises epoxidized Epon 161 (phenolic novolac resin) and Epon 165 (epoxidized cresol novolac resin), both from Momentive Specialty Chemicals Inc., Ohio, bisphenol A diglycidyl ether and bisphenol F diglycidyl ether from Sigma- Adrich, and PKHH from InChem Corp.
  • the composition comprises Epon 161, Epon 165, Bisphenol F and PKFE.
  • the composition comprises Epalloy 8330 (epoxidized phenolic novolac resin) from CVC Thermoset Specialties, NJ, bisphenol F diglycidyl ether, and glycerol triglycidyl ether from Sigma- Aldrich.
  • epoxy compositions (not including solvents and the epoxides from the hardener composition, if there is any) used herein are provided below.
  • the latent hardeners include controlled release-able or trigger-able curing agents or accelerators.
  • curing agents or accelerators typically used in epoxy adhesives or molding compounds include polyamide-polyamine-based compounds, aromatic polyamine compounds, imidazole compounds, imidazole-epoxide adducts, tetrahydrophthalic anhydride and the like.
  • the accelerator or curing agent may be liquid or solid.
  • Preferred liquid accelerators include, e.g., amine compounds, imidazole compounds and mixtures thereof.
  • Exemplary liquid accelerator compounds include l-(2- hydroxyethyl)imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, l-benzyl-2- methylimidizole, l-cyanoethyl-2-phenyl-4, 5-dihydroxymethyl imidazole, l-(2- hydroxyethyl)imidazole, 2-ethyl-4-methylimidazole, phenylimidazole, 2-phenyl-4- methylimidazole, l-cyanoethyl-2 -phenylimidazole, multifunctional mercaptans (e.g., Anchor 2031), and stannous octate.
  • multifunctional mercaptans e.g., Anchor 2031
  • Preferred solid accelerators include, e.g., urea, 2- phenyl-4, 5-dihydroxymethyl imidazole, and l-(2-hydroxyethyl)imidazole.
  • Other examples of curing agents include dicyanodiamide (DICY), adipic dihydrazide, amines such as ethylene diamine, diethylene triamine, triethylene tetraamine, BF3 amine adduct, Amicure from Ajinomoto Co., Inc, sulfonium salts such as diaminodiphenylsulphone, p- hydroxyphenyl benzyl methyl, and sulphonium hexafluoroantimonate.
  • DICY dicyanodiamide
  • adipic dihydrazide amines such as ethylene diamine, diethylene triamine, triethylene tetraamine, BF3 amine adduct
  • sulfonium salts such as diaminodiphenylsul
  • catalysts/accelerators may optionally be absorbed in a molecular sieve or in the form of microcapsules to enhance the curing processes as disclosed in Japanese Patent
  • microcapsules must be first broken or rendered permeable by pressure, shear, heat or combinations of above methods in order to cure the epoxy resin.
  • Examples of commercially available imidazole microcapsules include the Novacure series from Asahi Chemical Industry Co., Ltd. such as HX 3721 (2 -methyl imidazole).
  • the microcapsules may be formed by a polymer shell. In certain embodiments they are formed by a polyurethane or a polyurea shell.
  • the preferable concentration range of the latent catalyst/curing agent is from about 0.05% by weight to about 50% by weight, more preferably from about 2% by weight to about 40%> by weight based on the adhesive composition.
  • the more preferable concentration range is from about 5% by weight to about 40%> by weight and still more particularly about 25 to 40%> by weight based on the adhesive composition.
  • Novacure latent hardeners from Asahi Kasei are microcapsules of hardeners dispersed in low Mw epoxides.
  • imidazoles and their epoxide adducts are typical core materials used in the latent hardeners and, in a more particular embodiment they are encapsulated by a polymer shell such as a polyurethane or polyurea shell and in a more particular embodiment the microcapsules may be prepared by interfacial polymerization/crosslinking reactions.
  • the core materials may be released by heat or a solvent that may swell or plasticize the shell polymer to trigger the crosslinking or polymerization of epoxides in the
  • a group of secondary co-catalyst or co-curing agent is also disclosed.
  • a secondary co-catalyst or co-curing agent selected from a group consisting of ureas, urethanes, biurets,
  • amides and lactams comprising a N ⁇ , ⁇ -dialkylamino, N,N-diarylamino, N-alkyl-N-aryl-amino or a dicycloalkylamino functional group.
  • Useful examples include amide such as N-(3-(dimethyamino)propyl)lauramide, lactams such as 1,2- benzisothiazol-3(2H)-one, and benzothiazols such as 2-(2-benzothiazolylthio)ethanol.
  • leuco dyes particularly those comprising a N,N-dialkylamino, ⁇ , ⁇ -diarylamino, N-alkyl-N-aryl-amino, N- alkylamino, or N-arylamino functional group on at least one of their aromatic rings, function as very effective co-catalysts or co-accelerators to improve the curing characteristics of epoxy resins. More specifically, it discloses adhesive compositions comprising a leuco dye and a latent curing agent such as Novacure imidazole capsules. The leuco dyes have shown significant improvement in curing and conversion of the epoxides while maintaining acceptable shelf-life stability.
  • Suitable cocatalysts of the present invention include, but are not limited to, triarylmethane lactones, triarylmethane lactams, triarymethane sultones, fluorans, phthalides, azaphthalides, spiropyrans, spirofluorene phthalides, spirobenzantharacene phthalides.
  • Leuco dyes comprising a N,N-dialkylamino, ⁇ , ⁇ -diarylamino, N,N- dialkylaryl or N-alkyl-N-aryl-amino, N-alkylamino, or N-arylamino group on the aromatic ring are particularly useful.
  • the acrylic block copolymers can be diblock (A-B), triblock (A-B-A) or a multiblock (A-(B-A)n) where n is from 2 to 8 block copolymers that include a flexible elastomeric midblock.
  • the flexible (B) midblock is a poly alkyl (meth)acrylate wherein the alkyl group contains about 2 to 8 carbon atoms such as polybutyl acrylate, polyethyl acrylate, poly 2- ethylhexyl acrylate, poly(2-ethylhexyl) methacrylate and poly (isooctyl acrylate).
  • Polyether polyurethanes are also useful as flexible blocks.
  • the flexible mid block is a carboxyl terminated butadiene acrylonitrile (CTBN) rubber.
  • CTBN carboxyl terminated butadiene acrylonitrile
  • the block copolymer is one in which a poly(butyl acrylate) is positioned between two poly(methyl methacrylate) end blocks.
  • Acrylic block copolymers such as MAM Nanostrength ® block copolymers terminated in PMMA end blocks available from Arkema Corporation, particularly (PMMA-PBuA-PMMA) block copolymers such as M51, M52, and M53 and their functionalized derivatives such as M52N may be used as dispersants to prepare a stable dispersion of high molecular weight (Mw) phenoxy resins in a common weak coating solvents or diluents of low polarity or dielectric constant having a solubility parameter of less than 9.5 or even less than about 9.0 and more particularly about 8.0 to 9.4 and still more particularly about 8.2 to 9.2, such as ethyl acetate EtOAc (9.2), i-PrOAc (8.4), BuOAc (8.5), MIBK (8.4), MIPK (8.5), toluene (8.9), xylene (8.85), ethylbenzene (8.7) which provide good dispersibility of the epoxy resins in
  • a good solvent for the phenoxy resins is needed to assure a good coating quality in the absence of such a polymeric dispersant.
  • Typical good solvents for the same composition include, but are not limited to, DMSO, NMP, MEK, acetone, THF, alkoxyethers and cyclohexanone or their mixtures with a second good solvent or diluent.
  • Those good or strong solvents for the phenoxy resins are often hostile solvents for the latent hardeners. They tend to plasticize or soften the shell and reduce the barrier properties of the latent hardeners. In some cases, they are also goof solvents for the core materials or the hardeners therein.
  • the epoxy composition has to be prepared in at least a strong solvent for the phenoxy resins and the resultant adhesive coatings are either of poorer coating quality or of poorer shelf-life stability.
  • the weak solvents or diluents of the compositions comprising a phenoxy resin may also be defined by their dielectric constant, although the correlation may not be so direct as the solubility parameter mentioned above.
  • the weak solvents or diluents used in the adhesive composition have a dielectric constant of about 2 to 8.
  • the weak solvents or diluent are characterized by a dielectric constant of about 2.2 to 6.5.
  • the composition contains an LPA that is miscible with the epoxy resin and separates to form stress-absorbing nodules upon curing.
  • the LPA is not necessarily a block copolymer. Examples of copolymers that may be effective as LP As and/or block copolymer dispersants include those shown in the following table: Description EEW(g/eq)
  • Epon 58003 An elastomer modified epoxy functional 285-330 (Hexion Specialty adduct of a bisphenol-F epoxy resin and
  • Epon 58005 An elastomer modified epoxy functional 325-375 (Hexion Specialty adduct of bisphenol A epoxy resin and a
  • Epon 58034 An elastomer modified epoxy functional 275-305 (Hexion Specialty adduct formed from the reaction of
  • HELOXYTM Modifier 68 is a diglycidyl
  • HyPox R 84 (CVC Adduct of solid diglycidyl ether of 1200-1800
  • HyPox R 84L Adduct of solid diglycidyl ether of 1250-1500 CVC Thermoset Bisphenol A and a CTBN rubber.
  • HyPox UA10 A standard Bisphenol A epoxy resin which 210-220 (CVC Thermoset has been modified with a select
  • thermoplastic polyurethane TPU
  • HyPox UA11 A standard Bisphenol A epoxy resin system 210-220 (CVC Thermoset which has been modified with a select
  • thermoplastic polyurethane TPU
  • PMMA friendly crosslinking agents e.g., silicone crosslinking agents
  • crosslinking agents e.g., DICY, DDS.
  • a rigid polymer block is poly (methyl methacrylate).
  • this block is also compatible with the epoxy resin, such that the LPA can be mixed with the uncured resin without phase separation when the LPA is used in amounts effective to prevent shrinkage.
  • the (A) and (B) blocks of the LPA are selected such that the LPA and the epoxy resin form a homogeneous solution when the LPA is used in amounts up to 15% by weight.
  • M52N from Arkema, Inc. is a particularly useful LPA.
  • the LPA is not necessarily a block copolymer, but a polymer that is miscible with the epoxy resin and separates to form stress-absorbing nodules upon curing.
  • LP conjugated dienes having about 4 to 12 carbon atoms with polybutadiene and polyisoprene being two representative examples, provided they are compatible with the epoxy resin.
  • the compatibility of the LPA in the epoxy adhesive can be enhanced by epoxidizing the block copolymer as described in U.S. Patent 5,428,105.
  • the LPA copolymer includes unsaturated groups such as an unsaturated diene, a portion of these groups (e.g., about 1 to 15%) can be oxidized.
  • the LPA may be a core-shell polymer obtained by emulsion or dispersion polymerization.
  • core-shell rubbers include, but are not limited to, acrylic core-shell rubber such as ParaloidTM EXL-2335 from Dow Chemical.
  • the LPA may be used in amounts up to about 15% by weight based on the combined weight of the LPA and the epoxy resin.
  • the LPA is more typically used in an amount of about 4 to 10% and in one embodiment it is used in an amount of about 7%.
  • the amount of the LPA is adjusted to provide the required peeling strength.
  • the molecular weight (Mw) of the LPA may be about 15,000 to 200,000 and more typically about 50,000 to 100,000. In one embodiment, the molecular weight (Mw) is about 88,000. In one embodiment, the LPA contains about 5 to 50% of the flexible (B) block.
  • the LPA when mixed with the uncured epoxy resin forms a homogenous single phase.
  • the epoxy resin network is formed which phase separates from the initial solution and forms spherical nodules of the LPA. This is called "reaction induced phase separation.”
  • the size of the stress absorbing nodules will vary with the amount of LPA used, the Mw of the LPA and the interaction between the epoxy resin and the LPA.
  • ultimately a network is formed wherein the LPA nodules are connected to adjacent nodules by a polymer link.
  • the disclosed block copolymers have been found to be particularly effective.
  • the acrylic block copolymers such as M52N are dispersants for the phenoxy binders in weak solvents or diluents such as propyl acetate, i-propyl acetate, butyl acetate, toluene...etc. which are good solvents for epoxide monomers, dimers or other multifunctional epoxides, but are poor solvents for the binder and do not attack the latent hardeners thereby providing a long shelf-life in such weak solvents or diluents. It has been shown that the use of such block copolymers result in a coating of great film integrity and coating quality as well as a very long shelf-life stability.
  • Nanostrength® M52N and PKFE were used as the dispersant and binder, respectively, in the adhesive composition dispersed in a solvent mixture consisting of from about 60/40 to about 40/60 of EtOAc/i-PrOAc.
  • the weight ratio of M52N/PKFE was about from 1/4 to 1/12, preferably from 1/6 to 1/10.
  • the total % of solid of the coating fluid is typically from 20 to 40%, preferably from 25 to 35% depending on the composition.
  • the concentration of the latent hardener in the dried coating is typically from about 10 to 80% by weight, preferably from 20 to 60% by weight.
  • M52N as the dispersant, the coating fluid tended to be unstable and in some cases, even phase separated during the coating process and resulted in a poor coating quality.
  • the coating of the same composition prepared in a stronger solvent such as MEK, acetone, THF, NMP and cyclohexanone or their mixtures having a solubility parameter close to that of phenoxy resins is either of poor coating quality or of poor shelf-life stability.
  • the epoxy adhesive may comprise a filler or additive to control one or more properties of the epoxy adhesive such as rheology, wetting and moisture resistance.
  • a particulate rheology modifier may be added to the epoxy adhesive.
  • the rheology modifier may be a thixotropic agent having an average particle size between about 0.001 and about 10 microns, and more preferably between about 0.01 and about 5 microns.
  • particulate rheology modifiers include barium sulfate, talc, aluminum oxide, antimony oxide, kaolin, finely divided silicon dioxide which may be colloidal or rendered hydrophobic, micronized talcum, micronized mica, clay, kaolin, aluminum oxide, aluminum hydroxide, calcium silicate, aluminum silicate, magnesium carbonate, calcium carbonate, zirconium silicate, porcelain powder, glass powder, antimony trioxide, titanium dioxide, barium titanate, barium sulfate and mixtures thereof.
  • One particularly preferred rheology modifier is fumed silica such as Cab-O-Sil M-5 and hydrophobic silica such as TS530, TS610 and TS720 from Cabot Corp., MA.
  • a wetting agent may be added.
  • exemplary wetting agents include surfactants such as epoxy silanes, branch or block copolymers of siloxanes, fluoro-surfactants and hydrocarbon-type surfactants.
  • Suitable surfactants include FC4430 (formally referred to as FC-430) which is available from 3M Corp. of St. Paul Minn., Silwet series surfactants such as Silwet L7622 and L7608 from GE Silicones-OSi Specialties, BYK 322, BYK325 and BYK 63 IN from BYK-Chemie.
  • the Silwet surfactants are often used in an amount of about 0.05 to 1% by weight, preferably 0.1 to 0.5% by weight.
  • the moisture resistance or wet adhesion of the cured compound may be improved by including a coupling agent in the epoxy adhesive.
  • Typical coupling agents include organic metal compounds that comprise chromium, silane, titanium, aluminum and zirconium.
  • the most commonly used coupling agents comprise silane such as vinyl- triethoxy silane, vinyltris(2-methoxyethoxy)silane, 3- methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane (e.g., Silquest 187® from Crompton), 2-(3,4-epoxycyclohexyl)ethyltrimethoxy silane, N-2- (aminoethyl)-3-aminopropylmethyldimethoxy-silane, 3-aminopropyltriethoxysilane, and 3-chloro-propyltrimethoxy-silane.
  • the coupling agent frequently comprises less than about 5% by weight, preferably less than
  • reinforcement fibers such as glass fiber and carbon fiber are often included in the composition.
  • Natural fibers such as bamboo fibers, wood and other cellulose fibers are also useful. They may be in a pellet form prepared by extrusion followed by cutting or in a sheet form prepared by coating, lamination or impregnation.
  • the epoxy compositions of this invention may be applied in a conductive coating or adhesive layer or layers, the conductive particles either in the random or non- random arrays may be in the adhesive layer, on the adhesive layer or underneath the adhesive layer.
  • Flexible configurations may be conveniently arranged according to particular application requirements. These configurations may include an arrangement where the adhesive that comprises the improved epoxy compositions of this invention and the conductive particles are disposed in separate, adjacent or non-adjacent layer in an ACF of either a random or non-random particle array.
  • the conductive particles may be mixed with the adhesive composition before forming a film.
  • the adhesive may be coated first without the conductive particles and the conductive particles applied to the adhesive by a particle transfer process.
  • a ACF adhesive coating composition comprises about 100 to 300 parts of a coating solvent or solvent mixture, about 20-50 parts of a phenoxy resin such as PKFE, about 2 to 9 parts of the block copolymer dispersion agent such as M52N, about 20 to 70 parts of a latent hardener such as Novacure HXA3922 and HX3721, and about 0 to 20 parts of a multifunctional epoxide or a mixture of epoxides selected from a group comprising bisphenol F diglycidyl ether and glycerol triglycidyl ether, Epon 161, Epon 165, and Epalloy 8330 etc.
  • a combination of of M52N and PKFE is used in a weight ratio of M52N/PKFE of about 1/5 to 1/10, preferably from about 1/6 to 1/9.
  • the coating solvent is selected so that it does not (to a commercially adverse degree) attack or soften the shell of the latent hardener during the entire coating process including compounding, fluid delivery, coating, drying and converting.
  • the composition was then mixed with 3 to 20 parts of conductive particles and coated on a release substrate.
  • the adhesive composition is first coated on a release substrate.
  • a fixed array of particles is then transferred to the adhesive layer from a microcavity film prefilled with conductive particles.
  • Suitable materials for the web of an ACF include, but are not limited to polyesters such as poly ethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate, polyamides, polyacrylates, polysulfone, polyethers, polyimides, and liquid crystalline polymers and their blends, composites, laminates or sandwich films.
  • PET poly ethylene terephthalate
  • PEN polyethylene naphthalate
  • polycarbonate polyamides
  • polyacrylates polysulfone
  • polyethers polyethers
  • polyimides polyimides
  • the adhesive compositions can be prepared by dissolving the solid epoxy components in a 1/1 by volume EtOAc/i-PrOAc mixture to prepare stock solutions of each ingredient. The low molecular weight or low percentage components are mixed and vigorously blended together. Dispersions of the rheology modifier in the EtOAc/ i- PrOAc mixture are prepared and added to the coating composition followed by addition of the high Mw components and surfactants.
  • the hardener Before coating, the hardener is dispersed in i-PrOAc and added to the coating with agitation (5 min.) and continuous stirring rotation (0.5 hr.). The coating composition is filtered through an 11 ⁇ filter and then degassed by ultrasound for 5 min.
  • the ingredients useful in one embodiment are identified in the following table.

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

Abstract

La présente invention concerne une composition adhésive comprenant une résine phénoxy, un durcisseur latent, un dispersant copolymère séquencé acrylique et un solvant faible, le dispersant permettant à la résine phénoxy d'être dispersée dans un solvant faible qui n'attaque pas le durcisseur latent, fournissant ainsi une composition présentant une durée de conservation. Les compositions sont utiles dans la fabrication de films conducteurs anisotropes.
PCT/US2014/014581 2013-02-07 2014-02-04 Résine époxy mono-constituant comprenant un copolymère séquencé acrylique WO2014123849A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4186937A4 (fr) * 2020-07-21 2024-08-07 Kyocera Corp Feuille adhésive thermoconductrice et dispositif semi-conducteur

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6470523A (en) 1987-08-26 1989-03-16 Asahi Chemical Ind Masterbatch type curing agent for one-pack type epoxy polymer
US5001542A (en) 1988-12-05 1991-03-19 Hitachi Chemical Company Composition for circuit connection, method for connection using the same, and connected structure of semiconductor chips
US5428105A (en) 1993-01-29 1995-06-27 Gencorp Inc. Low-profile additives for thermosetting polyester compositions
US6936644B2 (en) 2002-10-16 2005-08-30 Cookson Electronics, Inc. Releasable microcapsule and adhesive curing system using the same
US20060280912A1 (en) 2005-06-13 2006-12-14 Rong-Chang Liang Non-random array anisotropic conductive film (ACF) and manufacturing processes
US20070116961A1 (en) * 2005-11-23 2007-05-24 3M Innovative Properties Company Anisotropic conductive adhesive compositions
US20080090943A1 (en) 2006-10-16 2008-04-17 Trillion, Inc. Epoxy compositions
EP2253666A1 (fr) * 2008-02-15 2010-11-24 Kuraray Co., Ltd. Composition de résine durcissable et résine durcie
WO2011005925A1 (fr) * 2009-07-10 2011-01-13 Dow Global Technologies Inc. Caoutchoucs cœur/écorce destinés à être utilisés dans des compositions de stratifié électrique
US20110253943A1 (en) * 2010-04-19 2011-10-20 Trillion Science, Inc. One part epoxy resin including a low profile additive

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0806434D0 (en) * 2008-04-09 2008-05-14 Zephyros Inc Improvements in or relating to structural adhesives

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6470523A (en) 1987-08-26 1989-03-16 Asahi Chemical Ind Masterbatch type curing agent for one-pack type epoxy polymer
US4833226A (en) 1987-08-26 1989-05-23 Asahi Kasei Kogyo Kabushiki Kaisha Hardener for curable one-package epoxy resin system
US5001542A (en) 1988-12-05 1991-03-19 Hitachi Chemical Company Composition for circuit connection, method for connection using the same, and connected structure of semiconductor chips
US5428105A (en) 1993-01-29 1995-06-27 Gencorp Inc. Low-profile additives for thermosetting polyester compositions
US6936644B2 (en) 2002-10-16 2005-08-30 Cookson Electronics, Inc. Releasable microcapsule and adhesive curing system using the same
US20060280912A1 (en) 2005-06-13 2006-12-14 Rong-Chang Liang Non-random array anisotropic conductive film (ACF) and manufacturing processes
US20070116961A1 (en) * 2005-11-23 2007-05-24 3M Innovative Properties Company Anisotropic conductive adhesive compositions
US20080090943A1 (en) 2006-10-16 2008-04-17 Trillion, Inc. Epoxy compositions
EP2253666A1 (fr) * 2008-02-15 2010-11-24 Kuraray Co., Ltd. Composition de résine durcissable et résine durcie
WO2011005925A1 (fr) * 2009-07-10 2011-01-13 Dow Global Technologies Inc. Caoutchoucs cœur/écorce destinés à être utilisés dans des compositions de stratifié électrique
US20110253943A1 (en) * 2010-04-19 2011-10-20 Trillion Science, Inc. One part epoxy resin including a low profile additive

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Structure Adhesives", 1986, PLENUM PRESS
H. LEE: "The Epoxy Resin Handbook", 1981, MCGRAW-HILL, INC.
J. A. BRYDSON: "Plastic Materials", 1999, BUTTERWORTH-HEINEMANN
J. K. FINK: "Reactive Polymers, Fundamentals and Applications", 2005, WILLIAM ANDREW PUBLISHING

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4186937A4 (fr) * 2020-07-21 2024-08-07 Kyocera Corp Feuille adhésive thermoconductrice et dispositif semi-conducteur

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