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WO2025107100A1 - Adhésif époxydique comprenant un durcisseur polymère et un photoamorceur cationique et son procédé d'utilisation - Google Patents

Adhésif époxydique comprenant un durcisseur polymère et un photoamorceur cationique et son procédé d'utilisation Download PDF

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Publication number
WO2025107100A1
WO2025107100A1 PCT/CN2023/132557 CN2023132557W WO2025107100A1 WO 2025107100 A1 WO2025107100 A1 WO 2025107100A1 CN 2023132557 W CN2023132557 W CN 2023132557W WO 2025107100 A1 WO2025107100 A1 WO 2025107100A1
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Prior art keywords
adhesive composition
substrate
present disclosure
polymeric toughener
groups
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PCT/CN2023/132557
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English (en)
Inventor
Yiwen Chu
Enzhong Zhang
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to PCT/CN2023/132557 priority Critical patent/WO2025107100A1/fr
Priority to PCT/CN2024/132581 priority patent/WO2025108217A1/fr
Publication of WO2025107100A1 publication Critical patent/WO2025107100A1/fr
Pending legal-status Critical Current
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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
    • C08G59/20—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
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G59/223—Di-epoxy compounds together with monoepoxy 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
    • C08G59/20—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
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • Adhesives have been used in many structural applications. Such structural applications have included vehicles, computer cases, computer components, cameras, buildings, and appliances. Epoxy compositions are known and have been used for structural adhesive applications. Camera modules mounted in cars, smartphones, and the like have a lens, a tubular lens holder for holding the lens, and an image capturing sensor fixed on a base plate for converting the light collected by the lens into an electrical signal. In an assembly of this camera module, it is necessary to firmly bond the lens holder and the base plate on which the image capturing sensor is fixed. A structural adhesive can be used for this bonding.
  • Adhesives that cure by both light and heat for example, that include a cationically curable epoxy resin composition comprising an epoxy resin component, a photocationic initiator, a thermal cationic initiator are described in U.S. Pat. No. 7,795,744 (Chen et al. ) and U.S. Pat. Appl. Pub. No. 2023/0027326 (Tsuno et al. ) .
  • Certain inks and hardcoat compositions including a photocationic initiator and/or a thermal cationic initiator are disclosed in U.S. Pat. No. 7,935,739 (Shimizu et al. ) .
  • Certain compositions including both epoxy groups and free-radically curing groups are disclosed in U.S. Pat.
  • Adhesive compositions and methods according to the present disclosure include a multifunctional epoxide comprising at least two oxirane rings and at least one of a cycloaliphatic or aromatic ring, an aliphatic compound comprising at least one of an oxirane ring or oxetane ring, a polymeric toughener, and a cationic photoinitiator.
  • the cationic photoinitiator provides a cure-on-demand feature to the adhesive composition of the present disclosure when the composition is exposed to a light trigger, for example, to provide at least a useful bonding strength for positioning or handling or, in some cases, to fully cure the composition.
  • the adhesive composition further includes a thermal initiator, which can provide several advantages.
  • the thermal initiator can help to fully cure the adhesive composition, in some cases, once the light source is removed. This can be accomplished by increasing the temperature of the adhesive composition. In some cases, exposure of the adhesive composition to a light trigger results in the heating of the composition to an extent that the thermal initiator is thermally triggered. Furthermore, the thermal initiator can provide the composition with a backup curing mechanism in cases in which photochemical irradiation is not an option, does not reach the entire composition (e.g., in unexposed areas) , or is inadvertently omitted. Adhesive compositions including the cationic photoinitiator and the thermal initiator can be cured into polymer networks having similar properties using light and heat or heat alone.
  • the adhesive composition can be formulated as a two-part composition, which can at least partially cure at room temperature.
  • the inclusion of a polymeric toughener in the adhesive composition provides a surprising increase in bonding strength and decrease in shrinkage.
  • Examples 1 to 9 could be dispensed easily as a bead and hold their shape.
  • the adhesive composition of the present disclosure can be cured at relatively low temperature and have a good open time at room temperature.
  • the adhesive composition can also have low outgassing and a relatively low coefficient of thermal expansion.
  • the present disclosure provides an adhesive composition that includes a multifunctional epoxide containing at least two oxirane rings and at least one of a cycloaliphatic or aromatic ring, an aliphatic compound comprising at least one of an oxirane ring or oxetane ring, a polymeric toughener, and a cationic photoinitiator.
  • the adhesive composition further includes a thermal cationic initiator, or the adhesive composition is packaged as a two-part adhesive composition, with a first part including the multifunctional epoxide and the aliphatic compound and a second part including the cationic photoinitiator. At least one of the first part or the second part includes the polymeric toughener.
  • the aliphatic compound is optional.
  • the present disclosure provides a method of making a bonded article including a first substrate and a second substrate.
  • the method includes applying the adhesive composition onto at least one of the first substrate or the second substrate, adhering the first substrate and the second substrate using the adhesive composition, and at least one of heating or irradiating the adhesive composition to at least partially cure the adhesive composition to make the bonded article.
  • the present disclosure provides a method of making a bonded article including a first substrate and a second substrate.
  • the method includes irradiating the second part, and afterward mixing the first part and the second part to form the adhesive composition, applying the adhesive composition onto at least one of the first substrate or the second substrate, adhering the first substrate and the second substrate using the adhesive composition, and allowing the adhesive composition to at least partially cure to make the bonded article.
  • curable refers to joining polymer chains together by covalent chemical bonds, usually via crosslinking molecules or groups, to form a network polymer. Therefore, in this disclosure the terms “cured” and “crosslinked” may be used interchangeably.
  • a cured or crosslinked polymer is generally characterized by insolubility but may be swellable in the presence of an appropriate solvent.
  • polymer refers to a molecule having a structure which includes the multiple repetition of units derived, actually or conceptually, from one or more monomers.
  • monomer refers to a molecule of low relative molecular mass that can combine with others to form a polymer.
  • polymer includes homopolymers and copolymers, as well as homopolymers or copolymers that may be formed in a miscible blend, e.g., by coextrusion or by reaction.
  • polymer includes random, block, graft, and star polymers.
  • polymer encompasses oligomers.
  • alkyl group and the prefix “alk-” are inclusive of both straight chain and branched chain groups and of cyclic groups. In some embodiments, alkyl groups have up to 30 carbons (in some embodiments, up to 20, 15, 12, 10, 8, 7, 6, or 5 carbons) unless otherwise specified. Cyclic groups can be monocyclic or polycyclic and, in some embodiments, have from 3 to 10 ring carbon atoms. Terminal “alkenyl” groups have at least 3 carbon atoms.
  • Alkylene is the multivalent (e.g., divalent or trivalent) form of the “alkyl” groups defined above.
  • Arylalkylene refers to an “alkylene” moiety to which an aryl group is attached.
  • Alkylarylene refers to an "arylene” moiety to which an alkyl group is attached.
  • aryl and “arylene” as used herein include carbocyclic aromatic rings or ring systems, for example, having 1, 2, or 3 rings and optionally containing at least one heteroatom (e.g., O, S, or N) in the ring optionally substituted by up to five substituents including one or more alkyl groups having up to 4 carbon atoms (e.g., methyl or ethyl) , alkoxy having up to 4 carbon atoms, halo (i.e., fluoro, chloro, bromo or iodo) , hydroxy, or nitro groups.
  • heteroatom e.g., O, S, or N
  • substituents including one or more alkyl groups having up to 4 carbon atoms (e.g., methyl or ethyl) , alkoxy having up to 4 carbon atoms, halo (i.e., fluoro, chloro, bromo or iodo) , hydroxy, or nitro groups.
  • aryl groups include phenyl, naphthyl, biphenyl, fluorenyl as well as furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, and thiazolyl.
  • the adhesive composition of the present disclosure and/or useful in the method of the present disclosure includes a multifunctional epoxide comprising at least two oxirane rings and at least one of a cycloaliphatic or aromatic ring.
  • a variety of multifunctional epoxides are useful in the adhesive composition.
  • a monomeric multifunctional epoxide may be a cycloalkylene, arylene, alkylarylene, arylalkylene, or alkylenearylalkylene having at least two epoxide groups, wherein any of the cycloalkylene, alkylarylene, arylalkylene, or alkylenearylalkylene are optionally interrupted by one or more ether (i.e., -O-) , ester (i.e., -O-C (O) -) , thioether (i.e., -S-) , or amine (i.e., -NR 1 -) groups and optionally substituted by alkoxy, hydroxyl, oxo, or halogen (in some embodiments, chloro, bromo, or iodo) .
  • ether i.e., -O-
  • ester i.e., -O-C (O) -
  • Cycloalkylene groups can include both ring carbon atoms and carbon atoms not in the ring.
  • Useful monomeric multifunctional epoxides may be diepoxides or epoxides with more than 2 (in some embodiments, 3 or 4) oxirane rings.
  • An epoxy resin may be prepared by chain-extending any of such multifunctional epoxides. It should be understood that the epoxy resin has reactive epoxide groups that can be cured, for example, using the photoinitiator that generates acid upon exposure to actinic radiation.
  • cycloaliphatic multifunctional epoxides examples include 2- (3, 4-epoxycyclohexyl-5, 5-spiro-3, 4-epoxy) cyclohexane-1, 4-dioxane, bis (3, 4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, 3, 4-epoxy-6-methylcyclohexyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3, 4-epoxycyclohexane) , dicyclopentadiene diepoxide, di (3, 4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3, 4-epoxy
  • glycidyl ethers of cycloaliphatic alcohols e.g., 1, 4-cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane or 2, 2-bis (4-hydroxycyclohexyl) propane
  • cycloaliphatic multifunctional epoxide includes 3′, 4′-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate.
  • Epoxy compounds useful for the adhesive compositions according to the present disclosure include aromatic multifunctional epoxide resins (e.g., a chain-extended diepoxide or novolac epoxy resin having at least two epoxide groups) and aromatic monomeric multifunctional epoxides.
  • aromatic multifunctional epoxide resins e.g., a chain-extended diepoxide or novolac epoxy resin having at least two epoxide groups
  • aromatic monomeric multifunctional epoxides typically will have at least two epoxy end groups.
  • the aromatic multifunctional epoxide typically contains at least one (in some embodiments, at least 2, in some embodiments, in a range from 1 to 4) aromatic ring that is optionally substituted by a halogen (e.g., fluoro, chloro, bromo, iodo) , alkyl having 1 to 4 carbon atoms (e.g., methyl or ethyl) , or hydroxyalkyl having 1 to 4 carbon atoms (e.g., hydroxymethyl) .
  • a halogen e.g., fluoro, chloro, bromo, iodo
  • alkyl having 1 to 4 carbon atoms e.g., methyl or ethyl
  • hydroxyalkyl having 1 to 4 carbon atoms e.g., hydroxymethyl
  • the rings may be connected, for example, by an alkylene group having 1 to 4 carbon atoms that may be branched or straight-chained may optionally be substituted by halogen (e.g., fluoro, chloro, bromo, iodo) .
  • halogen e.g., fluoro, chloro, bromo, iodo
  • aromatic multifunctional epoxides useful in the adhesive compositions disclosed herein include novolac epoxy resins (e.g., phenol novolacs, ortho-, meta-, or para-cresol novolacs or combinations thereof) , bisphenol epoxy resins (e.g., bisphenol A, bisphenol F, halogenated bisphenol epoxies, and combinations thereof) , resorcinol epoxy resins, tetrakis phenylolethane epoxy resins and combinations of any of these.
  • novolac epoxy resins e.g., phenol novolacs, ortho-, meta-, or para-cresol novolacs or combinations thereof
  • bisphenol epoxy resins e.g., bisphenol A, bisphenol F, halogenated bisphenol epoxies, and combinations thereof
  • resorcinol epoxy resins etrakis phenylolethane epoxy resins and combinations of any of these.
  • Useful multifunctional epoxides include diglycidyl ethers of difunctional phenolic compounds (e.g., p, p’ -dihydroxydibenzyl, p, p'-dihydroxydiphenyl, p, p'-dihydroxyphenyl sulfone, p, p'-dihydroxybenzophenone, 2, 2'-dihydroxy-1, 1-dinaphthylmethane, and the 2, 2', 2, 3', 2, 4', 3, 3', 3, 4', and 4, 4' isomers of dihydroxydiphenylmethane, dihydroxydiphenyldimethylmethane, dihydroxydiphenylethylmethylmethane, dihydroxydiphenylmethylpropylmethane, dihydroxydiphenylethylphenylmethane, dihydroxydiphenylpropylphenylmethane, dihydroxydiphenylbutylphenylmethane, dihydroxydiphenyl
  • epoxy resins having amine groups include poly (N-glycidyl) compounds obtainable by dehydrochlorinating the reaction products of epichlorohydrin with amines containing at least two amine hydrogen atoms.
  • examples of these amines include aniline, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane.
  • Bisphenol epoxy resins for example, may be chain extended to have any desirable epoxy equivalent weight. Chain extending epoxy resins can be carried out by reacting a monomeric diepoxide, for example, with a bisphenol in the presence of a catalyst to make a linear polymer.
  • the aromatic epoxy resin (e.g., either a bisphenol epoxy resin or a novolac epoxy resin) may have an epoxy equivalent weight of at least 150, 170, 200, or 225 grams per equivalent. In some embodiments, the aromatic epoxy resin may have an epoxy equivalent weight of up to 2000, 1500, or 1000 grams per equivalent. In some embodiments, the aromatic epoxy resin may have an epoxy equivalent weight in a range from 150 to 2000, 150 to 1000, or 170 to 900 grams per equivalent. Epoxy equivalent weights may be selected, for example, so that the epoxy resin may be used as a liquid or solid, as desired.
  • Adhesive compositions of the present disclosure can include two or more cycloaliphatic multifunctional epoxides, two or more aromatic multifunctional epoxides, or any combination of cycloaliphatic multifunctional epoxides and aromatic multifunctional epoxides.
  • the adhesive composition does not comprise an aromatic multifunctional epoxide or comprises less than 3, 2, or 1 percent by weight, based on the total weight of the adhesive composition of an aromatic multifunctional epoxide.
  • Aromatic multifunctional epoxides that may be excluded from the adhesive composition may be any of those described above.
  • the adhesive composition of the present disclosure and/or useful in the method of the present disclosure includes an aliphatic compound comprising at least one of an oxirane ring or oxetane ring, which typically comprises a straight-chain or branched aliphatic (i.e., non-aromatic) group.
  • an aliphatic compound comprising at least one of an oxirane ring or oxetane ring, which typically comprises a straight-chain or branched aliphatic (i.e., non-aromatic) group.
  • such aliphatic compounds can be useful as reactive diluents that may help control the flow characteristics of the adhesive composition.
  • such aliphatic compounds can provide flexibility to the cured epoxy.
  • An aliphatic epoxy useful in the adhesive compositions of the present disclosure can include a branched or straight-chain alkylene group having 1 to 20 carbon atoms optionally interrupted with at least one -O-and optionally substituted by hydroxyl.
  • the aliphatic epoxy can include a poly (oxyalkylene) group having a plurality (x) of oxyalkylene groups, OR 1 , wherein each R 1 is independently C 2 to C 5 alkylene, in some embodiments, C 2 to C 3 alkylene, x is 2 to about 6, 2 to 5, 2 to 4, or 2 to 3.
  • useful aliphatic epoxies will typically have at least two oxirane rings.
  • useful aliphatic compounds having at least two oxirane rings include glycidyl epoxy resins such as those based on diglycidyl ether compounds comprising one or more oxyalkylene units.
  • Examples of these include resins made from ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, propanediol diglycidyl ether, butanediol diglycidyl ether, and hexanediol diglycidyl ether.
  • Examples of useful epoxides having more than two epoxide groups include glycerol triglycidyl ether, and polyglycidyl ethers of 1, 1, 1-trimethylolpropane, pentaerythritol, and sorbitol.
  • Examples of multifunctional epoxides having thioether groups include di-S-glycidyl derivatives of dithiols (e.g., ethane-1, 2-dithiol or bis (4-mercaptomethylphenyl) ether) .
  • non-aromatic epoxy resins include a diglycidyl ether of neopentyl glycol, a triglycidyl ether of trimethylolpropane, a diglycidyl ether of 1, 4-butanediol, and a reaction product of epichlorohydrin and n-butylamine.
  • epoxides useful in the adhesive composition of the present disclosure and/or useful in the method of the present disclosure are commercially available.
  • epoxy resins of various classes and epoxy equivalent weights are available from Dow Chemical Company, Midland, MI; Momentive Specialty Chemicals, Inc., Columbus, OH; Huntsman Advanced Materials, The Woodlands, TX; CVC Specialty Chemicals Inc. Akron, OH (acquired by Emerald Performance Materials) ; and Nan Ya Plastics Corporation, Taipei City, Taiwan.
  • Examples of commercially available cycloaliphatic multifunctional epoxides include those obtained from Daicel ChemTech, Inc., Tokyo, Japan, under the trade designations “CELLOXIDE 2021 P” , “CELLOXIDE 2081” , “CELLOXIDE 2000” , and “CELLOXIDE 8010” , Shin-Etsu Chemical Co., Ltd., Tokyo, Japan, under the trade designation “KR470” , from Synasia, Inc., Metuchen, NJ, under the trade designation “SYNA EPOXY” in various grades, and from Hexion Specialty Chemicals GmbH, Columbus, Ohio, under the trade designation “HELOXY MODIFIER 107” .
  • Examples of commercially available glycidyl ethers include diglycidylethers of bisphenol A (e.g. those available under the trade designations “EPON 828” , “EPON 1001” , “EPON 1310” and “EPON 1510” from Hexion Specialty Chemicals GmbH, Rosbach, Germany, those available under the trade designation “D.E.R. ” from Dow Chemical Co. (e.g., D.E.R. 331, 332, and 334) , those available under the trade designation “EPICLON” from Dainippon Ink and Chemicals, Inc. (e.g., EPICLON 840 and 850) and those available under the trade designation “YL-980” from Japan Epoxy Resins Co., Ltd.
  • diglycidylethers of bisphenol A e.g. those available under the trade designations “EPON 828” , “EPON 1001” , “EPON 1310” and “EPON 1510” from Hexion Specialty Chemical
  • Crosslinked epoxies that is, epoxy polymers
  • crosslinked epoxies that is, epoxy polymers
  • the aliphatic compound useful in the adhesive composition comprises a straight-chain or branched aliphatic group and an oxetane ring, in some embodiments, at least two oxetane rings.
  • the oxetane compound is not particularly limited, and suitable examples include bis [1-ethyl (3-oxetanyl) ] methyl ether, 3-ethyl-3 ⁇ [ (3-ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane, 4, 4′-bis [3-ethyl- (3-oxetanyl) methoxymethyl] biphenyl, 3-ethyl-3- [ (2-ethylhexyloxy) methyl] oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (4-hydroxybutyl) oxymethyloxetane, 1, 4-bis (3-ethyl-3-
  • the oxetane equivalent weight of the aliphatic compound having two or more oxetane rings is 400 or less or 300 or less and 100 or more.
  • the aliphatic compound is 3-ethyl-3 ⁇ [ (3-ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane.
  • Examples of commercially available products of the aliphatic compound comprising the oxetane ring include those available, for example, from Toagosei Co., Ltd., Tokyo, Japan, under the trade designation “OXT-221” , “OXT-212” , “OXT-101” , and “OXT-121” and those available, for example, form Ube Industries, Ltd., Tokyo, Japan, under the trade designations “ETERNACOLL” .
  • the amount of the aliphatic compound is at least 20, 30, 40, or 50 weight percent (wt%) and up to 90, 80, 75, or 70 wt%, based on the total weight of the multifunctional epoxide and the aliphatic compound. In some embodiments, the amount of the aliphatic compound is in the range from 20 wt%to 90 wt%, from 30 wt%to 80 wt%, from 40 wt%to 75 wt%, or from 50 wt%to 70 wt%, based on the total weight of the multifunctional epoxide and the aliphatic compound.
  • the amount of the multifunctional epoxide is at least 10, 20, 25, or 30 wt%and up to 80, 70, 60, or 50 wt%, based on the total weight of the multifunctional epoxide and the aliphatic compound. In some embodiments, the amount of the multifunctional epoxide is in the range from 10 wt%to 80 wt%, from 20 wt%to 70 wt%, from 25 wt%to 60 wt%, or from 30 wt%to 50 wt%, based on the total weight of the multifunctional epoxide and the aliphatic compound.
  • Adhesive compositions according to the present disclosure and/or useful in the method of the present disclosure comprise a polymeric toughener.
  • Polymeric tougheners may be useful, for example, for improving the properties of some cured epoxies, for example, so that they do not undergo brittle failure in a fracture.
  • the polymeric toughener e.g., an elastomeric resin or elastomeric filler
  • the polymeric toughener may or may not be covalently bonded to the epoxy and ultimately the crosslinked network.
  • the polymeric toughener includes an epoxy-terminated compound, which can be incorporated into the polymer backbone.
  • Examples of useful polymeric tougheners which may also be referred to as elastomeric modifiers, include polymeric compounds having both a rubbery phase and a thermoplastic phase such as graft copolymers having a polymerized diene rubbery core and a polyacrylate or polymethacrylate shell; graft copolymers having a rubbery core with a polyacrylate or polymethacrylate shell; elastomeric particles polymerized in situ in the epoxide from free-radical polymerizable monomers and a copolymeric stabilizer; elastomer molecules such as polyurethanes, thermoplastic elastomers, polysulfides, and silicones; separate elastomer precursor molecules; combination molecules that include epoxy-resin segments and elastomeric segments; and, mixtures of such separate and combination molecules.
  • graft copolymers having a polymerized diene rubbery core and a polyacrylate or polymethacrylate shell
  • the combination molecules may be prepared by reacting epoxy resin materials with elastomeric segments; the reaction leaving reactive functional groups, such as unreacted epoxy groups, on the reaction product.
  • the polymeric toughener in the curable epoxy resin includes graft copolymers having a polymerized diene rubbery backbone or core to which is grafted a shell of an acrylic acid ester or methacrylic acid ester, monovinyl aromatic hydrocarbon, or a mixture thereof, such as those disclosed in U.S. Pat. No. 3,496,250 (Czerwinski) .
  • Rubbery backbones can comprise polymerized butadiene or a polymerized mixture of butadiene and styrene.
  • Shells comprising polymerized methacrylic acid esters can be lower alkyl (C 1-4 ) methacrylates.
  • Monovinyl aromatic hydrocarbons can be styrene, alpha-methylstyrene, vinyltoluene, vinylxylene, ethylvinylbenzene, isopropylstyrene, chlorostyrene, dichlorostyrene, and ethylchlorostyrene.
  • acrylate core-shell graft copolymers wherein the core or backbone is a polyacrylate polymer having a glass transition temperature (T g ) below about 0 °C, such as poly (butyl acrylate) or poly (isooctyl acrylate) to which is grafted a polymethacrylate polymer shell having a T g about 25 °C such as poly (methyl methacrylate) .
  • T g glass transition temperature
  • core will be understood to be acrylic polymer having T g ⁇ 0°C.
  • shell will be understood to be an acrylic polymer having T g > 25°C.
  • Some core/shell polymeric tougheners e.g., including acrylic core/shell materials and methacrylate-butadiene-styrene (MBS) copolymers wherein the core is crosslinked styrene/butadiene rubber and the shell is polymethylacrylate
  • PARALOID e.g., from Dow Chemical Company under the trade designation “PARALOID” .
  • Core-shell rubber particles as described in this document include a cross-linked rubber core, in most cases being a cross-linked copolymer of butadiene, and a shell which is preferably a copolymer of styrene, methyl methacrylate, glycidyl methacrylate and optionally acrylonitrile.
  • the core-shell rubber can be dispersed in a polymer or an epoxy resin.
  • Examples of useful core-shell rubbers include those sold by Kaneka Corporation under the designation Kaneka KANE ACE, including the Kaneka KANE ACE 15 and 120 series of products, including Kaneka “KANE ACE MX 153” , Kaneka “KANE ACE MX 154” , Kaneka “KANE ACE MX 156” , Kaneka “KANE ACE MX 257” and Kaneka “KANE ACE MX 120” core-shell rubber dispersions, and mixtures thereof.
  • the products contain the core-shell rubber (CSR) particles pre-dispersed in an epoxy resin, at various concentrations.
  • CSR core-shell rubber
  • KANE ACE MX 153 core-shell rubber dispersion comprises 33%CSR
  • KANE ACE MX 154 core-shell rubber dispersion comprises 40%CSR
  • KANE ACE MX 156 core-shell rubber dispersions comprises 25%CSR.
  • polymeric tougheners useful in the adhesive composition of the present disclosure are elastomeric particles that have a T g below about 25 °C and have been polymerized in situ in the epoxide before mixing with the other components of the curable composition.
  • These elastomeric particles are polymerized from free-radical polymerizable monomers and a copolymerizable polymeric stabilizer that is soluble in the epoxide.
  • the free-radical polymerizable monomers are ethylenically unsaturated monomers or diisocyanates combined with coreactive difunctional hydrogen compounds such as diols, diamines, and alkanolamines. Examples of these elastomeric particles are disclosed in U.S. Pat. No. 4,524,181 (Adam et al. ) . These particles are commonly referred to as "organosols" .
  • Still other polymeric tougheners are rubber modified liquid epoxy resins.
  • an ABA block copolymer elastomer with epoxy-reactive groups can be reacted with an epoxy resin to provide a rubber-modified liquid epoxy resin.
  • An ABA block copolymer elastomer generally is one where the A blocks are polystyrenic, and the B blocks are conjugated dienes (e.g., lower alkylene dienes) .
  • the A block is generally formed predominantly of substituted (e.g, alkylated) or unsubstituted styrenic moieties (e.g., polystyrene, poly (alphamethylstyrene) , or poly (t-butylstyrene) ) , having an average molecular weight from about 4,000 to 50,000 grams per mole.
  • the B block (s) is generally formed predominantly of conjugated dienes (e.g., isoprene, 1, 3-butadiene, or ethylene-butylene monomers) , which may be substituted or unsubstituted, and has an average molecular weight from about 5,000 to 500,000 grams per mole.
  • the A and B blocks may be configured, for example, in linear, radial, or star configurations.
  • An ABA block copolymer may contain multiple A and/or B blocks, which blocks may be made from the same or different monomers.
  • An example of such a resin is an elastomer available from Kraton Performance Polymers under the trade designation “KRATON RP6565” .
  • the modified epoxy resin is made from 85%by weight of epoxy resin “EPON 828” and 15%by weight of a rubber obtained under trade designation “KRATON” . Rubbers obtained under the trade designation “KRATON” are known in the industry as elastomeric block copolymers.
  • polymeric tougheners include epoxy-, hydroxy-, carboxyl-and amine-terminated acrylonitrile/butadiene elastomers such as those obtained from Huntsman Advanced Materials under the trade designation “HYPRO” (e.g., ETBN, HTBN, CTBN and ATBN grades) ; carboxyl-and amine-terminated butadiene polymers such as those obtained from Huntsman Advanced Materials under the trade designation “HYPRO” (e.g., CTB grade) ; amine-functional polyethers such as any of those described above; and amine-functional polyurethanes such as those described in U.S. Pat. Appl. No. 2013/0037213 (Frick et al. ) .
  • Polyurethane polymeric tougheners can also include polyurethane-modified epoxy resins, isocyanate-modified epoxy resins, and combinations thereof.
  • the polymeric toughener comprises at least one of a core-shell polymer, a butadiene nitrile rubber, a polysulfide, or a silicone.
  • the polymeric toughener comprises butadiene nitrile rubber having at least one of an amino, epoxy, hydroxyl, or carboxy group or a core-shell polymer comprising a shell comprising a C 1-4 alkyl methacrylate polymer or copolymer and a core comprising at least one of a cross-linked butadiene copolymer, a butadiene styrene copolymer, or a C 4-18 alkyl acrylate.
  • the polymeric toughener is present in an amount from one wt%to 60 wt%, from 5 wt%to 55 wt%, or 10 wt%to 40 wt%, based on the total weight of the multifunctional epoxide, the aliphatic compound, and the polymeric toughener. In some embodiments, the polymeric toughener is present in an amount of at least 1, 5, 10, 15 or 20 wt%, up to 60, 55, 50, 40, or 35 wt%, or any combination thereof, based on the total weight of the multifunctional epoxide, the aliphatic compound, and the polymeric toughener.
  • the adhesive composition of the present disclosure and/or useful for practicing the method of the present disclosure includes a cationic photoinitiator that generates acid on exposure to actinic radiation.
  • the photoinitiator that generates acid on exposure to actinic radiation absorbs light in a wavelength range from 200 nm to 700 nm.
  • the photoinitiator absorbs light in the ultraviolet A (UVA) and/or blue light regions, for example, in a wavelength range from 315 nm to 550 nm or 315 nm to 500 nm.
  • UVA light can be considered to have a wavelength range of 315 nm to 400 nm
  • blue light can be considered to have a wavelength range of 400 nm to 500 nm.
  • Any compound that generates an acid on exposure to actinic irradiation may be useful in the compositions of the present disclosure.
  • the acid generated may be a Lewis acid or a Bronsted acid.
  • Suitable acid generating compounds include onium salts and iodosyl salts, aromatic diazonium salts, metallocenium salts, o-nitrobenzaldehyde, the polyoxymethylene polymers described in U.S. Pat. No. 3,991,033, the o-nitrocarbinol esters described in U.S. Pat. No. 3,849,137, the o-nitrophenyl acetals, their polyesters, and end-capped derivatives described in U.S. Pat. No.
  • Suitable aromatic onium salts include those described U.S. Pat. Nos. 4,058,400 and 4,058,401.
  • Suitable aromatic sulfoxonium salts which can be used include those described in U.S. Pat. Nos. 4,299,938, 4,339,567, 4,383,025 and 4,398,014.
  • Suitable aliphatic and cycloaliphatic sulfoxonium salts include those described in European Patent Application Publication No. EP-AG 164 314.
  • Aromatic iodonium salts which can be used include those described in British Patent Specification Nos. 1 516 351 and 1 539 192.
  • Aromatic iodosyl salts which can be used include those described in U.S. Pat. No. 4,518,676.
  • the photoinitiator that generates acid upon exposure to actinic radiation is an aromatic iodonium salt or an aromatic sulfonium salt.
  • the photoinitiator typically generates both acid and free radicals.
  • Suitable aromatic groups for these salts include phenyl, thienyl, furanyl naphthyl, pyrazolyl groups, benzothienyl, dibenzothienyl, benzofuranyl, dibenzofuranyl, any of which may be unsubstituted or substituted by one or more of halogen, nitro, N-arylanilino groups, ester groups (e.g., methoxycarbonyl, ethoxycarbonyl, or phenoxycarbonyl) , sulfo ester groups (e.g., methoxysulfonyl, butoxysulfonyl, or phenoxysulfonyl) , amido groups (e.g., aceta
  • the aromatic groups may also be bridged, for example, by -S (O) 0-2 -, -O-, carbonyl, -N (aryl) -, a bond (e.g., as in biphenyl) , or an alkylene group.
  • Suitable counterions for the aromatic iodonium and sulfononium cations include tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, tetrakis (pentafluorophenyl) borate, phenyltris (pentafluorophenyl) borate, and tris (pentafluoroethyl) trifluorophosphate.
  • the photoinitiator that generates acid upon exposure to actinic radiation is an aromatic iodonium salt.
  • aromatic iodonium salt photoinitiators include diphenyliodonium tetrafluoroborate, di (4-methylphenyl) iodonium tetrafluoroborate, phenyl-4-methylphenyliodonium tetrafluoroborate, di (4-heptylphenyl) iodonium tetrafluoroborate, di (3-nitrophenyl) iodonium hexafluorophosphate, di (4-chlorophenyl) iodonium hexafluorophosphate, di (naphthyl) iodonium tetrafluoroborate, di (4-trifluoromethylphenyl) iodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, di (4-
  • the photoinitiator that generates acid on exposure to actinic radiation is an aromatic sulfonium salt.
  • the sulfur in the sulfonium salts is substituted with at one, two, or three aromatic groups.
  • the sulfur may also be substituted with one or two alkyl groups having 1 to 20 carbon atoms and optionally substituted by halogen, hydroxy, alkoxy, or aryl.
  • the sulfonium salt is a triaryl substituted sulfonium salt.
  • aromatic sulfonium salt photoinitiators include triphenylsulfonium tetrafluoroborate, methyldiphenylsulfonium tetrafluoroborate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritolysulfonium hexafluorophosphate, anisyldiphenylsulfonium hexafluoroantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, tris (4-phenoxyphenyl) sulfonium hexafluor
  • the aromatic iodonium and sulfonium salts can be made by known methods. See for example, U.S. Pat. Nos. 3,565,906; 3,712,920; 3,759,989; and 3,763,187; F. Beringer, et al., Diaryliodonium Salts IX, J. Am. Chem. Soc. 81, 342-51 (1959) and F. Beringer, et al., Diaryliodonium Salts XXIII, J. Chem. Soc. 1964, 442-51; F. Beringer, et al., lodonium Salts Containing Heterocyclic Iodine, J. Org. Chem. 30, 1141-8 (1965) ; J. Crivello et al., Photoinitiated Cationic Polymerization with Triarylsulfonium Salts, J. Polymer Science, 17, 977 (1979) . Some are available from commercial sources.
  • any of the cationic photoinitiators described herein may be used singly or in combinations of two or more.
  • the cationic photoinitiator is not N-benzylpyrazinium hexafluoroantimonate.
  • the adhesive composition of the present disclosure and/or useful in the method of the present disclosure includes a thermal cationic initiator.
  • the thermal cationic initiator is a compound that generates cationically active species by heat but does not generate a practical amount of a cationically active species by light irradiation.
  • the temperature at which the cationically active species is generated is at least 60 °C or 70 °C and not more than 120 °C, 100 °C, 90 °C, or 80 °C.
  • the thermal cationic initiator is also a salt having any of the anions described above for cationic photoinitiators: tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, tetrakis (pentafluorophenyl) borate, phenyltris (pentafluorophenyl) borate, and tris (pentafluoroethyl) trifluorophosphate.
  • the cation is an ammonium cation or a sulfonium cation.
  • Ammonium cations useful for the thermal cationic initiator have four substituents on a nitrogen atom that are each independently a hydrogen atom, a linear, branched-chain, or cyclic alkyl group having 1 to 20, 1 to 12, 1 to 8, 1 to 6, or 1 to 4 carbon atoms, an aryl group, an alkylarylenyl group, an arylalkylenyl group, or an alkylenearylalkylenyl group.
  • At least one substituent is aryl (e.g., phenyl) or alkylarylenyl group, an arylalkylenyl group, or an alkylenearylalkylenyl, and the remaining substituents are independently alkyl groups.
  • at least two substituents are aryl (e.g., phenyl) or an alkylarylenyl group, an arylalkylenyl group (e.g., benzyl) , or an alkylenearylalkylenyl, and the remaining substituents are independently alkyl groups.
  • the alkyl group or aryl group may have a substituent.
  • Examples of the substituent for the alkyl group include a phenyl group, an alkoxy group having 1 to 15 carbon atoms, and a hydroxy group.
  • the alkyl group has a substituent, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group.
  • Examples of the substituent for an aromatic ring include an alkyl group having 1 to 15 carbon atoms, a hydroxyalkyl group having 1 to 15 carbon atoms, and an alkoxy group having 1 to 15 or 1 to 8 carbon atoms (in some embodiments, a methoxy group and an ethoxy group) , and a phenylthio group.
  • ammoinium cations useful in the thermal cationic initiator include dimethylphenyl (4-methoxybenzyl) ammonium, methylphenyldibenzylammonium, phenyltribenzylammonium, and dimethylphenyl (3, 4-dimethylbenzyl) ammonium.
  • Sulfonium cations useful for the thermal cationic initiator have three substituents on a sulfur atom in which at least one among three substituents is alkyl group having 1 to 20, 1 to 12, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Alternatively, two among three groups bonding to the sulfur atom together form an alkylene group to form a ring with the sulfur atom.
  • the other groups may be an alkenyl group, an aryl group, an alkylarylenyl group, an arylalkylenyl group, or an alkylenearylalkylenyl group.
  • the sulfonium cation is represented by the formula
  • R 1 is phenyl or naphthyl, each optionally containing substituent
  • R 2 is alkyl having 1 to 18 carbon atoms
  • R 3 is phenyl or naphthyl, each optionally containing substituent, alkyl optionally containing substituent, cycloalkyl, alkenyl optionally containing substituent, or 2-indanyl.
  • Suitable substituents for phenyl or naphthyl include alkyl having about 1 to 18 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, and hexyl; alkoxy having about 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, hexyloxy, decyloxy, and dodecyloxy; carbonyloxy such as acetoxy, propyonyloxy, decylcarbonyloxy, dodecylcarbonyloxy, methoxycarbonyl, ethoxycarbonyl, and benzoyloxy; phenylthio; halogen (i.e., fluorine, chlorine, bromine, and iodine) ; cyano; nitro; and hydroxy.
  • alkyl having about 1 to 18 carbon atoms such as methyl, e
  • R 2 and/or R 3 is alkyl having 1 to 12 or 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or hexyl.
  • Suitable substituents for an alkyl group and an alkenyl group include alkoxy such as methoxy, ethoxy, propoxy, butoxy, hexyloxy, decyloxy, and dodecyloxy; carbonyloxy such as acetoxy, propyonyloxy, decylcarbonyloxy, dodecylcarbonyloxy, methoxycarbonyl, ethoxycarbonyl, and benzoyloxy; phenylthio; halogen (i.e., fluorine, chlorine, bromine, and iodine) ; cyano; nitro; hydroxy; and phenyl.
  • alkoxy such as methoxy, ethoxy, propoxy, butoxy, hexyloxy, decyloxy, and dodecyloxy
  • carbonyloxy such as acetoxy, propyonyloxy, decylcarbonyloxy, dodecylcarbonyloxy, methoxycarbon
  • R 3 is cycloalkyl having from 3 to 12 carbon atoms. In some embodiments, R 3 is cyclohexyl, cyclohexanonyl, cyclopentyl, 1-acenaphthenyl, bicyclononyl, norbornyl, coumarinyl, dihydrobenzofuranyl, or a camphor group.
  • the sulfonium cation is represented by formula
  • n 1, 2, or 3
  • R3 is as described above in any of its embodiments.
  • the thermal cationic initiator is copper (II) trifluoromethane sulfonate. Any of the thermal cationic initiators described herein may be used singly or in combinations of two or more.
  • the thermal cationic initiator comprises an antimony-containing compound. In some embodiments, the antimony compound makes up at least 5, 10, 20, 25, 50, 75, or 100 percent by weight based on the total weight of the thermal cationic initiator.
  • the adhesive composition is free of at least one of a free-radical initiator or ethylenically unsaturated functional groups.
  • the adhesive composition can contain cationic photoinitiators described herein without including other classes of photoinitiators such as those that do not generate cations upon exposure to actinic radiation such as acetophenones, benzilketal, alkylaminoacetophenones, benzoyl phosphine oxides, benzoin ethers, benzophenones, and benzoylformate esters.
  • the adhesive composition can be free of benzaldehyde, 2, 4, 6-trimethylbenzaldehyde, benzoic acid, 2, 4, 6-trimethylbenzoic acid, benzil, methyl benzoate, acetophenone, isopropanol, acetone, glycol, formaldehyde, toluene, acetaldehyde, diphenylphosphine oxide, or ethyl phenylphosphinate, which are typical residues from such free-radical photoinitiators and can be detected from Thermal Desorption Mass Spectrometry (TD-MS) .
  • TD-MS Thermal Desorption Mass Spectrometry
  • the adhesive composition of the present disclosure and/or useful for practicing the method of the present disclosure includes a compound having at least one hydroxyl group (in some embodiments, a polyol) .
  • a polyol refers to an organic compound having two or more hydroxy groups.
  • the polyol can be added as a chain extender for the epoxy resin and can be a source of protons for a cationic polymerization reaction.
  • the polyol is a diol (i.e., polyols with two hydroxy groups) .
  • Suitable diols include 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 2, 2-dimethyl-1, 3-propanediol, 2-ethyl-1, 6-hexanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, glycerol, trimethylolpropane, 1, 2, 6-hexanetriol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerine, 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol, 2-
  • the polyol When a polyol is included in the adhesive composition, the polyol is typically present in an amount up to 5 wt%or up to 2.5 wt%based on the total weight of the adhesive composition.
  • the polyol can be present in an amount of at least 0.5 wt%, at least 1 wt%, or at least 2 wt%based on the weight of the adhesive composition.
  • the polyol is often present in an amount of 0.5 wt%to 5 wt%, 1 wt%to 5 wt%, 0.5 wt%to 3.0 wt%, or 1 wt%to 2.5 wt%based on the total weight of the adhesive composition.
  • the polyol In a second part of a two-part composition, the polyol can be present in an amount of at least 10, 15, 20, or 25 wt%and up to 75, 60, 50, or 40 wt%, based on the total weight of the second part.
  • the adhesive composition of the present disclosure and/or useful for practicing the method of the present disclosure include a silane coupling agent.
  • suitable silane coupling agents include those represented by formula L- [R 2 Si (Y) 3 ] k .
  • L is an amino group (e.g., primary or secondary amino group) , a mercapto group (i.e., HS-) , or an epoxy group (i.e., ) .
  • Such L groups are capable of reacting with an epoxy resin.
  • L is an epoxy group.
  • k is typically 1, but when L is an amino group, k is 1 or 2.
  • R 2 is alkylene (e.g., having up to 8, 6, or 4 carbon atoms) optionally interrupted by at least one ether linkage
  • Y is a hydroylzable group such as halogen (i.e., fluoride, chloride, bromide, or iodide) , alkoxy (i.e., –O-alkyl) , acyloxy (i.e., -OC (O) alkyl) , or aryloxy (i.e., –O-aryl) .
  • Silane coupling agents can be useful for promoting adhesion between the epoxy resin and a filler (e.g., siliceous filler) in the composition or between the epoxy resin and a substrate onto which it is dispensed.
  • a filler e.g., siliceous filler
  • useful silane coupling agents include 3-glycidoxypropyltrimethoxysilane, available, for example, from The Dow Chemical Company under the trade designation "DOWSIL Z-6040 SILANE”; an epoxy-functional silane available from Sinopharm Chemical Reagent Co., Ltd., Shanghai, China, under the trade designation “KH-560” ; bis (trimethoxysilylpropyl) amine available, for example, from Gelest, Morrisville, PA; (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane) , (3-mercaptopropyl) trimethoxysilane, and (3-mercaptopropyl
  • the adhesive composition includes 3-glycidoxypropyltrimethoxysilane.
  • Silane coupling agents can be present in the adhesive composition in an amount of up to 5, 4, 3, 2, or 1 wt%, at least 0.1, 0.2, 0.3, 0.4, or 0.5 wt%, or any combination thereof, based on the total weight of the adhesive composition.
  • the silane coupling agent can be present in an amount of at least 5, 10, 15, 20, or 25 wt%and up to 50, or 40 wt%, based on the total weight of the second part.
  • additives may be included in the adhesive composition of the present disclosure and/or useful in the method of the present disclosure, for example, to alter the characteristics of the cured composition.
  • useful additives include corrosion inhibitors such as some silica gels, thixotropic agents such as fumed silica; pigments (e.g., ferric oxide, brick dust, carbon black, and titanium oxide) , reinforcing agents (e.g., silica, magnesium sulfate, calcium sulfate, and beryllium aluminum silicate) , clays such as bentonite, and any suitable filler (e.g., glass beads, talc, and calcium metasilicate) .
  • Amounts of up to about 30, 40, 50, 60, or 70 wt%, based on the total weight of the adhesive composition, may be effectively utilized.
  • the adhesive composition of the present disclosure and/or useful in the method of the present disclosure includes inorganic filler.
  • the inorganic filler comprises at least one of quartz glass, silica, titanium dioxide, zirconium tungstate, alumina, aluminum nitride, boron nitride, graphite (and expanded graphite or graphite-based nanotechnology products) , carbon nanotubes, or a metal filler.
  • quartz, quartz glass, or silica may be useful as a filler.
  • Materials with a negative coefficient of thermal expansion, such as zirconium tungstate, may also be useful.
  • Fillers such as alumina, aluminum nitride, boron nitride, graphite (and expanded graphite or graphite-based nanotechnology products) , carbon nanotubes, or metal fillers may be useful for increasing the thermal conductivity of the adhesive composition.
  • a metal filler or non-metallic filler coated with a conductive layer may be useful.
  • the so-called spacer particles having a narrowly defined particle shape and particle size distribution may be used as a filler.
  • the choice of filler is by no means limited. As known, various particle shapes or particle sizes or particle size distributions may be combined to achieve, for example, lower viscosity, higher maximum filling levels or high electrical and thermal conductivity.
  • the particle size of the filler is in a range from 5 to 50 micrometers.
  • the inorganic filler is free of or contains less than 0.75, 0.5, 0.25, 0.1, or 0.01 wt%of a filler selected from the group consisting of oxides, hydroxides, and carbonates containing a Group II element in the periodic table.
  • the present disclosure provides a method of making a bonded article comprising a first substrate and a second substrate.
  • the method includes applying the adhesive composition of any one of the first to twenty-fourth embodiments onto at least one of the first substrate or the second substrate, adhering the first substrate and the second substrate using the adhesive composition, and at least one of heating or irradiating the adhesive composition to at least partially cure the adhesive composition to make the bonded article. After irradiating, the adhesive composition gels and generally achieves handling strength.
  • the method comprises both heating and irradiating the adhesive composition.
  • the adhesive composition is a one-part composition that includes the multifunctional epoxide, the aliphatic compound, the polymeric toughener, the cationic photoinitiator, and the thermal cationic initiator. It can be useful to package the adhesive composition of the present disclosure in a container that protects it from premature exposure to light.
  • the adhesive composition can be stored at room temperature (20 °C to 25 °C) for at least 24, 48, or 72 hours.
  • the adhesive composition can also be stored below room temperature, for example, in a freezer at not more than 0 °C, -10 °C, or -20 °C.
  • compositions can be applied as a continuous bead, in intermediate dots, stripes, diagonals or any other geometrical form that will conform to forming a useful bond.
  • Adhesive compositions of the present disclosure may be useful, for example, for bonding a first substrate to a second substrate to provide a bonded article.
  • substrates may be bonded with compositions of the present disclosure such as metal (e.g., stainless steel or aluminum) , glass (e.g., which may be coated with indium tin oxide) , a polymer (e.g., a plastic, rubber, thermoplastic elastomer, or thermoset) , or a composite.
  • a composite material may be made from any two or more constituent materials with different physical or chemical properties. When the constituents are combined to make a composite, a material having characteristics different from the individual components is typically achieved.
  • useful composites include fiber-reinforced polymers (e.g., carbon fiber reinforced epoxies and glass-reinforced plastic) ; metal matrix compositions, and ceramic matrix composites.
  • Useful polymeric substrates that can be bonded include polymers such as polyolefins (polypropylene, polyethylene, high density polyethylene, blends of polypropylene) , polyamide 6 (PA6) , polyamide 6, 6, acrylonitrile butadiene styrene (ABS) , polycarbonate (PC) , PC/ABS blends, polyvinyl chloride (PVC) , polyamide (PA) , polyurethane (PUR) , thermoplastic elastomers (TPE) , polyoxymethylene (POM) , polystyrene, poly (methyl) methacrylate (PMMA) , polyvinyl chloride (PVC) , polyetheretherketone (PEEK) , polyphenylene sulfide (PP
  • a suitable light-emitting curing device has a radiometric energy from 0.1 -5 W/cm 2 , 0.1 –3 W/cm 2 , or 0.1 –2 W/cm 2 .
  • the light source and exposure time can be selected, for example, based on the nature and amount of the adhesive composition.
  • Sources of ultraviolet and/or visible light can be useful (for example, wavelengths ranging from about from about 200 nm to about 700 nm, 200 nm to about 650 nm, from about 315 nm to 550 nm, or from about 315 nm to 500 nm can be useful) .
  • Suitable light includes sunlight and light from artificial sources, including both point sources and flat radiators.
  • the light source is a source of at least one of UVA or blue light. In some embodiments, the light source is a blue light source.
  • Examples of useful light sources include carbon arc lamps; xenon arc lamps; medium-pressure, high-pressure, and low-pressure mercury lamps, doped if desired with metal halides (metal halogen lamps) ; microwave-stimulated metal vapor lamps; excimer lamps; superactinic fluorescent tubes; fluorescent lamps; incandescent argon lamps; electronic flashlights; xenon flashlights; photographic flood lamps; light-emitting diodes (LED) ; laser light sources (for example, excimer lasers) ; and combinations thereof.
  • the distance between the light source and the composition to be cured can vary widely, depending upon the particular application and the type and/or power of the light source. For example, distances up to about 150 cm, distances from about 0.01 cm to 150 cm, or a distance as close as possible without touching the composition can be useful.
  • the adhesive composition is packaged as a two-part adhesive composition, wherein a first part comprises the multifunctional epoxide and, optionally, the aliphatic compound, and a second part comprises the cationic photoinitiator.
  • the other components of the adhesive composition can be included in one or both the first and second parts.
  • the polymeric toughener can be added to the first part, the second part, or both.
  • the polymeric toughener can be pre-dispersed with an epoxy resin in the first part and/or pre-dispersed with a polyol in the second part, if desired.
  • the present disclosure further provides an adhesive dispenser comprising a first chamber and a second chamber. The first chamber comprises the first part, and the second chamber comprises the second part.
  • the curable adhesive composition is a two-part adhesive, in which a first part comprises the multifunctional epoxide and, optionally, the aliphatic compound and a second part comprises cationic photoinitiator.
  • the other components of the adhesive composition can be included in one or both the first and second parts.
  • Applying the curable adhesive composition can be carried out, for example, by dispensing the adhesive composition from an adhesive dispenser comprising a first chamber, a second chamber, and a mixing tip, wherein the first chamber comprises the first part, wherein the second chamber comprises the second part, and wherein the first and second chambers are coupled to the mixing tip to allow the first part and the second part to flow through the mixing tip.
  • the method comprises irradiating the second part of the two-part adhesive composition and, after irradiating the second part, mixing the first part and the second part to form the adhesive composition.
  • the method includes applying the adhesive composition onto at least one of the first substrate or the second substrate, adhering the first substrate and the second substrate using the adhesive composition, and allowing the adhesive composition to at least partially cure to make the bonded article. Irradiating, mixing, and applying can be carried out using any of the methods described above. After irradiating, the cationic species is generated from the cationic photoinitiator.
  • the cationic species remains active for at least six weeks, as shown in the Examples, below.
  • the two-part adhesive composition gels, reaches a desired handling strength, and may ultimately achieve a desired final strength.
  • the adhesive composition may be heated at an elevated temperature to effect further curing or curing in areas that were not exposed to light. While it is not practical to enumerate a particular temperature suitable for all situations, generally suitable temperatures are in a range from about 50 °C to about 100 °C, from 50 °C to 80 °C, or from 80 °C to 100 °C. In some embodiments, heating at 60 °C to 80 °C or 80 °C to 100 °C for 15 minutes to 60 minutes, for example, can be useful for enhancing the cure. However, in some embodiments, the curable composition according to the present disclosure does not require heat to cure (that is, it is a room temperature curable adhesive) yet still provides high performance (e.g., overlap shear strength) .
  • high performance e.g., overlap shear strength
  • the present disclosure provides an adhesive composition
  • a multifunctional epoxide comprising at least two oxirane rings and at least one of a cycloaliphatic or aromatic ring; optionally an aliphatic compound comprising at least one of an oxirane ring or an oxetane ring; a polymeric toughener; and a cationic photoinitiator, wherein at least one of the following limitations is met: the adhesive composition further comprises a thermal cationic initiator, or the adhesive composition is packaged as a two-part adhesive composition, wherein a first part comprises the multifunctional epoxide and the aliphatic compound, a second part comprises the cationic photoinitiator, and wherein at least one of the first part or the second part comprises the polymeric toughener.
  • the present disclosure provides an adhesive composition
  • a multifunctional epoxide comprising at least two oxirane rings and at least one of a cycloaliphatic or aromatic ring; an aliphatic compound comprising at least one of an oxirane ring or an oxetane ring; a polymeric toughener; a cationic photoinitiator; and a thermal cationic initiator.
  • the present disclosure provides the adhesive composition of the first or second embodiment, wherein the polymeric toughener comprises at least one of a core-shell polymer, a butadiene nitrile rubber, a polysulfide, or a silicone.
  • the present disclosure provides the adhesive composition of any one of the first to third embodiments, wherein the polymeric toughener comprises butadiene nitrile rubber having at least one of an amino, epoxy, hydroxyl, or carboxy group or a core-shell polymer comprising a shell comprising a C 1-4 alkyl methacrylate polymer or copolymer and a core comprising at least one of a cross-linked butadiene copolymer, a butadiene styrene copolymer, or a C 4-18 alkyl acrylate.
  • the polymeric toughener comprises butadiene nitrile rubber having at least one of an amino, epoxy, hydroxyl, or carboxy group or a core-shell polymer comprising a shell comprising a C 1-4 alkyl methacrylate polymer or copolymer and a core comprising at least one of a cross-linked butadiene copolymer, a butadiene styrene copolymer, or
  • the present disclosure provides the adhesive composition of any one of the first to fourth embodiments, wherein the polymeric toughener is present in an amount from one weight percent to 60 weight percent, 5 weight percent to 55 weight percent, or 10 weight percent to 40 weight percent, based on the total weight of the multifunctional epoxide, the aliphatic compound, and the polymeric toughener.
  • the present disclosure provides the adhesive composition of any one of the first to fifth embodiments, wherein the polymeric toughener is free of ethylenically unsaturated terminal groups.
  • the present disclosure provides the adhesive composition of any one of the first to sixth embodiments, wherein the multifunctional epoxide comprises at least two oxirane rings and at least two cycloaliphatic rings.
  • the present disclosure provides the adhesive composition of any one of the first to seventh embodiments, wherein the multifunctional epoxide comprises at least one of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate or bis ( (3, 4-epoxycyclohexyl) methyl) adipate.
  • the present disclosure provides the adhesive composition of any one of the first to eighth embodiments, wherein the multifunctional epoxide comprises a bisphenol epoxy resin, a novolac epoxy resin, or a combination thereof.
  • the present disclosure provides the adhesive composition of any one of the first to eighth embodiments, wherein the adhesive composition does not comprise an aromatic multifunctional epoxide or comprises less than 3, 2, or 1 percent by weight, based on the total weight of the adhesive composition of the aromatic multifunctional epoxide.
  • the present disclosure provides the adhesive composition of any one of the first to tenth embodiments, wherein the aliphatic compound comprises at least two oxetane groups.
  • the present disclosure provides the adhesive composition of the eleventh embodiment, wherein the aliphatic compound comprises 3-ethyl-3 ⁇ [ (3-ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane.
  • the present disclosure provides the adhesive composition of any one of the first to twelfth embodiments, wherein the aliphatic compound comprises at least two oxirane groups.
  • the present disclosure provides the adhesive composition of the thirteenth embodiment, wherein the aliphatic compound comprises a diglycidyl ether of polypropylene glycol.
  • the present disclosure provides the adhesive composition of any one of the first to fourteenth embodiments, wherein the thermal cationic initiator comprises an antimony-containing compound.
  • the present disclosure provides the adhesive composition of the fifteenth embodiment, wherein the antimony compound makes up at least 5, 10, 20, 25, 50, 75, or 100 percent by weight based on the total weight of the thermal cationic initiator.
  • the present disclosure provides the adhesive composition of any one of the first to sixteenth embodiments, further comprising a silane coupling agent.
  • the present disclosure provides the adhesive composition of any one of the first to seventeenth embodiments, further comprising a thixotropic agent.
  • the present disclosure provides the adhesive composition of any one of the first to eighteenth embodiments, further comprising inorganic filler.
  • the present disclosure provides the adhesive composition of the nineteenth embodiment, wherein the inorganic filler comprises at least one of quartz glass, silica, titanium dioxide, zirconium tungstate, alumina, aluminum nitride, boron nitride, graphite (and expanded graphite or graphite-based nanotechnology products) , carbon nanotubes, or a metal filler.
  • the present disclosure provides the adhesive composition of any one of the first to twentieth embodiments, wherein the inorganic filler is free of or contains less than 0.75, 0.5, 0.25, 0.1, or 0.01 percent by weight of a filler selected from the group consisting of oxides, hydroxides, and carbonates containing a Group II element in the periodic table.
  • the present disclosure provides the adhesive composition of any one of the first to twenty-first embodiments, further comprising a polyol.
  • the present disclosure provides the adhesive composition of the twenty-second embodiment, wherein the adhesive composition is packaged as a two-part adhesive composition, and wherein the second part further comprises a polyol.
  • the present disclosure provides the adhesive composition of any one of the twenty-first to twenty-third embodiments, wherein the adhesive composition is free of at least one of a free-radical initiator or ethylenically unsaturated functional groups.
  • the present disclosure provides a method of making a bonded article comprising a first substrate and a second substrate, the method comprising:
  • the present disclosure provides the method of the twenty-fifth embodiment, wherein the method comprises both heating and irradiating the adhesive composition.
  • the present disclosure provides an adhesive composition comprising: a multifunctional epoxide comprising at least two oxirane rings and at least one of a cycloaliphatic or aromatic ring; a polymeric toughener; and a cationic photoinitiator, wherein the adhesive composition is packaged as a two-part adhesive composition, wherein a first part comprises the p multifunctional epoxide, a second part comprises the cationic photoinitiator, and wherein at least one of the first part or the second part comprises the polymeric toughener.
  • the present disclosure provides the adhesive composition of the twenty-seventh embodiment, wherein the polymeric toughener comprises at least one of a core-shell polymer, a butadiene nitrile rubber, a polysulfide, or a silicone.
  • the present disclosure provides the adhesive composition of the twenty-seventh or twenty-eighth embodiment, wherein the polymeric toughener comprises butadiene nitrile rubber having at least one of an amino, epoxy, hydroxyl, or carboxy group or a core-shell polymer comprising a shell comprising a C 1-4 alkyl methacrylate polymer or copolymer and a core comprising at least one of a cross-linked butadiene copolymer, a butadiene styrene copolymer, or a C 4-18 alkyl acrylate.
  • the polymeric toughener comprises butadiene nitrile rubber having at least one of an amino, epoxy, hydroxyl, or carboxy group or a core-shell polymer comprising a shell comprising a C 1-4 alkyl methacrylate polymer or copolymer and a core comprising at least one of a cross-linked butadiene copolymer, a butadiene styrene copo
  • the present disclosure provides the adhesive composition of any one of the twenty-seventh to twenty-ninth embodiments, wherein the polymeric toughener is present in an amount from one weight percent to 60 weight percent, 5 weight percent to 55 weight percent, or 10 weight percent to 40 weight percent, based on the total weight of the multifunctional epoxide, the aliphatic compound, and the polymeric toughener.
  • the present disclosure provides the adhesive composition of any one of the twenty-seventh to thirtieth embodiments, wherein the multifunctional epoxide comprises at least two oxirane rings and at least two cycloaliphatic rings.
  • the present disclosure provides the adhesive composition of any one of the twenty-seventh to thirty-first embodiments, wherein the multifunctional epoxide comprises at least one of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate or bis ( (3, 4-epoxycyclohexyl) methyl) adipate.
  • the present disclosure provides the adhesive composition of any one of the twenty-seventh to thirty-second embodiments, wherein the multifunctional epoxide comprises a bisphenol epoxy resin, a novolac epoxy resin, or a combination thereof.
  • the present disclosure provides the adhesive composition of any one of the twenty-seventh to thirty-second embodiments, wherein the first part further comprises an aliphatic compound comprising at least one of an oxirane or oxetane group.
  • the present disclosure provides the adhesive composition of the thirty-third embodiment, wherein the aliphatic compound comprises at least two oxetane groups.
  • the present disclosure provides the adhesive composition of the thirty-fourth embodiment, wherein the aliphatic compound comprises 3-ethyl-3 ⁇ [ (3-ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane.
  • the present disclosure provides the adhesive composition of any one of the thirty-third to thirty-fifth embodiments, wherein the aliphatic compound comprises at least two oxirane groups.
  • the present disclosure provides the adhesive composition of the thirty-sixth embodiment, wherein the aliphatic compound comprises a diglycidyl ether of polypropylene glycol.
  • the present disclosure provides the adhesive composition of any one of the first to thirty-seventh embodiments, wherein the cationic photoinitiator comprises an irradiated onium salt.
  • the present disclosure provides the adhesive composition of any one of the first to thirty-eighth embodiments, wherein at least one of the first part or the second part comprises a silane coupling agent.
  • the present disclosure provides the adhesive composition of any one of the first to thirty-ninth embodiments, wherein at least one of the first part or the second part further comprises a thixotropic agent.
  • the present disclosure provides the adhesive composition of any one of the first to fortieth embodiments, wherein at least one of the first part or the second part further comprises inorganic filler.
  • the present disclosure provides the adhesive composition of the forty-first embodiment, wherein the inorganic filler comprises at least one of quartz glass, silica, titanium dioxide, zirconium tungstate, alumina, aluminum nitride, boron nitride, graphite (and expanded graphite or graphite-based nanotechnology products) , carbon nanotubes, or a metal filler.
  • the present disclosure provides the adhesive composition of any one of the twenty-seventh to forty-second embodiments, wherein the second part further comprises a polyol. In a forty-fourth embodiment, the present disclosure provides the adhesive composition of any one of the twenty-seventh to forty-third embodiments, wherein the adhesive composition is free of at least one of a free-radical initiator or ethylenically unsaturated functional groups.
  • the present disclosure provides a method of making a bonded article comprising a first substrate and a second substrate, the method comprising:
  • the present disclosure provides the method of the forty-fifth embodiment, further comprising heating the adhesive composition.
  • the present disclosure provides the method of any one of the twenty-fifth, twenty-sixth, forty-fifth, or forty-sixth embodiments, wherein the heating is carried out at a temperature in a range from 50 °C to 100 °C.
  • the density of the adhesive composition and the density of the cured adhesive was measured using a gas pycnometer (model Ultrapyc 5000 from Anton Paar GmbH, Graz, Austria) .
  • the cured adhesive was UV cured for 10 seconds (s) at 365 nanometers (nm) , at 400 milliwatts per square centimeter (mW/cm 2 ) and then thermally cured for 60 minutes at 100 °C.
  • the shrinkage was calculated as [density (adhesive) -density (cured adhesive) ] /density (adhesive) *100 according to ISO3521. The results are shown in Table 2, below.
  • T g data were collected by Dynamic Mechanical Analysis (DMA850 from TA Instruments, Shanghai, China) . Dogbone samples were first cured 10 s at 365 nm by LED, 400 mW/cm 2 and then cured at 80 °C for 1 hour. The Tg was measured after cooling the samples to room temperature (21-25 °C) for 24 hours. The results are shown in Table 2, below.
  • epoxides ER 1, ER 2, CAE 2, CAE 3, AE
  • polymeric toughener in the amounts shown in Table 3, below, were mixed in high-speed mixer to get a homogenous solution.
  • the first part and the second part were mixed together by hand.
  • the open time was determined to be the time when the viscosity had a sharp rise as determined by hand mixing to become a non-flowable material or when the temperature had an obvious increase.
  • the results are shown in Table 3, below, where “nm” means not measured. Ex 17 did not cure at room temperature.
  • Polyol was mixed with PI 1 in an 80: 20 ratio to provide Part B1. Polyol was mixed with PI 2 in an 80: 20 ratio to provide Part B2. Each was exposed to 1-W 365-nm LED for 10 minutes. 0.5 g of each of Part B1 and Part B2 was separately mixed with 10 grams of 85: 15 ER 1: TG 4 to provide Examples 23 and 24, respectively.
  • Example 23 had an open time of 8 to 10 minutes at 20 °C. Then a short exothermic polymerization took place, and the temperature reached 100 °C.
  • Example 24 had an open time of 20 to 30 minutes at 20 °C. Then it cured over a period of several hours.
  • Part B1 and Part B2 were stored for 1.5 months at room temperature. 0.5 g of each of Part B1 and Part B2 was then separately mixed with 10 grams of 85: 15 ER 1: TG 4 to provide Examples 25 and 26, respectively.
  • Example 25 had an open time of 8 to 10 minutes at 20 °C. Then a short exothermic polymerization took place, and the temperature reached 100 °C.
  • Example 26 had an open time of 20 to 30 minutes at 20 °C. Then it cured over a period of several hours.

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

Abstract

L'invention concerne une composition adhésive comprenant un époxyde multifonctionnel contenant au moins deux cycles oxirane et au moins un cycle parmi un cycle cycloaliphatique ou aromatique, un composé aliphatique comprenant au moins un cycle parmi un cycle oxirane ou un cycle oxétane, un durcisseur polymère, et un photoamorceur cationique. Au moins l'une des limitations suivantes est satisfaite : la composition adhésive comprend en outre un amorceur cationique thermique, ou la composition adhésive est conditionnée en tant que composition adhésive en deux parties, une première partie comprenant l'époxyde multifonctionnel et le composé aliphatique et une seconde partie comprenant le photoamorceur cationique. Au moins l'une de la première partie ou de la seconde partie comprend le durcisseur polymère. Des procédés d'utilisation de la composition adhésive sont également décrits.
PCT/CN2023/132557 2023-11-20 2023-11-20 Adhésif époxydique comprenant un durcisseur polymère et un photoamorceur cationique et son procédé d'utilisation Pending WO2025107100A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2023/132557 WO2025107100A1 (fr) 2023-11-20 2023-11-20 Adhésif époxydique comprenant un durcisseur polymère et un photoamorceur cationique et son procédé d'utilisation
PCT/CN2024/132581 WO2025108217A1 (fr) 2023-11-20 2024-11-18 Adhésif époxy comprenant un durcisseur polymère, photo-initiateur cationique et initiateur cationique thermique et son procédé d'utilisation

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PCT/CN2023/132557 WO2025107100A1 (fr) 2023-11-20 2023-11-20 Adhésif époxydique comprenant un durcisseur polymère et un photoamorceur cationique et son procédé d'utilisation

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PCT/CN2024/132581 Pending WO2025108217A1 (fr) 2023-11-20 2024-11-18 Adhésif époxy comprenant un durcisseur polymère, photo-initiateur cationique et initiateur cationique thermique et son procédé d'utilisation

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US20050061429A1 (en) * 2003-09-18 2005-03-24 Fuji Photo Film Co., Ltd. Photocurable adhesive and bonding process employing same
CN101755238A (zh) * 2007-04-13 2010-06-23 亨斯迈先进材料美国有限责任公司 二元光引发剂、可光固化的组合物、它们的用途以及制备三维制品的方法
CN103025839A (zh) * 2010-10-01 2013-04-03 理研科技株式会社 粘接剂组合物、涂料组合物及使用了其的底漆、喷墨油墨、粘接方法及层叠体
EP3835378A1 (fr) * 2019-12-13 2021-06-16 Henkel AG & Co. KGaA Composition adhésive durcissable à deux composants (2k)
WO2022179826A1 (fr) * 2021-02-26 2022-09-01 Henkel Ag & Co. Kgaa Composition d'adhésif ou d'agent d'étanchéité photodurcissable
WO2023072940A1 (fr) * 2021-10-25 2023-05-04 Sika Technology Ag Composition de résine époxy à deux composants résistante aux fissures
WO2023187507A1 (fr) * 2022-03-30 2023-10-05 3M Innovative Properties Company Composition durcissable, film adhésif durcissable et ruban adhésif

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Publication number Priority date Publication date Assignee Title
JP5229433B2 (ja) * 2011-04-19 2013-07-03 Ｄｉｃ株式会社 カチオン重合性接着剤及びそれを用いて得られた偏光板
JP2017179160A (ja) * 2016-03-30 2017-10-05 株式会社Adeka 光カチオン硬化型接着剤、熱カチオン硬化型接着剤およびそれらの硬化物の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050061429A1 (en) * 2003-09-18 2005-03-24 Fuji Photo Film Co., Ltd. Photocurable adhesive and bonding process employing same
CN101755238A (zh) * 2007-04-13 2010-06-23 亨斯迈先进材料美国有限责任公司 二元光引发剂、可光固化的组合物、它们的用途以及制备三维制品的方法
CN103025839A (zh) * 2010-10-01 2013-04-03 理研科技株式会社 粘接剂组合物、涂料组合物及使用了其的底漆、喷墨油墨、粘接方法及层叠体
EP3835378A1 (fr) * 2019-12-13 2021-06-16 Henkel AG & Co. KGaA Composition adhésive durcissable à deux composants (2k)
WO2022179826A1 (fr) * 2021-02-26 2022-09-01 Henkel Ag & Co. Kgaa Composition d'adhésif ou d'agent d'étanchéité photodurcissable
WO2023072940A1 (fr) * 2021-10-25 2023-05-04 Sika Technology Ag Composition de résine époxy à deux composants résistante aux fissures
WO2023187507A1 (fr) * 2022-03-30 2023-10-05 3M Innovative Properties Company Composition durcissable, film adhésif durcissable et ruban adhésif

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