# US 7,745,006 B2 · Low odor, fast cure, toughened epoxy adhesive > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,745,006 B2 - Document ID: US7745006B2 - Status: Granted - Kind: B2 - Application number: 11/639,539 - Filed: 2006-12-15 - Published: 2008-06-19 - Granted: 2010-06-29 - Earliest claimed: 2006-12-15 - Assignees: Ashland Licensing and Intellectual Property LLC - Inventors: Michael J. Barker - Web page: https://patentgrep.com/patent/US7745006B2 ## CPC - C08G 59/50: Amines - C08G 59/621: {Phenols} - C08G 59/686: {containing nitrogen} - C09J 163/00: Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins - Y10T 428/31511: Of epoxy ether - Y10T 428/31515: As intermediate layer - Y10T 428/31522: Next to metal - Y10T 428/31529: Next to metal - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract An epoxy adhesive composition of an epoxy resin and an amine hardener includes a synergistic accelerator of an effective amount of short chain polyol and an effective amount of a dihydric phenol having between about 6 and about 24 carbon atoms. Surfaces of adherends are joined with the dried residue of the epoxy adhesive composition by applying the epoxy resin composition to one or both surfaces, joining the surfaces, and applying pressure, optionally with heating. The joined adherends having the dried epoxy resin composition is another disclosed embodiment. ## Claims ### Claim 1 In an epoxy adhesive composition of an epoxy resin and an amine hardener, the improvement for enhancing reaction rate and adhesion to SMC substrates, which comprises: a synergistic accelerator comprising about 0.1% to about 3% based on weight of the epoxy resin of an aliphatic polyhydric polyol containing from about 2 to about 15 carbon atoms and bearing from about 2 to about 10 hydroxyl functionality groups, and an effective amount of an aromatic dihydric phenol having between about 6 and about 24 carbon atoms wherein the amine hardener is selected from the group consisting of an aliphatic polyamine modified by condensation with a tall oil fatty acid, a Mannich base, an aromatic polyamine, an amidoamine and a polyamide. ### Claim 2 (depends on 1) The epoxy adhesive composition of claim 1, wherein said dihydric phenol has between from about 6 and about 18 carbon atoms. ### Claim 3 (depends on 1) The epoxy adhesive composition of claim 1, wherein said dihydric phenol is one or more of catechol, resorcinol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, bisphenols having the formula: wherein R5 is a bivalent radical containing 1 to 8 atoms of one or more of C, O, S or N. ### Claim 4 (depends on 3) The epoxy adhesive composition of claim 3, wherein R5 is an alkylene or alkylidene group containing between 1 and 8 carbon atoms. ### Claim 5 (depends on 4) The epoxy adhesive composition of claim 4, wherein R5 is an alkylene or alkylidene group containing between 1 and 6 carbon atoms. ### Claim 6 (depends on 3) The epoxy adhesive composition of claim 3, wherein said bisphenol is one or more of methylene bisphenol, isopropylidene bisphenol, butylidene bisphenol, octylidene bisphenol, bisphenol sulfide, bisphenol sulfone, bisphenol ether, or bisphenol amine. ### Claim 7 (depends on 1) The epoxy adhesive of claim 1, wherein said dihydric phenol is a single aromatic ring molecule of the following general formula: wherein, R10 is hydroxyl, R11 is hydroxyl, hydrogen or alkyl, R12 is hydroxyl, hydrogen or alkyl, and R13 is hydroxyl, hydrogen or alkyl. ### Claim 8 (depends on 7) The epoxy adhesive composition of claim 7, wherein said dihydric phenol is one or more of catechol, resorcinol, hydroquinone, or methyl resorcinol. ### Claim 9 (depends on 1) The epoxy adhesive composition of claim 1, wherein said dihydric phenol ranges from between about 0.1 to about 25 percent based on weight of the epoxy resin. ### Claim 10 (depends on 9) The epoxy adhesive composition of claim 9, wherein said dihydric phenol ranges from between about 0.1 to about 10 percent. ### Claim 11 (depends on 10) The epoxy adhesive composition of claim 10, wherein said dihydric phenol ranges from between about 1 to about 5 percent. ### Claim 12 (depends on 1) The epoxy adhesive composition of claim 1, wherein said polyol is one or more of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, dipropylene glycol, tripropylene glycol, 2-methyl-1,3-propanediol, pentaerythritol, trimethylopropane, 1,4,6-octanetriol, butanediol, pentanediol, hexanediol, dodecanediol, octanediol, chloropentanediol, glycerol monoethyl ether, diethylene glycol, 2-ethylhexanediol, 1,4-cyclohexanediol, 1,2,6-hexanetriol, 1,3,5-hexanetriol, or 1,3-bis-(2-hydroxyethoxy)propane. ### Claim 13 (depends on 1) The epoxy adhesive composition of claim 1, wherein said polyol ranges from about 0.5 to about 1.5 percent. ### Claim 14 (depends on 1) The epoxy adhesive composition of claim 1, wherein the amine hardener comprises xylenediamine. ### Claim 15 A method for joining a first substrate having a first surface to a second substrate having a second surface with an adhesive composition, which comprises the steps of: (a) applying said adhesive composition to one or more of said first surface or said second surface, said adhesive composition comprising: (i) an epoxy resin; (ii) an amine hardener for said epoxy resin selected from the group consisting of an aliphatic polyamine modified by condensation with a tall oil fatty acid, a Mannich base, an aromatic polyamine, an amidoamine and a polyamide; and (iii) a synergistic accelerator comprising about 0.1% to about 3% based on weight of the epoxy resin of an aliphatic polyhydric polyol containing from about 2 to about 15 carbon atoms and bearing from about 2 to about 10 hydroxyl functionality groups, and an effective amount of an aromatic dihydric phenol having between about 6 and about 24 carbon atoms; (b) joining said first and second surfaces; and (c) applying pressure to said joined first and second surfaces to cure said adhesive composition. ### Claim 16 (depends on 15) The method of claim 15, wherein said substrates are one or more of sheet molding compound (SMC) or metal. ### Claim 17 (depends on 16) The method of claim 16, wherein said metal is one or more of hot dipped galvanized steel, electro galvanized steel, e-coat steel, cold rolled steel, bare aluminum, anodized aluminum, etched aluminum, or magnesium. ### Claim 18 (depends on 15) The method of claim 15, which comprises the additional step of heating said joined surfaces. ### Claim 19 (depends on 18) The method of claim 18, wherein said joined surfaces are heated at a temperature above about 82° C. ### Claim 20 (depends on 15) The method of claim 15, wherein said dihydric phenol has between from about 6 and about 18 carbon atoms. ### Claim 21 (depends on 15) The method of claim 15, wherein said dihydric phenol is one or more of catechol, resorcinol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, bisphenols having the formula: wherein R5 is a bivalent radical containing 1 to 8 atoms of one or more of C, O, S or N. ### Claim 22 (depends on 21) The method of claim 21, wherein R5 is an alkylene or alkylidene group containing between 1 to 8 carbon atoms. ### Claim 23 (depends on 22) The method of claim 22, wherein R5 is an alkylene or alkylidene group containing 1 to 6 carbon atoms. ### Claim 24 (depends on 21) The method of claim 21, wherein said bisphenol is more or more of methylene bisphenol, isopropylidene bisphenol, butylidene bisphenol, octylidene bisphenol, bisphenol sulfide, bisphenol sulfone, bisphenol ether, or bisphenol amine. ### Claim 25 (depends on 15) The method of claim 15, wherein said polyol is one or more of propylene glycol, dipropylene glycol, tripropylene glycol, 1,4 butanediol, or 2-methyl-1,3-propanediol. ### Claim 26 A joined product of a first substrate having a first surface and a second substrate having a second surface, said surfaces joined by the dried residue of an adhesive composition, said adhesive composition comprising: an epoxy adhesive composition comprising: (a) an epoxy resin; (b) an amine hardener for said epoxy resin selected from the group consisting of an aliphatic polyamine modified by condensation with a tall oil fatty acid, a Mannich base, an aromatic polyamine, an amidoamine and a polyamide; and (c) a synergistic accelerator comprising about 0.1% to about 3% based on weight of the epoxy resin of an aliphatic polyhydric polyol containing from about 2 to about 15 carbon atoms and bearing from about 2 to about 10 hydroxyl functionality groups, and an effective amount of an aromatic dihydric phenol having between about 6 and about 24 carbon atoms. ### Claim 27 (depends on 26) The joined product of claim 26, wherein said dihydric phenol has between from about 6 and about 18 carbon atoms. ### Claim 28 (depends on 26) The joined product of claim 26, wherein said dihydric phenol is one or more of catechol, resorcinol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, bisphenols having the formula: wherein R5 is a bivalent radical containing 1 to 8 atoms of one or more of C, O, S or N. ### Claim 29 (depends on 28) The joined product of claim 28, wherein R5 is an alkylene or alkylidene group containing between 1 to 8 carbon atoms. ### Claim 30 (depends on 29) The joined product of claim 29, wherein R5 is an alkylene or alkylidene group containing 1 to 6 carbon atoms. ### Claim 31 (depends on 28) The joined product of claim 28, wherein said bisphenol is more or more of methylene bisphenol, isopropylidene bisphenol, butylidene bisphenol, octylidene bisphenol, bisphenol sulfide, bisphenol sulfone, bisphenol ether, or bisphenol amine. ### Claim 32 (depends on 26) The joined product of claim 26, wherein said polyol is one or more of propylene glycol, dipropylene glycol, tripropylene glycol, 1,4butanediol, or 2-methyl-1,3-propanediol.