WO2016191403A1 - Composition d'adhésif époxyde à deux composants (2k) pour coller des métaux huileux - Google Patents

Composition d'adhésif époxyde à deux composants (2k) pour coller des métaux huileux Download PDF

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Publication number
WO2016191403A1
WO2016191403A1 PCT/US2016/033866 US2016033866W WO2016191403A1 WO 2016191403 A1 WO2016191403 A1 WO 2016191403A1 US 2016033866 W US2016033866 W US 2016033866W WO 2016191403 A1 WO2016191403 A1 WO 2016191403A1
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Prior art keywords
adhesive composition
epoxy
composition
core
oil
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PCT/US2016/033866
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English (en)
Inventor
Bharati BALIJEPALLI
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Dow Global Technologies Llc
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Publication of WO2016191403A1 publication Critical patent/WO2016191403A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

Definitions

  • the present invention relates to a novel epoxy adhesive composition with properties suitable in some particular applications such as bonding oily metals.
  • Epoxy resin based adhesives are used in many applications. In the automotive industry, epoxy resin adhesives are used in many bonding applications, including metal- metal bonding in frame and other structures in automobiles. Some of these adhesives must strongly resist failure during vehicle collision situations. Adhesives of this type are sometimes referred to as “crash durable adhesives", or "CD As”.
  • Structural epoxy adhesive compositions have replaced spot welding and other methods of mechanical fastening in automotive assembly processes.
  • the surface of the metal substrate is often contaminated with oils, processing aids and/or lubricants.
  • Two part (2K) epoxy structural adhesives offer many benefits over IK adhesives such as ability to bond together nearly all, similar as well as dissimilar, substrates, fast cures at ambient temperatures, high humidity resistance, dimensional stability, fewer shelf life issues, easy global production, and shipping and so on.
  • the two parts of a 2K epoxy adhesive composition are typically an epoxy resin part, and a hardener part.
  • 2K epoxy adhesives could play a key role in the efforts towards light- weighting of vehicles as they enable mixed material bonding.
  • the present invention is based on the surprising finding that the addition of a small amount of an organic polymeric solid greatly improves the oil absorption capability of a two part epoxy adhesive composition at low cure temperature of about 60°C.
  • the improved oil absorption capability using the present invention is also demonstrated at ever lower temperature of about 23°C.
  • an organic mesoporous solid such as polystyrene hydroxide (poly-p-vinylphenol)
  • polystyrene hydroxide poly-p-vinylphenol
  • this organic solid additive does not adversely affect the other required mechanical properties such as impact peel strength. In fact, a slight improvement in impact peel strength was achieved.
  • This invention is a two-part structural adhesive with an epoxy resin side
  • composition A comprises: a urethane toughener in an amount of 7 to 9 wt% of composition A; a core shell rubber toughener in an amount of 30 to 35 wt% of composition A; an epoxy resin in an amount of 30 to 35 wt% of composition A, a silane modified epoxy resin in an amount of 2.5 to 3 wt% of composition A, and an oil absorbing polymeric solid in the amount of 2.5 to 5 wt% of composition A.
  • Composition B comprises: a curing accelerator; a polymeric amine or amide, or combination thereof, in the amount of 55 wt% of composition B; and a flexibilizer in the amount of 35 wt% of composition B.
  • composition A Composition A
  • composition A it was surprisingly found that the inclusion of the organic polymeric solid significantly improves the performance of the adhesive composition to adhere oily substrate. Furthermore, other inorganic and organic solids may be used in conjunction with the organic polymeric solid of the invention to enhance oil absorption.
  • the inorganic solids may include zeolites, clays, ceramics, fly ash ceramics, hollow glass spheres.
  • Organic solids may include ion exchange resins, vinyl esters, acrylates and cross- linked acrylate resins, hollow spheres of these resins, cellulosics powders derived from waste paper, cotton etc, cellulosic powders like methyl cellulose, ethyl cellulose, hydroxyl ethyl cellulose etc, super absorbant polymers derived from polyacrylic acid, polyacrylamide or copolymers of the same.
  • organic polymeric solid of the invention is an organic powder containing vinyl phenol moiety, e.g., a copolymer of poly-p-vinylphenol and methyl methacrylate, commercially available as MARUKA LYNCUR CMMTM or copolymer of poly-p-vinylphenol and styrene commercially available as MARUKA LYNCUR CST, both from Maruzen Petrochemical Co. Ltd.
  • the preferred average molecular weight of these copolymers is in the range of 5000 to 20,000 as indicated in the commercially available products from Maruzen Petrochemical Co. Ltd.
  • Another preferred organic solid useful in the present invention is a homo-polymer of p-vinyl phenol (polystyrene hydroxide) with an average molecular weight -10,000 with the chemical structure shown below which is also an organic mesoporous powder:
  • n is an integer in the range 40 to 500.
  • This homo-polymer solid is commercially available as MARUKA LYNCUR M from Maruzen Petrochemical Co. Ltd.
  • the polymeric solids of this invention could have a mesoporous structure which enables oil absorption.
  • Materials whose structures allow fluids to flow through the materials are porous.
  • Porous materials can be characterized by their pore sizes. Very small pores having diameters ⁇ 2 nm are called micropores, while very large pores (>50 nm) are called macropores. Pores of intermediate size (between 2 and 50 nm) are called mesopores.
  • One aspect of mesopores is that they have pores that are large enough to readily allow liquids to enter the material. At the same time, large pores do not provide as much surface area in a given volume of material as do smaller pores.
  • mesoporous materials provide liquid access to more surface area per unit volume of material than either microporous or macroporous materials. Because of their large liquid-accessible surface areas, mesoporous materials are useful as sorbents.
  • the organic polymeric powder is used in the composition A is an amount of 1 to 7 wt%, preferably in an amount of 2 to 6 wt%, and more preferably in an amount of 2.5 to 5 wt%, all based on the total weight of composition A.
  • the epoxy resins used in composition A can be a mixture of solid and liquid epoxy resins or simply liquid epoxy resins.
  • the epoxy resin may include one epoxy or may include a combination of two or more epoxy compounds.
  • the epoxy compounds useful in the present invention are those compounds containing at least one vicinal epoxy group and may include a wide variety of epoxy compounds.
  • the epoxy compound may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted.
  • the epoxy compound may be monomeric or polymeric.
  • one embodiment of the epoxy compound used in the curable composition of the present invention may be for example a single epoxy compound used alone; or a combination of two or more other epoxy compounds known in the art such as any of the epoxy compounds described in Lee, H. and Neville, K., Handbook of Epoxy Resins, McGraw-Hill Book Company, New York, 1967, Chapter 2, pages 2-1 to 2-27, incorporated herein by reference.
  • the epoxy compound may include for example epoxy resins based on reaction products of polyfunctional alcohols, phenols, cycloaliphatic carboxylic acids, aromatic amines, or aminophenols with epichlorohydrin.
  • a few non- limiting embodiments include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, resorcinol diglycidyl ether, and triglycidyl ethers of para-aminophenols.
  • Other suitable epoxy resins known in the art include for example reaction products of epichlorohydrin with o-cresol novolacs, hydrocarbon novolacs, and, phenol novolacs.
  • the epoxy compound may also be selected from commercially available epoxy resin products such as for example, D.E.R. ® 330, D.E.R. 331, D.E.R. 332, D.E.R. 354, D.E.R. 383, D.E.R.
  • D.E.R. 331 will be the preferred one.
  • Tougheners used in composition A may include a urethane toughener and a core shell rubber toughener.
  • the preferred urethane tougheners are those tougheners described in US Patent No. 8,404,787 ('787 patent), incorporated herein by reference in its entirety.
  • One preferred urethane toughener for the present invention is Example 2 of the '787 patent which is a compound terminated with diisopropylamine. Similar compound terminated with bisphenol A molecule may also be used as a preferred urethane toughener.
  • a core shell rubber toughener is also used in the present adhesive composition as a toughener in the toughener combination.
  • the core-shell rubber component is a particulate material having a rubbery core. Any core-shell rubber material may be used in the present invention. Some preferred core-shell rubber compositions are disclosed in U.S. Patent Nos. 7,642,316 and 7,625,977, both incorporated herein by reference in their entireties.
  • the rubbery core of such core shell rubber preferably has a Tg of less than -25° C, more preferably less than - 50° C, and even more preferably less than -70° C.
  • the Tg of the rubbery core may be well below -100° C.
  • the core-shell rubber also has at least one shell portion that preferably has a Tg of at least 50° C.
  • core it is meant an internal portion of the core-shell rubber.
  • the core may form the center of the core- shell particle, or an internal shell or domain of the core-shell rubber.
  • a shell is a portion of the core-shell rubber that is exterior to the rubbery core.
  • the shell portion (or portions) typically forms the outermost portion of the core-shell rubber particle.
  • the shell material is preferably grafted onto the core or is cross-linked.
  • the rubbery core may constitute from 50 to 95%, especially from 60 to 90%, of the weight of the core-shell rubber particle.
  • the core of the core- shell rubber may be a polymer or copolymer of a conjugated diene such as butadiene, or a lower alkyl acrylate such as n-butyl-, ethyl-, isobutyl- or 2-ethylhexylacrylate.
  • the core polymer may in addition contain up to 20% by weight of other copolymerized monounsaturated monomers such as styrene, vinyl acetate, vinyl chloride, methyl methacrylate, and the like.
  • the core polymer is optionally cross-linked.
  • the core polymer optionally contains up to 5% of a copolymerized graft- linking monomer having two or more sites of unsaturation of unequal reactivity, such as diallyl maleate, monoallyl fumarate, allyl methacrylate, and the like, at least one of the reactive sites being non-conjugated.
  • a copolymerized graft- linking monomer having two or more sites of unsaturation of unequal reactivity, such as diallyl maleate, monoallyl fumarate, allyl methacrylate, and the like, at least one of the reactive sites being non-conjugated.
  • the core polymer may also be a silicone rubber. These materials often have glass transition temperatures below -100° C.
  • Core-shell rubbers having a silicone rubber core include those commercially available from Wacker Chemie, Kunststoff, Germany, under the trade name GenioperlTM.
  • a particularly preferred core shell rubber is one described in U.S. 2007/0027233 (EP 1 632 533 Al), incorporated herein by reference in its entirety.
  • Core-shell rubber particles as described in the 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 is preferably dispersed in a polymer or an epoxy resin, also as described in the document.
  • Preferred core-shell rubbers include those sold by Kaneka Corporation under the designation Kaneka Kane AceTM, including the Kaneka Kane Ace 15 and 20 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 mixtures thereof.
  • the products contain the core-shell rubber (CSR) particles pie-dispersed in an epoxy resin, at various concentrations.
  • Kane Ace MX 154 comprises 40% CSR
  • Kane Ace MX 257 comprises 37% CSR.
  • the preferred core shell rubber is KANE ACE MX 156 commercially available from Kaneka Corporation.
  • Composition A may also comprise some other typical components and fillers in their typical amounts used in crash durable adhesive composition.
  • the adhesive can further contain other additives such as diluents, plasticizers, extenders, pigments and dyes, fire- retarding agents, thixotropic agents, flow control agents, such as silicones, waxes and stearates, which can, in part, also be used as mold release agents, adhesion promoters, antioxidants and light stabilizers.
  • Hardener composition B comprises at least one hardener that is capable of cross-linking with epoxy groups on the epoxy resin.
  • Any hardener e.g., suitable for a 2K epoxy, may be used.
  • Preferred hardeners include polymeric amines (polyamines) and polymeric amides (polyamides) (including, e.g., polyamido- amines), low molecular weight amines, polyimines and combinations thereof.
  • the polyamine may be any amine prepolymer that has at least two amine groups in order to allow cross-linking to take place.
  • the amine prepolymer comprises primary and/or secondary amine groups, and preferably comprises primary amine groups.
  • the polyamine compound with one or more primary and/or secondary amino groups may be chosen from aliphatic or cycloaliphatic di- or polyamines including polyether di- and triamines as well as polyamines, and mixtures thereof. Polyether triamine is preferred.
  • the polyether amines may be linear, branched, or a mixture. Branched polyether amines are preferred. Any molecular weight polyetheramine may be used, with molecular weights in the range of 200 to 6000 or above being suitable. Molecular weights may be above 1000, or more preferably above 3000. Molecular weights of 3000 or 5000 are preferred.
  • Suitable commercially available polyetheramines include those sold by Huntsman under the Jeffamine trade name.
  • Suitable polyether diamines include Jeffamines in the D, ED, and DR series. These include Jeffamine D-230, D-400, D-2000, D-4000, HK-511 ,
  • Suitable polyether triamines include Jeffamines in the T series. These include Jeffamine T-403, T-3000, and T-5000. Polyether triamines are preferred, and Jeffamine T-403 is the most preferred. The equivalents of any of the above may also be used in partial or total replacement.
  • any polyamide hardener may be used.
  • Some preferred polyamides include reaction products of a dimerized fatty acid and a polyamine. Examples of such polyamides include those available from Cognis under the trade designations Versamid® 115, Versamid® 125 and Versamid®.
  • the polyamine is preferably a polyetheramine.
  • the polyamine or polyamide is preferably present in an amount greater than 10 wt%, more preferably greater than 15 wt%, 20 wt% or 25 wt%.
  • the polyamine or polyamide is preferably present in an amount of less than 60 wt%, more preferably less than 55 wt%, 50 wt% or 45 wt%. For example, some preferred amounts may be 25 wt%, 30 wt%, 40 wt%, and 42.5 wt%.
  • the weight percents are expressed in terms of the composition (e.g., resin composition or hardener composition, preferably hardener composition) where the polyamine and/or polyamide are included.
  • Hardener composition B also preferably comprises a low molecular weight (non- polymeric) amine hardener.
  • This component preferably acts as a cross-linking and/or chain- extending agent.
  • the additional hardener preferably contains primary or secondary amine groups and has an equivalent weight per primary or secondary amine group of not more than 150, more preferably not more than 125.
  • the additional low molecular weight amine compound is selected from the group consisting of
  • hardener composition B preferably comprises at least 5 wt%, 10 wt%, or 15 wt% of the agent.
  • One preferred amount is 9 wt% of the agent based on weight of hardener composition B.
  • Polyethyleneimine polymers are particularly useful additional hardeners which are conveniently blended into the B component.
  • a polyethyleneimine polymer is used as an additional hardener, it is most preferably used in an amount from 1 to 5 weight percent of the hardener component B.
  • the epoxy curative component preferably also includes a heat activated curing agent, also known as a latent hardener.
  • a heat activated curing agent also known as a latent hardener.
  • Any latent hardener that does not cause hardening under ambient conditions (“ambient conditions” meaning, e.g., typical room temperature) may be used. When used, this can allow for faster curing by the application of heat, e.g., by raising the temperature of a work piece above ambient.
  • the latent curing agent used in the new compositions may be any substance that remains inert towards epoxide resins below a certain "threshold" temperature, which is usually at least about 80° C, and preferably at least about 100° C or above, but reacts rapidly to effect curing once that threshold temperature has been exceeded.
  • Such materials are well known and commercially available and include boron trichloride/amine and boron trifluoride/amine complexes, dicyandiamide, melamine, diallylmelamine, guanamines such as acetoguanamine and benzoguanamine, aminotriazoles such as 3-amino-l,2,4-triazole, hydrazides such as adipic dihydrazide, stearic dihydrazide, isophthalic dihydrazide, semicarbazide, cyanoacetamide, and aromatic polyamines such as diaminodiphenylsulphones.
  • dicyandiamide is particularly preferred.
  • latent hardener Any amount of latent hardener may be used as appropriate for any particular composition according to the present invention.
  • the amount of latent hardener is preferably at least 0 wt% or 0.5 wt%, more preferably at least 1 wt% of the epoxy adhesive.
  • the amount of epoxy latent hardener is preferably up to about 3 wt%, more preferably up to about 2 wt% of the epoxy adhesive.
  • a preferred amount includes 1.3 wt%.
  • the epoxy curative component preferably also includes at least one flexibilizer.
  • the flexibilizer is present in an amount of about 25 or greater weight percent, based on the total weight of the epoxy curative component. In accordance with another preferred embodiment of the present invention, the flexibilizer is present in an amount of about 35 weight percent, based on the total weight of the epoxy curative component.
  • the flexibilizer can comprise an amine terminated butadiene nitrile.
  • the flexibilizer is comprised of HYCAR 1300X16, an amine terminated butadiene nitrile, which is readily commercially available from Noveon Specialty Chemicals (Cleveland, Ohio).
  • the epoxy- curing agent preferably comprises a tertiary amine curing agent, more preferably a phenolic- type tertiary amine curing agent, and still more preferably is comprised of
  • the tertiary amine curing-agent e.g., 2,4, 6-Tri (dimethylaminomethyl) phenol
  • the tertiary amine curing agent e.g., 2,4, 6-Tri (dimethylaminomethyl) phenol
  • the tertiary amine curing-agent e.g., 2,4, 6-Tri (dimethylaminomethyl) phenol
  • the tertiary amine curing-agent is present in an amount of about 5 or greater weight percent, based on the total weight of the epoxy curative component formulation.
  • the tertiary amine curing-agent e.g., 2,4, 6-Tri (dimethylaminomethyl) phenol
  • the tertiary amine curing-agent e.g., 2,4, 6-Tri (dimethyl aminomethyl) phenol
  • the curing accelerator and hardeners should be used in suitable proportions and amounts to decrease the required curing temperature and enable the combined parts of the 2K adhesive to cure at a suitable temperature.
  • the curing temperature is preferably less than 100° C, more preferably less than 90° C, 60, or 50° C, or 40° C.
  • the epoxy adhesive compositions preferably cure at ambient temperature, e.g., 20° C or 25° C or there between. There is no particular preferred lowest curing temperature. As a general matter, however, curing temperature will generally be above 0° C, 10° C, or 15° C.
  • curing can take place in a range of, e.g., 10° to 40° C, more preferably 15° to 35° C. It is permissible to heat the inventive epoxy adhesive, e.g., in order to further reduce curing time or to obtain more complete curing.
  • Impact peel resistance is a particularly important property of the cured adhesive.
  • Impact peel resistance is conveniently measured according to ISO 11343 wedge impact method, with testing being performed at an operating speed of 2 m/sec on a 0.75 mm cold rolled steel 1403 substrate with a bonded area of 30 X 20 mm and an adhesive layer of 0.2 mm.
  • the cured adhesive preferably exhibits an impact peel strength of at least 20 N/mm when measured at 23° C.
  • the impact peel strength under these conditions is preferably at least 12 N/mm and even more preferably at least 14 N/mm.
  • Epoxy resin composition A and hardener composition B can be combined in any suitable proportion as determined by one of ordinary skill in the art, using usual considerations of, e.g., the resin content in A, the amount and type of curing agent and/or accelerator in B, the amounts of reactive toughener in A and/or B, the amounts of fillers or functional additives in A and/or B, etc. Indeed, the amounts of actives, fillers, or other additives, can be selected so as to provide convenient (e.g., integer-valued) volume ratios.
  • Mixing ratios are generally expressed in terms of volume. Some preferred mixing ratios include 2: 1, 3:2, 1:1, 2:3, or 1:2, or there between (e.g., 2:1 to 1:2, or 2:1 to 1:1), expressed as parts by volume of A:B.
  • Table 1 listed various components used in generating the samples and the sources of these components.
  • Urethane toughener is prepared using the method of WO2005007766A1, incorporated herein in its entirety. Specifically, Toughener B on page 18 of
  • WO2005007766A1 is used for illustration purposes of the present invention and is made as follows: 66.6 g of Polytetrahydrofuran having a molecular weight of approximately 2000 (Mw) were preheated at 90° C. The resulting liquid was then poured into a vessel and 20.7 g of bisphenol A and 0.3 g of trimethylolpropane were added. The resulting suspension was heated up to 140° C and stirred until all bisphenol A was dissolved. After the mixture was cooled down to 60° C, 12.3 g hexamethylene diisocyanate were added. The mixture was stirred to homogeneity. Then 0.02 g dibutyltin-dilaurate was added.
  • the adhesive compositions were prepared by mixing stoichiometric amounts of the Part B (hardener part) with a small amount of the Part A (typically 20 grams) in a Flack Tek speedmixer DAC 400 FVZ.
  • Failure modes were classified as adhesive failure (AF), cohesive failure (CF) or thin film cohesive failure (TFCF).
  • Lap shear specimens were prepared and tested according to ISO 4587. 1" X 4" strips were cut from the substrate. Each coupon was thoroughly cleaned with acetone for clean metal testing. For oily metal testing, the bonding area was first cleaned with acetone and then re-greased with a thin layer of Anticorit PL 3802-39S oil. The adhesive composition was then applied to the prepared coupon. Typical glue line thicknesses of 0.2 mm were obtained by adding 10 mil size glass spacer beads.
  • the lap shear strength of the specimens was measured at a cross head speed of 10 mm/min.
  • Impact peel specimens were prepared and tested according to ISO 11343 with testing being performed at an operating speed of 2 m/sec on a 0.75 mm substrate with a bonded area of 30 X 20 mm and an adhesive layer of 0.2 mm.
  • a thin layer of Anticorit 3802-39S oil was applied to the bonding area.
  • Tables 2 and 3 list the components of three samples of Part A.
  • Sample Al is the comparative example.
  • Samples A2 and A3 are the inventive examples and comprise about 3 and 5 wt% of the poly-p-vinylphenol. All values are in grams.
  • Table 2 Components of Part A
  • the comparative example was prepared by mixing epoxy Part Al with hardener component Part Bl in a 2:1 weight ratio.
  • the inventive Example 1 is a 2:1 combination of epoxy component (Part A) A2 and hardener component (Part B) B 1.
  • the second inventive Example 2 is a 2:1 combination of epoxy component A3 and hardener component Bl.
  • the mechanical performance of the three examples is compared in Tables 4 and 5.

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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)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une nouvelle composition adhésive 2K dont le composant de résine époxyde comprend un solide polymère organique contenant une fraction phénolique vinylique. Ladite composition adhésive permet d'obtenir une forte liaison à des substrats métalliques contaminés par de l'huile, lorsqu'elle durcit à température ambiante, tout en présentant simultanément une bonne résistance aux chocs.
PCT/US2016/033866 2015-05-28 2016-05-24 Composition d'adhésif époxyde à deux composants (2k) pour coller des métaux huileux WO2016191403A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020082006A1 (fr) * 2018-10-18 2020-04-23 Illinois Tool Works Inc. Adhésif époxy durci à deux composants et à faible teneur en halogène
WO2020115041A1 (fr) 2018-12-04 2020-06-11 Hexcel Composites Limited Composition adhésive
CN111315839A (zh) * 2017-08-15 2020-06-19 Ddp特种电子材料美国公司 室温可固化的双组分增韧的环氧粘合剂

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021403A (en) * 1974-02-07 1977-05-03 Maruzen Oil Co. Ltd. Flame resistant thermosetting resin composition and metal clad laminate composed of the thermosetting resin composition
US4659779A (en) * 1985-04-02 1987-04-21 Ciba-Geigy Corporation Solid solution of amine and polymerized phenol as epoxy resin cure accelerator
EP0351365A2 (fr) * 1988-07-09 1990-01-17 Ciba-Geigy Ag Compositions durcissables de résine époxyde
EP0365479A2 (fr) * 1988-10-18 1990-04-25 Ciba-Geigy Ag Compositions durcissables de résines époxydes
JPH02243334A (ja) * 1989-03-17 1990-09-27 Toshiba Chem Corp 多層銅張積層板
EP0706548A1 (fr) * 1993-06-24 1996-04-17 Minnesota Mining And Manufacturing Company Composition adhesive epoxy pour coller des metaux contamines par de l'huile
WO2005007766A1 (fr) 2003-07-07 2005-01-27 Dow Global Technologies Inc. Composition de colle epoxyde et son procede d'application
EP1632533A1 (fr) 2003-06-09 2006-03-08 Kaneka Corporation Procede de production d'une resine epoxy modifiee
EP1695990A1 (fr) * 2005-02-28 2006-08-30 Dow Global Technologies Inc. Composition adhesive epoxy a deux composants
WO2007025007A1 (fr) * 2005-08-24 2007-03-01 Henkel Kommanditgesellschaft Auf Aktien Compositions d'epoxyde presentant une resistance superieure aux chocs
US7625977B2 (en) 2007-06-20 2009-12-01 Dow Global Technologies Inc. Adhesive of epoxy resin, toughener and blocked isocyanate polytetrahydrofuran toughener
US7642316B2 (en) 2004-10-14 2010-01-05 Dow Global Technologies, Inc. Rubber modified monovinylidene aromatic polymers and fabricated articles prepared therefrom
WO2012158336A1 (fr) * 2011-05-19 2012-11-22 Dow Global Technologies Llc Nouvel adhésif structural et son utilisation
US8404787B2 (en) 2005-06-02 2013-03-26 Dow Global Technologies Llc Toughened epoxy adhesive composition

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021403A (en) * 1974-02-07 1977-05-03 Maruzen Oil Co. Ltd. Flame resistant thermosetting resin composition and metal clad laminate composed of the thermosetting resin composition
US4659779A (en) * 1985-04-02 1987-04-21 Ciba-Geigy Corporation Solid solution of amine and polymerized phenol as epoxy resin cure accelerator
EP0351365A2 (fr) * 1988-07-09 1990-01-17 Ciba-Geigy Ag Compositions durcissables de résine époxyde
EP0365479A2 (fr) * 1988-10-18 1990-04-25 Ciba-Geigy Ag Compositions durcissables de résines époxydes
JPH02243334A (ja) * 1989-03-17 1990-09-27 Toshiba Chem Corp 多層銅張積層板
EP0706548A1 (fr) * 1993-06-24 1996-04-17 Minnesota Mining And Manufacturing Company Composition adhesive epoxy pour coller des metaux contamines par de l'huile
US20070027233A1 (en) 2003-06-09 2007-02-01 Katsumi Yamaguchi Process for producing modified epoxy resin
EP1632533A1 (fr) 2003-06-09 2006-03-08 Kaneka Corporation Procede de production d'une resine epoxy modifiee
WO2005007766A1 (fr) 2003-07-07 2005-01-27 Dow Global Technologies Inc. Composition de colle epoxyde et son procede d'application
US7642316B2 (en) 2004-10-14 2010-01-05 Dow Global Technologies, Inc. Rubber modified monovinylidene aromatic polymers and fabricated articles prepared therefrom
EP1695990A1 (fr) * 2005-02-28 2006-08-30 Dow Global Technologies Inc. Composition adhesive epoxy a deux composants
US8404787B2 (en) 2005-06-02 2013-03-26 Dow Global Technologies Llc Toughened epoxy adhesive composition
WO2007025007A1 (fr) * 2005-08-24 2007-03-01 Henkel Kommanditgesellschaft Auf Aktien Compositions d'epoxyde presentant une resistance superieure aux chocs
US7625977B2 (en) 2007-06-20 2009-12-01 Dow Global Technologies Inc. Adhesive of epoxy resin, toughener and blocked isocyanate polytetrahydrofuran toughener
WO2012158336A1 (fr) * 2011-05-19 2012-11-22 Dow Global Technologies Llc Nouvel adhésif structural et son utilisation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LEE, H.; NEVILLE, K.: "Handbook of Epoxy Resins", 1967, MCGRAW-HILL BOOK COMPANY, pages: 2 - 1,2-27

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111315839A (zh) * 2017-08-15 2020-06-19 Ddp特种电子材料美国公司 室温可固化的双组分增韧的环氧粘合剂
WO2020082006A1 (fr) * 2018-10-18 2020-04-23 Illinois Tool Works Inc. Adhésif époxy durci à deux composants et à faible teneur en halogène
WO2020115041A1 (fr) 2018-12-04 2020-06-11 Hexcel Composites Limited Composition adhésive

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