Patent Application
20250043127
The present disclosure relates to curable epoxy compositions for low temperature curing, structural adhesives therefrom, especially impact resistant structural adhesives and assemblies, along with related methods of using the same. The curable epoxy compositions and structural adhesives can be used, for example, in automotive industrial bonding applications.
With the increase in the use of adhesives for both vehicle assembly and vehicle repair. Industry sources have predicted a sustaining structural adhesive market growth annually. During both vehicle assembly and collision repairs, structural adhesives are typically used along with mechanical fasteners or spot welding which is referred to as cold joining using a hybrid joint. The joint is considered a hybrid because it uses both an adhesive and a fastener together. Hybrid joining combines the strengths of both the adhesive and the fastener together to overcome their individual vulnerabilities. Vehicle manufacturers also desire an adhesive that can absorb collision energy as the bonded parts deform during a collision. This requirement for higher performance standards for structural bonding has inspired more adhesive makers to create what they deem impact resistant structural adhesives (IRSA).
IRSA requires the adhesive has comprehensive performance, including shear strength, peel strength, impact peel strength, modulus, tensile strength and good environmental aging performance. The Original equipment manufacturers (OEMs) always apply the adhesive in welding workshop and cure it in paint workshop. Thus, the adhesive needs to match the OEM's production line and has good washing-off resistant as it will go through the pre-treatment line. Due to these requirements, one-component epoxy adhesive is usual a good choice for this application. It has good adhesion strength, good high temperature performance, high modulus. However, traditional epoxy system has a weakness of brittleness, and this will affect the peel and impact peel properties, finally affect the crash test performance and safety result. Thus, toughness is a desired property of epoxy based ISRA system.
More and more auto makers ensure energy efficient production lines to achieve the carbon neutral requirement by cutting down the operating temperature and operating time. Adhesive curing requires high temperature and enough time, which is a question may need to be improved.
It is therefore the object of the present invention to overcome the above-mentioned drawbacks by providing a high-performance structural adhesive composition which has excellent bonding performance after curing at a low curing temperature, such as 130-150° C., and good storage stability at room temperature.
It has been surprisingly found that structural adhesive prepared from a curable epoxy composition comprising at least an epoxy resin; a core-shell rubber; a capped polyurethane prepolymer; a hardener, at least an accelerator and a multifunctional epoxy-terminated prepolymer, provides very good strength properties within a wide application temperature range.
According to one aspect, the present invention relates to a curable epoxy composition, the curable epoxy composition comprising: A) at least one epoxy resin present in an amount of 10-40 parts by weight; B) a core shell rubber present in an amount of 10-40 parts by weight; C) a capped polyurethane prepolymer present in an amount of 3-15 parts by weight; D) an effective amount of a hardener; E) an effective amount of at least an accelerator; F) 5-20 parts by weight of a multifunctional epoxy-terminated prepolymer, wherein the multifunctional epoxy-terminated prepolymer being represented by the following formulas:
wherein, independently, R1 being bisphenol A, or bisphenol F, or bisphenol S, or halogenated bisphenol or aliphatic chain having from 1 to 18 carbon atoms; R2 being one or more selected from the group of polybutadiene, or polyacrylonitrile, or polypentadiene; R3 being aliphatic chain having from 10 to 400 carbon atoms; X being amine group or ester group; n being 1 to 10; and m being 1 to 10;
According to one aspect, the present invention is directed to a structural adhesive, which is a cured product of the curable epoxy composition of present invention.
According to still another aspect, the present invention also relates to an article comprising a first substrate, a second substrate and a cured composition disposed between and adhering the first substrate and the second substrate, wherein the cured composition is the cured product of the curable epoxy composition of this disclosure.
According to still another aspect, the present invention also relates to an automotive frame, which comprises the article of this disclosure.
In still another aspect, the present invention is directed to a method of using a curable epoxy composition which comprises applying a curable epoxy composition of at least one of this disclosure on a first substrate, attaching a second substrate to the first substrate, and curing the curable epoxy composition in contact with the first substrate and the second substrate to prepare a composite article.
In the following passages the present invention is described in more detail. Each aspect so described may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particularly, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
In the context of the present invention, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.
As used herein, the singular forms “a”, “an” and “the” include both singular and plural referents unless the context clearly dictates otherwise. For example, reference to “a filler” encompasses embodiments having one, two or more fillers. As used in this specification and the appended claims, the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
The terms “comprising”, “comprises” and “comprised of” as used herein are synonymous with “including”, “includes” or “containing”, “contains”, and are inclusive or open-ended and do not exclude additional, non-recited members, elements or process steps.
The term “ambient temperature” refers to a temperature in the range of 20° C. to 25° C., inclusive.
The recitation of numerical end points includes all numbers and fractions subsumed within the respective ranges, as well as the recited end points.
Unless otherwise defined, all terms used in the disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of the ordinary skills in the art to which this invention belongs to. By means of further guidance, term definitions are included to better appreciate the teaching of the present invention.
In the context of this disclosure, several terms shall be utilized.
The terms “polymer” is used herein consistent with its common usage in chemistry. Polymers are composed of many repeated subunits. The term “polymer” is used to describe the resultant material formed from a polymerization reaction.
As used herein, the term “cure” refers to exposing to radiation in any form, heating, or allowing to undergo a physical or chemical reaction that results in hardening or an increase in viscosity.
As discussed previously, embodiments of the present disclosure are directed to a curable epoxy composition comprising at least an epoxy resin; a core-shell rubber;
The curable epoxy composition comprises at least one epoxy resin. Suitable epoxy resins include the diglycidyl ethers of polyhydric phenol compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-I-phenyl ethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, diglycidyl ethers of aliphatic glycols and polyether glycols such as the diglycidyl ethers of C2-24 alkylene glycols and poly(ethylene oxide) or poly(propylene oxide) glycols; polyglycidyl ethers of phenol-formaldehyde novolac resins, alkyl substituted phenol-formaldehyde resins (epoxy novalac resins), phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins and dicyclopentadiene-substituted phenol resins, and any combination thereof.
Commercially available epoxy resins include those sold as DER 331 by Dow Chemical, EPON 828 by Hexion, YD 128 by Kukdo Chemical.
Other suitable additional epoxy resins are cycloaliphatic epoxides. A cycloaliphatic epoxide includes a saturated carbon ring having an epoxy oxygen bonded to two vicinal atoms in the carbon ring, as illustrated by the following structure I:
wherein R is an aliphatic, cycloaliphatic and/or aromatic group and n is a number from 1 to 10, preferably from 2 to 4. When n is 1, the cycloaliphatic epoxide is a monoepoxide. Dior epoxy resins are formed when n is 2 or more. Mixtures of mono-, di- and/or epoxy resins can be used. Cycloaliphatic epoxy resins of particular interest are (3,4-epoxycyclohexyl-methyl)-3,4-epoxy-cyclohexane carboxylate, bis-(3,4-epoxy-cyclohexyl) adipate, vinylcyclohexene monoxide and mixtures thereof.
The epoxy resin preferably is a bisphenol-type epoxy resin or mixture thereof with up to 10 percent by weight of another type of epoxy resin. Preferably the bisphenol type epoxy resin is a liquid epoxy resin, or a mixture of a solid epoxy resin dispersed in a liquid epoxy resin. The most preferred epoxy resins are bisphenol-A based epoxy resins and bisphenol-F based epoxy resins.
An especially preferred epoxy resin is a mixture of a diglycidyl ether of at least one polyhydric phenol, preferably bisphenol-A or bisphenol-F, having an epoxy equivalent weight of from 170 to 299, especially from 170 to 225, and at least one second diglycidyl ether of a polyhydric phenol, again preferably bisphenol-A or bisphenol-F, this one having an epoxy equivalent weight of at least 300, preferably from 310 to 600. The proportions of the two types of resins are preferably such that the mixture of the two resins has an average epoxy equivalent weight of from 225 to 400.
In embodiments of the present invention, the curable epoxy composition comprising, at least 10 parts by weight, or at least about 15 parts by weight, or at least about 20 parts by weight of the epoxy resin. In some preferred embodiments, up to about 40 parts by weight, or up to about 30 parts by weight, or up to about 25 parts by weight of the epoxy resin. A preferred amount includes 15-30 parts by weight.
The curable epoxy composition of the present invention comprises core-shell as toughener.
In some embodiments, the core-shell rubber component is a particulate material having a rubbery core.
The rubbery core 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. By “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 crosslinked. 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 crosslinked. 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.
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 AG, Munich, Germany, under the trade name Genioperl.
The shell polymer, which is optionally chemically grafted or crosslinked to the rubber core, is preferably polymerized from at least one lower alkyl methacrylate such as methyl methacrylate, ethyl methacrylate or t-butyl methacrylate. Homopolymers of such methacrylate monomers can be used. Further, up to 40% by weight of the shell polymer can be formed from other monovinylidene monomers such as styrene, vinyl acetate, vinyl chloride, methyl acrylate, ethyl acrylate, butyl acrylate, and the like. The molecular weight of the grafted shell polymer is generally between 20,000 and 500,000.
A preferred type of core-shell rubber has reactive groups in the shell polymer which can react with an epoxy resin or an epoxy resin hardener. Glycidyl groups are suitable. These can be provided by monomers such as glycidyl methacrylate.
Examples of commercially available core-shell rubbers include, for example, 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 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 particles pre-dispersed in an epoxy resin, at concentrations of approximately 33% or 25%.
10-40 parts by weight of core-shell rubber may be used. The curable epoxy composition of the invention preferably has a total core-shell rubber content of at least 10 parts by weight, or at least 15 parts by weight, or at least 20 parts by weight, or at least 22 parts by weight. The epoxy adhesive of the invention preferably has a total core-shell rubber content up to 40 parts by weight, or up to 30 parts by weight, or up to 25 parts by weight. A preferred amount includes 15-30 parts by weight.
The curable epoxy composition of the present invention comprises capped polyurethane prepolymer could surprisingly improve peel strength, especially low temperature peel strength.
The capped polyurethane prepolymer is prepared from at least one diisocyanate or triisocyanate and from a polymer having terminal amino groups, thiol groups or hydroxyl groups and/or from an optionally substituted polyphenol.
The capped polyurethane prepolymer is an isocyanate-functionalized polyurethane prepolymer in which at least a portion of the isocyanate groups have been reacted or blocked. The isocyanate groups of the prepolymer may be blocked or reacted with any suitable reactant such as an alcohol (e.g., a phenol), oxime, amine, lactam (e.g., caprolactam), acetoacetate, malonate or the like. In some embodiments, “de-blocking” takes place such that the capped polyurethane prepolymer is capable of reacting with other components of the adhesive composition when the composition is cured.
In compositions and methods of the present invention, the capped polyurethane prepolymer preferably presents at least 3 parts by weight, or at least 5 parts by weight, or at least 8 parts by weight. The capped polyurethane prepolymer preferably presents up to 15 parts by weight, or up to 13 parts by weight. One preferred amount is 3-15 parts by weight, or 8-13 parts by weight. When the capped polyurethane prepolymer presents up to 20 parts by weight, it will cause the operation difficulty due to high viscosity.
Any hardener (curing agent) appropriate for a one-component (IK) epoxy adhesive may be used. As is known in the art, a one component epoxy adhesive contains all of the ingredients for the adhesive in a single composition and does not cure until exposed to the appropriate conditions (e.g., heat or radiation), which activates the latent hardener.
The hardener, preferably for a one component adhesive composition, preferably comprises a latent hardener. Any latent hardener that does not cause hardening under ambient conditions (“ambient conditions” meaning, e.g., typical room temperature and normal lighting conditions) may be used. A latent hardener that causes the epoxy adhesive to be curable by application of heat is preferred. Some preferred hardeners include dicyandiamide, imidazoles, amines, amides, polyhydric phenols, and polyanhydrides. Dicyandiamide (also known as DICY, dicyanodiamide, and 1- or 2-cyanoguanidine) is preferred.
Any amount of hardener may be used as appropriate for any particular composition according to the present invention. The effective amount of hardener is preferably at least 1 part by weight, or at least 2 parts by weight, or at least 3 parts by weight, or at least 3.5 parts by weight. The amount of epoxy hardener is preferably up to about 5 parts by weight, or up to about 4 parts by weight. Some preferred amounts include 3.1, 3.3, 3.5 and 3.6 parts by weight.
Examples of commercially available sources of the hardeners are, for example, DYHARD 100 SH from Evonik, OMICURE DDA 5 from Huntsman, AMICURE CG1200 from Evonik.
The curable epoxy composition of the present invention comprises at least an accelerator selected from substituted amine, substituted imidazole and a combination of substituted imidazole and substituted urea.
In some embodiments, the accelerator comprises a substituted amine.
Examples of commercial products of substituted amine curing accelerators include FUJICURE FXR-1020 (m.p.=115-130° C.), FUJICURE FXR-1030 (m.p.=135-145° C.), FUJICURE FXR-1081 (m.p.=115-125° C.), FUJICURE FXR-1090FA (m.p.=110-120° C.), FUJICURE FXR-1121 (128-138° C.), SANCURE LC-125 (110-125° C.) from T&K Toka co, Ltd. Tokyo, Japan.
In some embodiments, the accelerator comprises a substituted imidazole. The substituted imidazole is selected from 1-N substituted imidazole, 2-C substituted imidazole, and imidazole metal salts.
In some embodiments, the accelerator comprises a combination of substituted imidazole and substituted urea. The substituted urea comprises disubstituted urea.
Examples of commercial products of substituted imidazole curing accelerators include CUREZOL 2PHZ-S, CUREZOL 2MZ-AZINE and CUREZOL 2MA-OK from Air Products and Chemicals. Examples of commercial products of substituted urea curing accelerators include Dyhard UR 700 and Dyhard UR 700 from Evonik.
Any effective amount of curing accelerators may be used in the present invention. The adhesive composition of the invention preferably has a total curing accelerators content of at least 0.1 parts by weight, more preferably at least 0.5 parts by weight, more preferably at least 1.0 parts by weight. The epoxy adhesive of the invention preferably has a total curing accelerators content up to 5.0 parts by weight, more preferably up to 4.0 parts by weight, more preferably up to 3.0 parts by weight.
In some embodiments, the accelerator comprises a substituted amine in an amount of 1-4 parts by weight.
In some embodiments, the accelerator comprises a substituted imidazole in an amount of 0.3-0.85 parts by weight, or 0.35-0.7 parts by weight.
In some embodiments, the accelerator comprises a combination of substituted imidazole and substituted urea in an amount of 0.5-1.5 parts by weight. And the mass ratio of the substituted imidazole to the substituted urea is from 1:2 to 4:1. To possess a good strength properties after high temperature curing, the mass amount of the substituted imidazole is at most 0.88 parts by weight, or at most 0.85 parts by weight, or at most 0.8 parts by weight, or at most 0.7 parts by weight. In addition, excess amount of substituted imidazole in the curable epoxy compositions may cause gelation and impact the storage stability.
A cured epoxy composition can be improved by the inclusion of a multifunctional epoxy-terminated prepolymer. This prepolymer combined the hydrophobic chain and hydrophilic chain in one molecular. It is surprisedly found this prepolymer can provide the environmental resistance performance of the cured epoxy composition. The final cured product has high impact peel strength at low temperature, such as −40° C.
In some embodiments, the multifunctional epoxy-terminated prepolymer, wherein the multifunctional epoxy-terminated prepolymer being represented by the following formulas:
wherein, independently,
In some embodiments, the multifunctional epoxy-terminated prepolymer is a reaction product of a difunctional epoxy, a rubber dicarboxylic acid or a rubber base diamine, and a polyamine comprising aliphatic chain.
The difunctional epoxy resins have at least about two epoxy groups per molecule. Preferred difunctional epoxy resins include those discussed below.
Any effective amount of polyetheramine-epoxy adduct may be used in the present invention. The epoxy adhesive of the invention preferably has a total polyetheramine-epoxy adduct content of at least 3 wt. %, more preferably at least 5 wt. %, more preferably at least 10 wt. %. The epoxy adhesive of the invention preferably has a total polyetheramine-epoxy adduct content up to 60 wt %, more preferably up to 40 wt. %, more preferably up to 20 wt. %. Some preferred amounts include 10, 15, and 20 wt. %.
The rubber dicarboxylic acid or rubber base diamine comprises a liquid rubber that has epoxide-reactive groups, such as carboxyl or amino groups.
Suitable rubber dicarboxylic acid or rubber base diamine materials are commercially available from Noveon under the tradenames Hypro 2000X162 carboxyl-terminated butadiene homopolymer and Hypro 1300X31 Hypro 1300X8, Hypro 1300X13, Hypro 1300X9 and Hypro 1300X18 carboxyl-terminated butadiene/acrylonitrile copolymers. A suitable amine-terminated butadiene/acrylonitrile copolymer is sold under the tradename Hypro 1300X21.
The polyamine comprising aliphatic chain comprises a linear amine-terminated polyoxyethylene ether having the following formula:
H2N—(CH2)2—[O—(CH2)2—O—(CH2)2]n—NH2
wherein n is 17-27.
The polyamine comprising aliphatic chain also comprises a linear amine-terminated polyoxypropylene ether having the following formula:
wherein n is 5-100. They are available from Huntsman Chemical under the trade name JEFFAMINE (D-series). The number average molecular weight of the amine-terminated polyoxypropylene ether is, for example, about 300 to about 5000.
The polyamine comprising aliphatic chain further comprises a trifunctional compound with the following formula:
wherein A is:
and x, y and z are independently 1-40 and x+y+z is preferably >6. Typical examples of these trifunctional compounds are commercially available from Huntsman Chemical under the trade name of JEFFAMINE (T series). The number average molecular weight of the above-mentioned materials is generally about 300 to about 6000.
The polyamine comprising aliphatic chain also comprises capped polymers of aminosilane, such as those that can be included in the following formula:
wherein R1, R2, R3 and R4 may be the same or different and selected from hydrogen, hydroxy, alkyl, alkoxy, alkenyl, alkenyloxy, aryl, and aryloxy; R5 and R6 may be the same or different and selected from hydrogen, alkyl, and aryl; and X is selected from alkylene, alkenylene, arylene, with or without heteroatom interruption; polyurethane; polyether; polyester; polyacrylate; polyamide, polydiene; polysiloxane; and polyimide.
For example, amine-terminated siloxanes can be used, such as the diaminosiloxane included in the following formula:
wherein R11 and R12 may be the same or different and selected from alkylene, arylene, alkylene oxide, arylene oxide, alkylene ester, arylene ester, alkylene amide or arylene amide; R9 And R10 may be the same or different and selected from alkyl or aryl; R7 and R8 are as defined above, and n is 1-1,200.
This application may use certain amino-modified silicone fluids commercially available from Shin-Etsu under the trade names KF857, KF858, KF859, KF861, KF864, and KF880. In addition, Wacker Silicones commercially provides a series of amino-functional silicone fluids called L650, L651, L653, L654, L655, and L656, as well as amino-functional polydimers under the trade name WACKERFINISHWR 1600 Methylsiloxane.
Other amino-functional silanes or siloxanes used to form adducts include materials purchased from the Sivento branch of Degussa, such as a proprietary amino-functional silane composition (called DYNASYLAN 1126), oligomeric aminosilane system (called DYNASYLAN 1146), N-vinylbenzyl-N′-aminoethyl-e-aminopropyl polysiloxane (DYNASYLAN 1175), N-(n-butyl)-3-amino Propyltrimethoxysilane (DYNASYLAN 1189), proprietary amino-functional silane composition (calledDYNASYLAN 1204), N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane (DYNASYLAN 1411), 3-aminopropylmethyldiethoxysilane (DYNASYLAN 1505), 3-aminopropylmethyldiethoxysilane (DYNASYLAN 1506), 3-aminopropyltriethoxy Silane (DYNASYLAN AMEO), proprietary aminosilane composition (called DYNASYLAN AMEO-T), 3-aminopropyltrimethoxysilane (DYNASYLAN AMMO), N-2-aminoethyl-3-aminopropyl Trimethoxysilane (DYNASYLAN DAMO), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (DYNASYLAN DAMO-T) and triamino-functional propyltrimethoxysilane (Referred DYNASYLAN TRIAMO).
In compositions and methods of the present invention, the multifunctional epoxy-terminated prepolymer preferably presents at least 5 parts by weight, or at least 5.5 parts by weight, or at least 7 parts by weight, or at least 7.5 parts by weight, or at least 9 parts by weight, or at least 12 parts by weight. The multifunctional epoxy-terminated prepolymer preferably presents up to 20 parts by weight, up to 16 parts by weight, or up to 15.5 parts by weight, or up to 15 parts by weight, or up to 14 parts by weight. One preferred amount is 5-20 parts by weight, or 5-16 parts by weight, or 5.5-15.5 parts by weight, or 7-13 parts by weight.
The curable epoxy composition of the present invention comprises multifunctional epoxy-terminated prepolymer could surprisingly improve corrosion resistance, water resistance and peel strength, especially low temperature peel strength.
The combination of multifunctional epoxy-terminated prepolymer and accelerator could decrease the curing temperature of the curable epoxy composition, and surprisingly provide a cured structural adhesive having both good low temperature impact peel strength and room temperature impact peel strength.
Optional additives include epoxy resin diluent.
Epoxy resin diluent include a wide variety of epoxy resin compounds. Any epoxy diluent compound that improves the mechanical and thermal performance of the final composition is preferably used as the epoxy resin diluent composition. For example, the epoxy diluents, (or polyepoxides) useful in the present invention may include aliphatic, cycloaliphatic, aromatic, hetero-cyclic epoxy diluents, and mixtures thereof. In one preferred embodiment, the epoxy diluent may contain, on the average, one or more reactive oxirane groups. Epoxy resins useful in the embodiments described herein may include for example mono-functional epoxy resins, multi- or poly-functional epoxy resins, and combinations thereof.
Suitable examples of the epoxy resin diluent useful in the present invention may include, but are not limited to, butyl glycidyl ether (BGE), phenyl glycidyl ether (PGE), cresol glycidyl ether (CGE), benzyl glycidyl ether, p-tert-butylphenyl glycidyl ether, 2-ethyl hexyl glycidyl ether, decyl glycidyl ether, alkyl (C12-C14) glycidyl ether (AGE), polyglycol diglycidyl ether, polypropylene diglycidyl ether, 1, 4-butanediol diglycidyl ether (BDDGE), 1, 6-hexanediol diglycidyl ether (HDDGE), ethylene glycol diglycidyl ether, neopentane glycol diglycidyl ether, rescorcinol diglycidyl ether, trimethyl propane triglycidyl ether (TMPTGE); and mixtures thereof.
Other examples of the epoxy resin diluent may include commercially available resins such as D.E.R. TM 331, D.E.R. 337, D.E.R. 736 and mixtures thereof. The above D.E.R. epoxy resins are commercial products available from Dow Chemical Company.
Optional additives also include some fillers which could increase the thixotropic, decrease density or keep modulus.
In some embodiments, the composition of the present invention comprises known fillers such as various ground or precipitated chalk, quartz powder, alumina, non-flaky clay, dolomite, carbon fiber, glass fiber, polymeric fibers, titanium dioxide, calcined silica, carbon black, calcium oxide, calcium carbonate, calcium magnesium carbonate, barite, and especially silicate-like fillers of the type of aluminum magnesium silicate calcium, such as wollastonite and chlorite. Generally, the compositions of the present invention may contain from about 5 to about 30 parts by weight of side fillers.
In yet other embodiments, hollow glass bubbles are present in the composition as fillers. Commercially available hollow glass bubbles include materials sold under the trademark SCOTCHLITE by 3M, and suitable grades include those available under the names B38, C15, K20, and VS5500. The hollow glass microspheres preferably have a diameter of about 5-200 microns and/or a density of about 0.3 to about 0.5 g/cc. Generally, the composition may contain about 0.5 to about 5 parts by weight of hollow glass bubbles.
In some embodiments, filler loadings may be at least 10 parts by weight, or at least 20 parts by weight, or at least 30 parts by weight, or at least 40 parts by weight. In some embodiments, filler loadings may be between 5-40 parts by weight, or 10-35 parts by weight.
Methods according to the present invention also include obtaining (e.g., manufacturing; purchasing; mixing components of a 1 K curable epoxy composition; etc.) a structural adhesive according to the present invention and exposing the curable epoxy composition to conditions to partially or completely cure the epoxy adhesive composition to form a structural adhesive.
In some embodiments of the present invention, the multifunctional epoxy-terminated prepolymer is preferably prepared by steps of:
As used herein, “Mw” refers to the weight average molecular weight and means the theoretical value as determined by Gel Permeation Chromatography (GPC) relative to linear polystyrene standards of 1.1 M to 580 Da and may be performed using Waters 2695 separation module with a Waters 2414 differential refractometer (RI detector).
In some embodiments of the present invention, the curable epoxy composition is preferably cured by steps of:
wherein, independently, R1 being bisphenol A, or bisphenol F, or bisphenol S, or halogenated bisphenol or aliphatic chain having from 1 to 18 carbon atoms;
The present invention will be further described and illustrated in detail with reference to the following examples. The examples are intended to assist one skilled in the art to better understand and practice the present invention, however, are not intended to restrict the scope of the present invention. All numbers in the examples are based on weight unless otherwise stated.
For the synthesis of P1, DER 331 (300 g) and CTBN1300X13 (200 g) were added into a reactor. Then the system was heated to 150° C. with the stirring and kept for 3 h. After that, D 2000 (200 g) and DER 331 (300 g) were added into the mixture and were stirred for another 2 h. When the reaction was stopped, the P1 was obtained.
For the preparation of curable epoxy composition E1, DER 331 (25 g), MX 154 (22 g), QR9466 (9 g), P1 (12.5 g) and NC 513 (2 g) were added into a container and mixed by Speedmixer for 1 min at 1000 rpm. Then, Fujicure FXR 1030 (2.2 g), 100 SH (3.5 g), VS 5500 (2.2 g), Omyacarb 2 (21 g), CaO (2 g) and Garamite 7305 (1 g) were added into the system and mixed by Speedmixer for 1 min at 1600 rpm for twice, vacuum is needed during mixing.
The coupons of cold rolled steel (CRS) were washed with acetone and wiped with paper towels, after which 3 g/m2 FERROCOTE 61AUS oil was coated on one side. The adhesive was then heat-coated on the oiled surface of the sample. Glass beads (0.25 mm) were sprayed on the adhesive layer before covering the test specimen. The metal clamp was used to clamp the two samples together during the baking cycle. All samples/adhesive assemblies were cured at different temperatures:
The cured structural adhesive samples were subjected to various of tests.
The curable epoxy compositions of E2 to E9, CE1 to CE5 were prepared in reference to Example 1. There is no multifunctional epoxy-terminated prepolymer in CE4. CE1-CE3 comprise comparative accelerator. The curable epoxy composition of E2 to E9 and CE1 to CE5 were cured in reference to Example 1. More details are listed in below result part.
The sample suitable for the shear test has a 12.5 mm cover and a width of 25 mm and is pulled at a speed of 5 mm/min using an Instron tester. The plateau average load is used to calculate the shear strength.
Shear strength results are recorded and ranked as follows:
The sample suitable for the t-peel test has a 100 mm cover and a width of 25 mm and is pulled at a speed of 50 mm/min using an Instron tester. The plateau average load is used to calculate the peel strength.
The specimen with the ISO 11343 test geometry (30 mm cover, 20 mm width) used for the impact peel test was subjected to a 90 J impact load at a drop weight speed of 2 m/s. The impact peel strength was measured using an Instron Dynatup 9250HV impact test machine under a steady state average impact load. The specimen is loaded in an environment box with the temperature of 23° C. or −40° C. The experimental results obtained are shown in Table 3.
T-peel strength results are recorded and ranked as follows:
Room temperature (23° C.) impact peel strength results are recorded and ranked as follows:
Low temperature (−40° C.) impact peel strength results are recorded and ranked as follows:
Rheological analysis was performed using an MCR 302 rheometer from Anton Paar GmbH. Measurements were performed using 25 mm stainless steel plates and a fixed gap of 0.5 mm. Adhesive was loaded onto the plates, the gap was set, excess material was removed. A 60 second pre-shear at 0.5 s−1 was applied prior to measurement at 10 s−1 over a 60 second interval. The test was under 45° C. and the viscosity is reported as the average viscosity over this interval.
A portion of each adhesive was placed in a plastic container and the placed in a resealable plastic bag. The adhesive was stored at 40° C. for 21 days and analyzed to determine the change in viscosity upon aging. The percent change in viscosity of the aged versus the initial material is reported and used to assess shelf-stability of each formulation. The percent change in viscosity of equal to or less than 80% and no gelation occurs was marked as pass.
Table 1 shows the formulations of two multifunctional epoxy-terminated prepolymers (P1-P2).
The multifunctional epoxy-terminated prepolymers have flexible chain and can be polymerized in the curable epoxy composition. Prepolymers (P1-P2) provide the toughening property to the epoxy structural adhesives.
Table 2 shows compositions of the curable epoxy adhesive E1-E9 and CE1-CE5.
Table 3 shows testing results of the curable epoxy adhesive E1-E9 and CE1-CE5.
This IRSA will focus on some properties like shear strength, peel strength, impact peel strength at both room temperature and low temperature (−40° C.). And all of the examples were cured at three types of curing condition, at 130° C. for 40 mins, or at 140° C. for 15 mins, or at 190° C. for 1 h. The substrate is cold rolled steel.
It can be seen that the designed accelerator and multifunctional epoxy-terminated prepolymer can help the low temperature curing (from 130° C. to 15000) and the cured adhesives provide good impact peel strength within a wide temperature range (from −40° C. to room temperature). Also, the formulations have good storage stability after long time storage (<80% change after 21 d 40° C. storage and no gelation occurred).
In Examples 1 to 9, the curable epoxy compositions were prepared according to the formulations provided by the present invention. These formulations especially included the epoxy resin, core-shell rubber, capped polyurethane prepolymer, hardener, designed accelerator and designed multifunctional epoxy-terminated prepolymer. It can be seen that when the contents of the claimed components of the present invention are within certain ranges, multifunctional epoxy-terminated prepolymer can act synergistically with accelerator, such that the prepared epoxy compositions could be cured at low temperature (such as 130° C. to 150° C.). And prepared cured epoxy compositions have impact peel strength within a wide temperature range (from −40° C. to room temperature). It can be seen from E9, for ensuring both low temperature curing condition (such as 130° C. to 150° C.) and high temperature curing condition (such as 180° C. to 190° C.), the curable epoxy compositions comprising the substituted amine accelerator or the accelerator combination of substituted urea and substituted imidazole are preferred.
In comparative examples 1 to 2, the curable epoxy compositions were prepared by a comparative accelerator. The cured epoxy compositions don't have desired good strength properties (shear strength, peel strength, impact peel strength at both room temperature and low temperature (−40° C.)) when the curing temperature range is from 130° C.-150° C. In comparative example 3, the curable epoxy composition was prepared by a comparative accelerator. The cured epoxy composition has bad storage stability, the composition gelated after long time storage (<80% change after 21 d 40° C. storage and no gelation occurred). It can be seen that the curable epoxy compositions comprising comparative accelerators can't have good strength properties and storage stability simultaneously.
In comparative example 4, the curable epoxy composition didn't comprise multifunctional epoxy-terminated prepolymer. The cured epoxy composition doesn't have good impact peel strength at both room temperature and low temperature (−40° C.), especially when the curing temperature range is from 130° C.-150° C.
| Number | Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/088112 | Apr 2022 | WO | international |
This application claims the benefit of PCT Application No. PCT/CN2022/088112, filed Apr. 21, 2022, the disclosure of which is incorporated by reference herein in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2022/139616 | Dec 2022 | WO |
| Child | 18919967 | US |
