BR112021008212B1 - MATERIAL, USE OF MATERIAL AND METHOD FOR ADHESION OF A FIRST SUBSTRATE TO A SECOND SUBSTRATE - Google Patents

Abstract

MATERIAL, USE OF MATERIAL AND METHOD FOR ADHESION OF A FIRST SUBSTRATE TO A SECOND SUBSTRATE. A material comprising an epoxy/elastomer adduct, a polymeric particle, from about 0.05 to about 20 weight percent of an epoxy/diacid adduct, and, optionally, an amine reaction product.

Description

FIELD OF INVENTION

[001] The present teachings generally relate to an activatable material, a method for forming the activatable material, and a method for using the activatable material to adhere components of articles of manufacture, such as automotive vehicles. The activatable material provides improved adhesion to individual substrates, especially when exposed to environmental stresses, improved adhesion between dissimilar substrates, improved breaking strength, improved strain-to-break, and improved adhesion durability.

BACKGROUND OF THE INVENTION

[002] For many years, industry, particularly the transportation industry, has been concerned with the adhesion and reinforcement of articles of manufacture, such as motor vehicles. A particular concern is the production of lightweight, energy-efficient vehicles in response to pressures from government regulations and other industry demands. In turn, the industry has developed a wide variety of activatable grip and seal materials to provide these lightweight, fuel-efficient vehicles. One approach to reducing vehicle weight includes replacing heavy components with counterparts composed of materials that are lighter than those currently used, for example, replacing galvanized steel with aluminum or polymer composites.

[003] Furthermore, joining various materials (such as steel to aluminum) often requires fastening means that are different from traditional welding. Different materials present significant challenges to traditional welding processes, so adhesives are often used in place of solders. To meet the needs presented in bonding different materials, these adhesives often need to have highly specific physical properties while adhering to a variety of different substrates.

[004] One concern with the use of such adhesives is the wide disparity in coefficients of thermal expansion between components composed of different materials. For example, the coefficient of thermal expansion of aluminum is approximately twice that of steel. Consequently, problems such as delamination, warping, flaw propagation, or other types of assembly distortion arise when automotive vehicles are heated to cure coatings and adhesives. As such, a suitable adhesive material must have sufficient tensile strength so as not to offset the increased relative displacement from differences in the coefficients of thermal expansion of materials bonded to each other.

[005] Another concern when different metals are close to each other is galvanic corrosion (e.g., as a result of ion transfer that can occur when the interface of the two metals is exposed to the environment (e.g., hot, humid, corrosive environments) ) Consequently, a suitable activatable material must have sufficient adhesion durability in hot, humid and corrosive environments.

[006] Some of the other desirable properties for these materials include high breaking strength, appropriate modulus of elasticity, improved wash resistance prior to activation (e.g., in its green state) and improved ease of dispensing when the material is located in a surface before activation. These properties, including strain-to-break and bond durability, have a generally inverse relationship, where an increase in one is followed by a decrease in the other. It is therefore a significant challenge to provide simultaneous improvements to both properties.

[007] The present teachings, therefore, seek to provide a material with deformation to failure, adhesion, T-peel and wedge impact and/or improved post-activation durability, while maintaining the appropriate modulus of elasticity (e.g., a modulus very consistent over a temperature range of -40°C to 80°C), ease of distribution and resistance to washing (before activation) compared to existing activatable materials.

SUMMARY OF THE INVENTION

[008] The teachings herein provide a material comprising an epoxy/elastomer adduct, a polymer particle, from about 0.05 to about 20 weight percent of an epoxy/diacid adduct, and optionally an amine reaction product.

[009] The material may have a T-bond of at least 14. The material may have a deformation to failure greater than 8%. The material may have a glass transition temperature, as defined by ASTM D7028-07, of at least 80°C. The material may include an amine reaction product. The epoxy/elastomer adduct may comprise a polydisulfide polymer. The epoxy elastomer adduct may be present in an amount of at least about 5% but less than about 50% by weight or even at least about 15% but less than about 30% by weight. The polymeric particle may be present in an amount of at least about 3% but less than about 60% by weight or even at least about 27% but less than about 32% by weight. The epoxy/diacid adduct may be present in an amount of from about 0.2% to about 15% by weight or even from about 2% to about 5% by weight.

[010] The amine reaction product may be present in an amount of from about 0.01% to about 15% by weight or even from about 0.5% to about 5% by weight. The amine reaction product may be present in an amount sufficient for the material to exhibit a T-peel strength of about 6 N/mm to about 30 N/mm. The amine reaction product can be chosen from 1-naphthylamine, 2-naphthylamine, ethanolamine, phenethylamine, oleylamine or a combination thereof. The amine reaction product can be added to an epoxy.

[011] The material may comprise phenoxy dissolved in an epoxy resin in the range of about 2% to about 10% by weight of the material. The material may comprise silane-modified epoxy resin in the range of about 8% to 18% by weight of the material.

[012] The material may include a curing agent. The material may include a flexibilizer. An epoxy component of the epoxy/diacid adduct may include epoxy bisphenol-F diglycidyl ether (DGEBF). The diacid component of the epoxy/diacid adduct may be one or more of a C18 or C36 diacid. The epoxy can be chosen from a bisphenol-F diglycidyl ether epoxy (DGEBF), a silane-modified epoxy, or a combination thereof.

[013] The material can have a deformation until failure of at least 16%. The material may have a modulus of at least 900 MPa.

[014] The polymeric particle may include polybutadiene core modifiers, styrene-butadiene rubber or a combination thereof. The polymeric particle may include core/shell rubber particles with an average size of about 100-200 nm. The polymeric particle may be substantially free of agglomerated particles. The elastomer in the epoxy/elastomer adduct may be selected from polydisulfide polymer, CTBN, ETBN, Epoxonic 328, or any combination thereof.

[015] The material may include a curing accelerator in the range of about 0.5% to about 5.0% by weight of the material. The material may include a curing agent in the range of about 2% by weight to about 7% by weight of the material. The material when cured can exhibit an elastic modulus of about 900 MPa to about 1700 MPa. The material when cured can exhibit a shear strength of at least about 20 MPa. The material can exhibit a T-peel strength when cured of about 6 N/mm to about 18 N/mm.

[016] The material may include one or more reinforcing components. The one or more reinforcing components may be selected from silica, diatomaceous earth, glass, clay (e.g., including nanoclay), glass spheres or microspheres, carbon or ceramic fibers, nylon, aramid or polyamide fibers (e.g., Kevlar), pyrophyllite, sauconite, saponite, nontronite, wollastonite, or montmorillonite. The material may include a silica and/or calcium-based reinforcing component. The silica-based reinforcing component may be fumed silica.

[017] The ratio of the epoxy/elastomer adduct to the reinforcement component can be from about 1 to 30 parts of epoxy/elastomer adduct to about 1 to 4 parts of reinforcement component. The ratio of epoxy/elastomer adduct to reinforcing component may be about 15 to 30 parts of epoxy/elastomer adduct to about 1 to 2 parts of reinforcing component. The ratio of epoxy/elastomer adduct to epoxy/diacid adduct can be about 1 to 6 parts epoxy/elastomer adduct to about 1 to 4 parts epoxy/diacid adduct. The ratio of epoxy/elastomer adduct to epoxy/diacid adduct can be about 3 to 7 parts epoxy/elastomer adduct to about 1 to 3 parts epoxy/diacid adduct. The ratio of epoxy/diacid adduct to amine reaction product can be about 1 to 12 parts epoxy/diacid adduct to about 1 to 3 parts amine reaction product.

[018] The teachings in the present invention are also directed to a material comprising less than about 30% by weight of a polymeric particle including core/shell rubber particles dispersed in epoxy resin, the core/shell rubber particles present in a concentration of at least 20% of the polymer particle, an epoxy/elastomer adduct, an amine reaction product.

[019] The material may include a silane-modified epoxy resin. The material may include a reinforcing component. The material may include an epoxy/diacid adduct. The material may have a strain to break of greater than 8% and a modulus of at least 900 MPa. The material may include a curing agent. The material may contain from about 15% to about 30% by weight epoxy/elastomer adduct. The material may have a strain to break of at least 16%. The material may have a modulus of at least 1100 MPa. The ratio of epoxy/elastomer adduct to silane-modified epoxy resin may be from about 1 to 20 parts epoxy/elastomer adduct to about 1 to 13 parts silane-modified epoxy resin. The ratio of epoxy/elastomer adduct to reinforcing component is about 1 to 30 parts epoxy/elastomer adduct to about 1 to 4 parts reinforcing component.

[020] The teachings in this document are further directed to the use of the materials described in this document as an adhesive. The teachings in this document are also directed to the use of the materials described in this document to adhere limbs to a transportation vehicle. The teachings in this document are further directed to the use of the materials described in this document to adhere steel to aluminum. The teachings in the present invention are also directed to the use of the materials described herein to adhere steel to the polymer composite or to adhere aluminum to the polymer composite.

[021] The teachings in the present invention also contemplate a method for adhering a first substrate to a second substrate, including: applying the material of any of the preceding claims to the first substrate; then place the material in contact with the second substrate after activating the material; and activation of the material.

BRIEF DESCRIPTION OF THE DRAWINGS

[022] Figure 1 shows a graph describing the storage modulus as a function of temperature to identify the glass transition temperature of an exemplary material in accordance with the present teachings.

DETAILED DESCRIPTION

[023] The explanations and illustrations presented in this document are intended to familiarize others skilled in the art with the present teachings, their principles and their practical application. The specific embodiments of the present teachings, as set forth, are not intended to be exhaustive or limiting of the present teachings. The scope of the present teachings should be determined with reference to the appended claims, together with the full scope of equivalents to which such claims are entitled. Disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. Other combinations are also possible, as will be gleaned from the following claims, which are also hereby incorporated by reference into this specification. Percentages here refer to percentages by weight unless otherwise noted.

[024] This application is related to provisional application US 62/751786, filed on October 29, 2018, the contents of that application being incorporated herein by reference for all purposes.

[025] The present teachings are based on providing an improved material (for example, an activatable material) and articles incorporating the same. The activatable material may assist in providing adhesion to a surface of a structure or to one or more structural members of an article of manufacture. As used herein, the phrase activatable material includes any material that can be activated to melt, flow, cure (e.g., thermoset) or a combination thereof by an ambient or other condition. For example, the material may flow, melt, cure, a combination thereof or the like upon exposure to a condition such as heat, pressure, chemical exposure, combinations thereof or the like.

[026] The activatable material typically includes an epoxy/elastomer adduct, a polymer particle, an epoxy/diacid adduct, an amine reaction product, a flexibilizer, phenoxy resin, a curing agent, a curing accelerator and a or more reinforcement charges.

[027] The activatable material of the present teachings can be applied to various articles of manufacture to add structural integrity to portions or members of the articles. Examples of such articles of manufacture include, without limitation, household or industrial appliances, furniture, storage containers, buildings, structures or the like. The activatable material can be applied to portions of transportation vehicles, including boats, trucks, trains, airplanes, motor vehicles, or the like. The material may be used in an automotive vehicle, such as with body or chassis members (e.g., a vehicle side member) of the automotive vehicle.

[028] The material can be formulated to include an adduct, which can be an epoxy/elastomer adduct. The epoxy/elastomer adduct imparts flexibility and the ability to create a separate phase when cured to the activatable material and the ability to absorb energy during plastic deformation and can impart the ability to create phase separation. This phase separation can improve deformation until failure. Various adducts may be employed in the present teachings. The epoxy/elastomer adduct may be included in an amount of up to about 75% by weight of the activatable material. The epoxy/elastomer adduct may be approximately at least about 5% by weight, more typically at least about 10% by weight, more typically at least about 15% by weight, and even more typically at least about 20%. by weight of the activatable material. The epoxy/elastomer adduct may be approximately about 75% or less by weight, more typically about 70% or less by weight, more typically about 65% or less by weight, and even more typically 60% or less by weight. weight of the activatable material. The epoxy/elastomer adduct may be a combination of two or more particular adducts. The adducts may be solid adducts, liquid or semisolid adducts at a temperature of 23°C or may also be some combination thereof. It is possible that the adduct is composed substantially (i.e., at least 70%, 80%, 90% or more) of one or more adducts that are solid at a temperature of 23°C. The adduct (if solid) may be in the form of a dissolution to facilitate simplified incorporation during mixing operations. The adduct can be used together with the polymeric particle, such as a core/shell material, styrene-butadiene rubber (SBR) or polybutadiene (PBd), an epoxy/diacid adduct, and an amine reaction product, which can achieve desirable adhesive performance and physical properties over a wide range of temperatures, even when employing a relatively small amount of the adduct.

[029] The adduct itself generally includes about 1:5 to 5:1 parts of epoxy to elastomer, and more preferably about 1:3 to 3:1 parts of epoxy to elastomer. More typically, the adduct includes at least about 10%, more typically at least about 20% and or even at least about 30% elastomer and also typically includes no more than about 60%, although higher percentages or lowest possible. The suitable elastomer compound for the adduct may be a thermosetting elastomer, although this is not necessary. Exemplary elastomers include, without limitation, natural rubber, SBR (styrene-butadiene rubber), polyisoprene, polyisobutylene, PBd (polybutadiene), isoprene-butadiene copolymer, neoprene, nitrile rubber, butyl rubber, carboxyl terminated polymer (e.g. carboxyl butadiene-acrylonitrile functional), polydisulfide polymer, acrylic elastomer, acrylonitrile elastomers, silicone rubber, polysiloxanes, polyester rubber, diisocyanate-bonded condensation elastomer, EPDM (ethylene propylene diene rubbers), carboxyl terminated polymer , carboxyl-terminated butadiene-acrylonitrile (CTBN), chlorosulfonated polyethylene, fluorinated hydrocarbons and the like. Examples of additional or alternative epoxy/elastomer or other adducts suitable for use in the present teachings are disclosed in US patent application 2004/0204551.

[030] An example of preferred adducts or preferred components for the production of the epoxy/elastomer adduct is an epoxidized polydisulfide polymer, such as products sold under the trade names Thioplast™ G and Thioplast™ EPS. Particularly preferred grades of epoxy/elastomer adducts are Thioplast™ G10 and Thioplast™ EPS-80, commercially available from Akzo Nobel. Another example is Hypro™ 1300X13NA (CTBN), commercially available from Emerald Performance Materials®, added with bisphenol-F diglycidyl ether. Yet another example of a preferred epoxy/elastomer adduct is Hypro™ 1300X63 (ETBN (glycidyl ester of butadiene butadiene acrylonitrile)). Another example of a preferred epoxy/elastomer adduct can be produced using Epoxonic 328.

[031] The elastomer-containing adduct can be included to modify the structural properties of the activatable material, such as strength, deformation to rupture, resistance to rupture (G1C), peeling, adhesion durability, rigidity or other properties. CTBN can be particularly useful for developing adhesion to contaminated surfaces, especially with stamping lubricants typical of the automotive industry. The material may include a carboxyl-terminated polymer adduct. The carboxyl-terminated polymer adduct can impart an improved strain at break greater than about 2% or even greater than about 3% for post-activation of the material.

[032] For exemplary purposes, Table A is produced below to illustrate an exemplary composition for creating the epoxy/elastomer adduct reaction product. TABLE A

[033] Generally, it is preferred that the activatable material include at least one type of polymeric particle. Such polymeric particles can be used to improve yield strength (G1C), peel strength, and impact strength. As used herein, the term “polymeric particle” is defined as a particle comprising a polymeric material. As with any other ingredients of the present teachings, the term “polymeric particle” can include one or more polymeric particles. Various polymeric particles can be employed in the practice of the present teachings and often include one or more elastomers. It is generally preferred that the polymeric particles be at least 4%, more typically at least 7%, even more typically at least 10%, even more typically at least 13%, and even more typically at least 16% by weight of the activatable material, and also preferred that the polymeric particle be less than 90%, more typically less than 40%, and even more typically less than 30% by weight of the activatable material, although greater or lesser amounts may be used in particular embodiments.

[034] The polymeric particle can include one or more core/shell polymers that can be pre-dispersed in an epoxy. The process for forming core-shell materials in a liquid epoxy prevents agglomeration of the core/shell particles as may be common with “dry” core/shell polymeric particles (e.g., agglomeration may occur during the drying process). . An example of products made by this process can be described in one or more of US patents 3984497; US 4096202; US 4034013; US 3944631; US 4306040; US 4495324; US 4304709; and US 4536436. Polymeric particles can be formed through an emulsion polymerization process. This process may include adding a solvent to the resin. As a result of incompatibility between the resin/solvent and water, water settles from the material as the core/shell particles move into the resin, resulting in reduced agglomeration. Alternatively, high-speed dispersion may be effective in deagglomerating core/shell materials. However, the surfactant may remain after spray drying or coagulating the core/shell material. This residual surfactant can be detrimental to the material's resistance to environmental exposure conditions involving water, such as salt spray and humidity. Materials not exposed to environmental exposure conditions typically do not show a difference between dry and liquid as long as there is sufficient deagglomeration of the dry material. The polymeric particle may include one or more core/shell polymers pre-dispersed in an epoxy, such as a bisphenol-A or bisphenol-F type epoxy.

[035] As used herein, the term core/shell polymer may denote a polymeric material in which a substantial portion (e.g., more than 30%, 50%, 70% or more by weight) thereof may be composed of a first polymeric material (i.e., the first material or core material) that can be substantially fully encapsulated by a second polymeric material (i.e., the second material or shell material). The first and second polymeric materials, as used in the present invention, may be comprised of one, two, three or more polymers that are combined and/or reacted together (e.g., sequentially polymerized) or may be part of core systems. /shell separate or equal. The core/shell polymer must be compatible with the formulation and preferably have a ductile core and a rigid shell that has favorable adhesion with the other components of the activatable material.

[036] The first and second polymeric materials of the core/shell polymer may include elastomers, polymers, thermoplastics, copolymers, other components or combinations thereof. The first polymeric material, the second polymeric material, or both may include or may be substantially entirely composed (e.g., at least 70%, 80%, 90% or more by weight) of one or more thermoplastics. Exemplary thermoplastics include, without limitation, styrenics, acrylonitriles, acrylates, vinyl esters, polyamides, polyethylenes, PBd (polybutadienes), SBR (styrene-butadiene rubber) or combinations thereof.

[037] Examples of useful core/shell graft copolymers may be those in which hard compounds, such as styrene, acrylonitrile or methyl methacrylate, can be grafted onto a core made of polymers of soft or elastomeric compounds, such as butadiene or methyl methacrylate. butyl. US patent 3985703 describes useful core-shell polymers, the cores of which are made of butyl acrylate, but may be based on ethyl isobutyl, 2-ethylhexyl or other alkyl acrylates or mixtures thereof. The core polymer may also include other copolymerizable containing compounds, such as styrene, vinyl acetate, methyl methacrylate, butadiene, isoprene or the like. The core polymer material may also include a cross-linking monomer having two or more unconjugated double bonds of approximately equal reactivity, such as ethylene glycol diacrylate, butylene glycol dimethacrylate and the like. The core polymeric material may also include a graft-bonded monomer having two or more unconjugated double bonds of unequal reactivity, such as, for example, diallyl maleate and allyl methacrylate.

[038] The shell portion can be polymerized from methyl acrylates, such as methyl methacrylate and, optionally, other alkyl (meth) acrylates and (meth) acrylates, such as ethyl, butyl or mixtures thereof. Up to 40 weight percent or more of the shell monomers may be styrene, vinyl acetate, vinyl chloride and the like. Additional core/shell graft copolymers useful in embodiments of the present teachings are described in US patents 3,984,497; US 4096202; US 4034013; US 3944631; US 4306040; US 4495324; US 4304709; and US 4,536,436. Examples of core/shell graft copolymers include, but are not limited to, MBS (methacrylate-butadiene-styrene) polymers, which are made by polymerizing methyl methacrylate in the presence of PBd (polybutadiene) or a rubber of polybutadiene copolymer. MBS graft copolymer resin can generally have an SBR (styrene-butadiene rubber) core and a polymer or acrylic copolymer shell. Examples of other useful core/shell graft copolymer resins include PBd (polybutadiene), ABS (acryloni-trile-butadiene-styrene), MABS (methacrylate-acrylonitrile-butadiene-styrene), ASA (acrylate-styrene-acrylonitrile), SA EPDM (styrene-acrylonitrile grafted onto ethylene-propylene diene monomer elastomeric structures), MAS (methacrylic-acrylic rubber styrene) and mixtures thereof.

[039] Examples of useful polymeric particles include, but are not limited to, those sold under the trade name, Kane Ace™, commercially available from Kaneka Americas Holding, Inc. Particularly preferred grades of Kane Ace™ are sold under the designations MX-134 and MX-267. The polymeric particles may have an average size of not less than 50 nm and not more than 300 nm. The polymeric particles may be from about 5% to about 30% by weight of the activatable material.

[040] The material may include an epoxy/diacid adduct. The use of the term diacid can refer to any polyfunctional molecule with two carboxylic acid moieties. Some diacid compounds are introduced into an epoxy structure to increase the flexibility and strength of the formulations and the ability to separate phases. The diacid component of the epoxy/diacid adduct may be a C8-C40 or more diacid compound that is adducted with an epoxy. The epoxy component of the epoxy/diacid adduct may be DGEBF (bisphenol-F diglycidyl ether). Diacids can be saturated or unsaturated. Preferably, the diacid is derived from an unsaturated fatty acid. An example of a preferred epoxy/diacid adduct is the esterification product of Epotec® YDF-172LV (DGEBF) and a C18 diacid. Another example of a preferred epoxy/diacid adduct is HyPox® DA323 (DGEBA and dimeric fatty acid adduct) available from Emerald Performance Materials®.

[041] The adduct generally includes about 1:6 to 6:1 parts of diacid to epoxy and more preferably about 1:4 to 4:1 parts of diacid to epoxy. More typically, the adduct includes at least about 10%, more typically at least about 20%, and even more typically at least about 40% diacid and typically includes no more than about 60%, although higher percentages or lowest possible.

[042] The material may include an amine reaction product. Such a reaction product can be used to improve peel strength and impact strength without having detrimental effects on other properties such as joint shear, modulus as measured by ASTM D7029-07, ultimate strength, or others. The amine reaction product may include an amine moiety and a hydrophobic moiety. The hydrophobic portion may be aliphatic, cyclic or a combination thereof. The hydrophobic portion may be C36 or less, C18 or less, C10 or less, or C4 or less. The amine reaction product can be selected to include one or more low molecular weight components. As a non-limiting example, the amine reaction product may include 1-naphthylamine, 2-naphthylamine, ethanolamine, phenethylamine, oleylamine or a combination thereof. The amine reaction product can be adducted with epoxy. The amine reaction product can be adducted with bisphenol-F epoxy, silane-modified epoxy, or a combination thereof. An example of a suitable epoxy may include Epotec® YDF 172LV (DGEBF). Another example of a suitable epoxy may include Epokukdo KSR-177 (bifunctional silane modified epoxy resin). The amine reaction product can be added with epoxy before adding to the material. It is possible for high molecular weight components to be selected as long as there are minimized deleterious effects on the viscosity of the material (e.g., so that the material can still flow as needed during an application process.

[043] For exemplary purposes, Table B is produced below to illustrate an exemplary composition for creating the amine reaction product with an epoxy. TABLE B

[044] The material may include a flexibilizer. The use of the term flexibilizer may refer to a single flexibilizer or to a combination of several different flexibilizers. Although other flexibilizers may be employed, preferred flexibilizers include polymers that are amine-modified, epoxy-modified, urethane-modified, or any combination thereof. Such polymers may include thermoplastics, thermosets or thermosets, elastomers, combinations thereof, or the like. Such polymers may be modified with urethane, aromatic or non-aromatic epoxy, and/or may be modified with bisphenol-F type, bisphenol-A type, combinations thereof, or another type of epoxy. An example of a preferred flexibilizer, which may be a phenol-terminated urethane-based curing agent, is Rez-Cure® EP 1820 (available from Innovative Resin Systems).

[045] An example of other preferred flexibilizers are polyurethane-modified epoxies sold under the trade names GME-3210 and GME-3220, commercially available from GNS Technologies. Without being limited by theory, it is believed that when a polyurethane-modified epoxy flexibilizer is included, the activatable material can substantially maintain impact strength (e.g., impact resistance) at low temperatures, while minimizing temperature reduction. glass transition (Tg) (e.g. compared to other flexibilizers). Still other examples of preferred flexibilizers are epoxy-terminated polyethers or amine precursor for producing epoxy-terminated polyethers, such as JEF-FAMINE M series or SD series, commercially available from Huntsman and DER 732, commercially available from Dow Chemical Company. Cashew nut shell liquid-based flexibilizers such as Cardolite NC-514 and Cardolite Lite 2513 HP epoxidized liquids are also useful flexibilizers. All of the individual flexibilizers discussed herein can be used separately or in combination with each other in the material of the present invention, unless otherwise indicated.

[046] Typically, the flexibilizer is at least 1%, more typically at least 2% and even possibly at least 5% by weight of the material, but is typically less than 50%, more typically less than 35% and even possibly less than 20% by weight of material, although higher and lower values may also be possible unless otherwise noted.

[047] The material described here may include an epoxy resin. An epoxy resin can be added to the activatable material to increase the material's adhesion, flow properties, or both. An exemplary epoxy resin may be a phenolic resin, which may be of the novolac type or another type of resin. An example of suitable epoxy resins is Epotec® YDF 172LV (DGEBF), available from Aditya Birla. Other preferred epoxy-containing materials may include modified epoxy resins. Epoxy resins can be silane-modified epoxy resins or silane-free epoxy resins. For example, a silane-modified epoxy resin can help allow the activatable material to adhere to metal, such as aluminum. The silane-modified epoxy resin may be a reaction product between at least one epoxy resin and a silane compound. An example of a suitable silane-modified epoxy resin is Epokukdo KSR-177 (difunctional silane-modified epoxy resin) available from Kukdo Chemical. Additionally, various mixtures of several different epoxy resins can also be employed. Epoxy resins may be present in other formulation components, such as the epoxy/elastomer adduct, the polymer particle dispersion and the epoxy/diacid adduct. The concentrations and type of epoxy resins present in the formulation components vary depending on the manufacturer and the specific grade. Epoxy resins may be present in the formulation components as adducts, unreacted epoxy, or both.

[048] The material may include a phenoxy resin component. Phenoxy resins are high molecular weight thermoplastic condensation products of bisphenol-A and epichlorohydrin and their derivatives. The phenoxy resins that can be used may have the basic formula: where n is typically 30 to 100, preferably 50 to 90. Modified phenoxy resins can also be used. Examples of phenoxy resins that can be used are products sold by Gabriel Performance Products. Examples of suitable materials are PKHB, PKHC, PKHH, PKHJ, PKHP granules and powder. Alternatively, phenoxy/polyester hybrids and epoxy/phenoxy hybrids can be used. In order to increase the production of the activatable material, it is preferred that the phenoxy resin is supplied to the other components as a solution. Although any solvent can be used, it is particularly preferred to use a low molecular weight epoxy resin as the solvent, as this can also contribute to the adhesive properties after activation.

[049] In certain embodiments, it may be desirable to include one or more thermoplastic polyethers and/or thermoplastic epoxy resins in the activatable material. When included, one or more thermoplastic polyethers preferably comprise between about 1% and about 90% by weight of the activatable material, more preferably between about 3% and about 60% by weight of the activatable material, and even more preferably between about 4% and about 25% by weight of the activatable material. As with other materials, however, more or less thermoplastic polyether may be employed depending on the intended use of the activatable material.

[050] Thermoplastic polyethers typically include pendant hydroxyl moieties. Thermoplastic polyethers can also include aromatic ether/amine repeating units in their backbones. The thermoplastic polyethers of the present teachings preferably have a melt index between about 5 and about 300, more preferably between about 30 and about 250 grams per 10 minutes for samples weighing 2.16 kg at a temperature of about 190° W. Obviously, thermoplastic polyethers can have higher or lower melt indices depending on the intended application. Preferred thermoplastic polyethers include, without limitation, polyetheramines, poly(amino ethers), copolymers of monoethanolamine and diglycidyl ether, combinations thereof, or the like.

[051] According to one embodiment, the thermoplastic polyether is formed by the reaction of a primary amine, a bis(secondary) diamine, a cyclic diamine, a combination of the same or similar (for example, monoethanolamine) with a diglycidyl ether or by reaction of an amine with an epoxy-functionalized poly(alkylene oxide) to form a poly(aminoether). According to another embodiment, the thermoplastic polyether is prepared by reacting a bifunctional amine with a diglycidyl ether or diepoxy-functionalized poly(alkylene oxide) under conditions sufficient to cause the amine moieties to react with the epoxy moieties to form a polymer backbone with amine bonds, ether bonds, and pendant hydroxyl moieties. Optionally, the polymer may be treated with a monofunctional nucleophile which may or may not be a primary or secondary amine.

[052] Furthermore, it is contemplated that amines (e.g., cyclic amines) with a reactive group (e.g., a reactive hydrogen) may be employed to form the thermoplastic polyether. Advantageously, such amines can assist in controlling the molecular weight of the thermoplastic ether formed.

[053] Examples of preferred thermoplastic polyethers and their formation methods are disclosed in US patents 5275853; US 5464924 and US 5962093, which are incorporated herein by reference for all purposes. Advantageously, thermoplastic polyethers can provide the activatable material with several desirable characteristics, such as desirable physical and chemical properties for a wide variety of applications, as further described herein.

[054] One or more curing agents and/or curing agent accelerators can be added to the activatable material. The amounts of curing agents and curing agent accelerators can vary widely within the activatable material, depending on the desired structural properties of the activatable material and the like. Exemplary ranges for the curing agents present in the activatable material vary from about 2% by weight to about 7% by weight. Exemplary ranges for the curing agent accelerator present in the material vary from about 0% to about 5% by weight.

[055] Preferably, the curing agents assist the activatable material in curing by cross-linking polymers, epoxy resins or both. Useful classes of curing agents are materials selected from aliphatic or aromatic amines or their respective adducts, amidoamines, polyamides, cycloaliphatic amines, anhydrides, polycarboxylic polyesters, isocyanates, phenol-based resins (e.g., phenol or cresol novolak resins, copolymers such as terpene phenol, polyvinyl phenol or bisphenol-A formaldehyde copolymers, bishydroxyphenyl alkanes or the like), or mixtures thereof. Particularly preferred curing agents include modified and unmodified polyamines or polyamides, such as triethylenetetramine, diethylenetriamine, tetraethylenepentamine, cyanoguanidine, dicyandiamides and the like. An accelerator for the curing agents (e.g., a modified or unmodified urea, such as methylenediphenyl bisurea, an imidazole, or a combination thereof) may also be provided to prepare the activatable material.

[056] An example of a suitable curing agent may be a polyamide curing agent, such as Amicure® CG 1200 (dicyanamide micronized curing agent) available from Evonik Resource Efficiency GmbH. An example of a suitable curing accelerator may be a substituted urea accelerator, such as Omicure® U-52M (phenyl substituted urea) available from Emerald Performance Materials®.

[057] The activatable material may also include one or more reinforcement components. Preferably, the reinforcing components include a material that is generally non-reactive with the other components present in the activatable material. It is contemplated that the reinforcing components may also impart properties such as strength and impact resistance to the activatable material.

[058] Examples of reinforcing components include wollastonite, silica, diatomaceous earth, glass, clay (for example, including nanoclay), glass spheres or microspheres, carbon or ceramic fibers, nylon fibers, aramid or polyamide fibers and the like. . An example of a suitable filler may be a fumed silica, such as CAB-O-SIL® TS-720 (polydimethylsiloxane-treated fumed silica) available from Cabot Corporation.

[059] When employed, the reinforcing components in the activatable material can range from 10% or less to 90% or more by weight of the activatable material, but more typically from about 20 to 55% by weight of the activatable material. According to some embodiments, the activatable material may include from about 0% to about 30% by weight, and more preferably, slightly less than 10% by weight of reinforcing components.

[060] Other additives, agents or performance modifiers may also be included in the activatable material as desired, including, but not limited to, a UV resistant agent, a flame retardant, a heat stabilizer, a dye, a processing, a lubricant or similar.

[061] It is contemplated that almost any additional chemicals, materials or any other may be added to the activatable material, assuming that they are suitable for the activatable material and suitable for a chosen application of the activatable material.

[062] It is possible that the specific combination and relative quantities of one or more materials described herein may assist in providing improved values for one or more modulus of elasticity, adhesion durability, T-peel, deformation to failure or shear of gasket (all post-activation). As another example, the combination of epoxy/elastomer adduct and epoxy/amine adduct can help impart improved strain rate at break and adhesion durability. The ratio of epoxy/elastomer adduct to epoxy/amine adduct is about 1 to 9 parts epoxy/elastomer adduct to about 1 to 3 parts epoxy/amine adduct. The ratio of epoxy/elastomer adduct to epoxy/amine adduct can be about 3 to 7 parts epoxy/elastomer adduct to about 1 to 3 parts epoxy/amine adduct. As another example, the combination of epoxy/elastomer adduct and silane-modified epoxy resin can help provide improved adhesion durability. The ratio of epoxy/elastomer adduct to silane-modified epoxy resin is about 1 to 10 parts of epoxy/elastomer adduct to about 1 to 7 parts of silane-modified epoxy resin. Another example is the combination of amine adduct and diacid adduct which can improve peel strength and impact strength.

[063] When determining the appropriate components for the activatable material, it may be important to form the material in such a way that it will only be activated (e.g., flow, melt, cure, or otherwise change state) at appropriate times or temperatures. For example, in some applications, it is undesirable for the material to be reactive at room temperature or otherwise at ambient temperatures in a production environment. More typically, the activatable material becomes activated to flow and develop adhesion at higher exposure temperatures. As an example, temperatures such as those found in an automobile assembly plant may be suitable, especially when the activatable material is processed together with the other components at elevated temperatures or at higher applied energy levels, for example during the preparation steps. of painting. Temperatures encountered in many coating operations (e.g., in a paint curing and/or electrophoretic deposition oven), for example, range up to about 250°C or more.

[064] The formation of the activatable material can be carried out according to a variety of new or known techniques. Preferably, the activatable material is formed as a material of substantially homogeneous composition. However, it is contemplated that various combination techniques may be used to increase or decrease the concentration of certain components at certain locations of the activatable material.

[065] According to another embodiment, the activatable material can be formed by heating one or more of the components that are generally easier to soften or liquefy, such as polymer-based materials to induce these components into a mixable state. After that, the remaining components can then be mixed with the softened components. The material can be compounded using a melt processing operation such as a twin screw, twin arm mixer, or planetary mixer.

[066] Depending on the components used, it may be important to ensure that the temperature of the components remains below certain activation temperatures that may cause the activatable material to cure before the intended cure time. In situations where it is desirable to maintain the activatable material at lower temperatures, it may be desirable to maintain the components in a semi-solid or viscoelastic state by using pressure or a combination of pressure and heat to mix the activatable material components. Various machines have been designed to avoid applying heat, pressure, or both to the materials.

[067] After formation of the activatable material, the material is typically applied to a surface and activated. When applied to a surface, the material may be in the form of a paste, a film, a solid extrudate, a liquid, or a seam. The material can be applied by robotic application, which can be a robotic extrusion device.

[068] It should be understood that, depending on the intended application, the activatable material can be applied and activated in different ways and at different times. Thus, exemplary uses of the activatable material are discussed below to illustrate preferred methodologies for applying and activating the activatable material. In particular, the activatable material can be used for, among others, reinforcement, adhesion or the like.

[069] According to one embodiment, it is contemplated that an activatable material in accordance with the present teachings can be employed as a structural adhesive material. In such an embodiment, the material is typically activated and cured (e.g., at temperatures common for electrophoretic deposition or automotive painting operations) to adhere to a first member and a second member. Contact with the attachment surface of the first member and the second member may occur before or during activation and curing of the material. Examples of structural adhesive applications are disclosed in US patent applications 10/234,902; US 10/386,287; US 60/451,811, all of which are incorporated herein by reference for all purposes.

[070] Certain activatable materials formed in accordance with the present teachings have exhibited post-activation modulus of elasticity greater than about 900 MPa, greater than about 1200 MPa, and even possibly greater than about 1500 MPa when determined in accordance with ASTM D638 Type IV test method. In addition, the activatable material, post-activation, particularly when provided as a solid, is typically less susceptible to rupture (e.g., spalling or the like).

[071] Certain activatable materials formed in accordance with the present teachings have exhibited post-activation joint shear strength greater than about 30 MPa, greater than about 35 MPa and even possibly greater than 40 MPa when determined in accordance with ASTM D5868.

[072] Certain activatable materials formed in accordance with the present teachings have exhibited post-activation deformation to failure greater than about 1%, greater than about 5%, greater than 8% and even possibly greater than 15% . The strain at failure was measured by performing a tensile test (ISO 527, for example), using an extensometer to record the strain which is then used to calculate the strain of the material.

[073] Certain activatable materials formed in accordance with the present teachings exhibited glass transition (TG) greater than 80 degrees Celsius, greater than 85 degrees Celsius and even greater than 90 degrees Celsius when determined by ASTM D7028-07. The glass transition temperature determined by this test method (referred to as Dynamic Mechanical Analysis Tg or “DMA Tg”) may not be the same as that reported by other measurement techniques on the same specimen. The test method is commonly used to determine the upper usage temperature for composite materials. Figure 1 shows the storage modulus as a function of temperature for an exemplary material of the present teachings. The glass transition temperature is identified as the temperature at which the storage modulus begins a more rapid decrease.

[074] For exemplary purposes, Tables C to D are produced below to illustrate two exemplary formulations for forming the activatable material. TABLE C TABLE D

[075] The comparative examples shown below demonstrate the change in physical properties based on the inclusion/removal of certain components of the materials disclosed in this document. TABLE E * 0.060” EG60/0.060 EG60 ** 0.060” EG60/0.080”Alu 6061 *** 0.080” Alu/0.080”Alu 6061 **** 0.030” EG60 TABLE F * 0.060” EG60/0.060 EG60 ** 0.060” EG60/0.080”Alu 6061 *** 0.080” Alu/0.080”Alu 6061 **** 0.030” EG60

[076] As shown in Table E, Sample 1 includes all components, but no amine reaction products. Sample 2 is free of the CTBN adduct and demonstrates lower elongation and impact resistance over a reduced wedge at -40°C. Sample 3 is free of the polysulfide adduct and demonstrates less T-bonding and reduced salt spray resistance for aluminum-to-aluminum bonding. Sample 4 is free of any diacid adducts and demonstrates reduced elongation.

[077] As shown in Table F, Sample 5 is a control sample compared to Samples 6-10, including no amine reaction products or diacid adducts. Sample 6 includes the diacid adduct. Sample 7 includes the amine reaction product and the diacid adduct. Sample 8 includes only the amine reaction product. Sample 9 includes the amine reaction product and the diacid adduct, but no polymer particles. Sample 10 includes the amine reaction product and diacid adduct, but no polysulfide adducts, flexibilizers, or epoxon adducts (e.g., no elastomeric materials). Sample 7 demonstrates the best physical properties. The presence of the amine adduct shows a significant improvement for T-bonding. Both Samples 9 and 10 show reduced physical properties overall due to the lack of polymeric particles and elastomeric components, respectively.

[078] As used herein, unless otherwise indicated, the teachings provide that any member of a genus (list) may be excluded from the genus; and/or any member of a Markush cluster may be excluded from the cluster.

[079] Unless otherwise indicated, any numerical values indicated herein include all values from the lower value to the upper value in one-unit increments, provided that there is a separation of at least 2 units between any lower value and any higher value higher. By way of example, if it is stated that the amount of a component, a property or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably 30 to 70, intermediate range values such as (e.g., 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc.) are intended to be within the teachings of this specification. Likewise, individual intermediate values are also within the present teachings. For values less than one, one unit is considered 0.0001, 0.001, 0.01, or 0.1, as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest enumerated value should be considered expressly stated in this application in a similar manner. As can be seen, the teaching of quantities expressed as “parts by weight” here also covers the same ranges expressed in terms of percentage by weight. Thus, an expression in a range in terms of “'x' parts by weight of the resulting polymeric mixture composition” also contemplates a teaching of ranges of the same indicated amount of “'x' in percentage by weight of the resulting polymeric mixture composition”. ”

[080] Unless otherwise noted, all ranges include both terminals and all numbers between terminals. The use of “about” or “approximately” in connection with a range applies to both ends of the range. Thus, “about 20 to about 30” is intended to cover “about 20 to about 30,” including at least the specified endpoints.

[081] Disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The term “consisting essentially of” to describe a combination shall include the identified elements, ingredients, components or steps, and such other elements, ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms “comprising” or “including” to describe combinations of elements, ingredients, components or steps herein also contemplates embodiments that consist of, or consist essentially of, the elements, ingredients, components or steps.

[082] Elements, ingredients, components or steps in the plural can be provided by a single integrated element, ingredient, component or step. Alternatively, a single integrated element, ingredient, component or step may be divided into several separate elements, ingredients, components or steps. The disclosure of “a” or “a” to describe an element, ingredient, component or step is not intended to exclude additional elements, ingredients, components or steps.

[083] It is understood that the above description is intended to be illustrative and not restrictive. Many embodiments, as well as many applications beyond the examples provided, will be apparent to those skilled in the art after reading the above description. The scope of the invention must therefore be determined not with reference to the above description, but instead must be determined with reference to the appended claims, together with the full scope of equivalents to which such claims are entitled. Disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The omission in the following claims of any aspect of the subject matter disclosed herein is not a waiver of such subject matter, nor should it be deemed that the inventors have not considered such subject matter to be part of the disclosed inventive subject matter.

Claims (43)

1. MATERIAL, characterized by comprising: i) an epoxy/elastomer adduct; ii) less than 30% by weight of a polymeric particle including core/shell rubber particles dispersed in epoxy resin; iii) from 0.05 to 20 weight percent of an epoxy/diacid adduct selected from an adduct of DGEBA (diglycidyl ether of bisphenol-A) and dimeric fatty acid, or an adduct of DGEBF (diglycidyl ether of bisphenol-F) and a C18 diacid; and iv) optionally, an amine reaction product wherein, when cured, the material exhibits a strain to failure greater than 8% and an elastic modulus of 900 MPa to 1700 MPa. 2. MATERIAL, according to claim 1, characterized in that the material has a T-peel of at least 14. 3. MATERIAL, according to any of the preceding claims, characterized in that the material has a glass transition temperature, as defined by ASTM D7028-07, of at least 80°C. 4. MATERIAL according to any one of the preceding claims, characterized in that the material includes an amine reaction product. 5. MATERIAL, according to any of the preceding claims, characterized in that the epoxy/elastomer adduct comprises a polydisulfide polymer. 6. MATERIAL according to any one of the preceding claims, characterized in that the epoxy/elastomer adduct is present in an amount of at least 5%, but less than 50% by weight or even at least 15%, but less than 30% by weight. 7. MATERIAL, according to any one of the previous claims, characterized in that the polymeric particle is present in an amount of at least 3% or even at least 27%. 8. MATERIAL according to any of the preceding claims, characterized in that the epoxy/diacid adduct is present in an amount of 0.2% to 15% by weight or even 2% to 5% by weight. 9. MATERIAL according to any of the preceding claims, characterized in that the amine reaction product is present in an amount of 0.01% to 15% by weight or even 0.5% to 5% by weight. 10. MATERIAL, according to any of the preceding claims, characterized in that the amine reaction product is present in an amount sufficient for the material to present a T-peel resistance of 6 N/mm to 30 N/mm. 11. MATERIAL, according to any of the preceding claims, characterized in that the material comprises phenoxy dissolved in an epoxy resin in the range of 2% to 10% by weight of the material. 12. MATERIAL, according to any of the preceding claims, characterized in that the material comprises epoxy resin modified with silane in the range of 8% to 18% by weight of the material. 13. MATERIAL, according to any one of the preceding claims, characterized in that it includes a curing agent. 14. MATERIAL, according to any one of the previous claims, characterized by including a flexibilizer. 15. MATERIAL according to any one of the preceding claims, characterized in that an epoxy component of the epoxy/diacid adduct includes epoxy based on bisphenol-F diglycidyl ether (DGEBF). 16. MATERIAL according to any one of the preceding claims, characterized in that the diacid component of the epoxy/diacid adduct is one or more of a C18 or C36 diacid. 17. MATERIAL according to any one of the preceding claims, characterized in that the amine reaction product is chosen from 1-naphthylamine, 2-naphthylamine, ethanolamine, phenethylamine, oleylamine or a combination thereof. 18. MATERIAL, according to any of the preceding claims, characterized in that the amine reaction product is adducted with an epoxy. 19. MATERIAL, according to claim 15, characterized in that the epoxy is chosen from a bisphenol-F diglycidyl ether epoxy (DGEBF), a silane-modified epoxy or a combination thereof. 20. MATERIAL, according to any of the previous claims, characterized in that the material presents a deformation until failure of at least 16%. 21. MATERIAL according to any one of the preceding claims, characterized in that the polymeric particle includes polybutadiene core modifiers, styrene-butadiene rubber or a combination thereof. 22. MATERIAL according to any one of the preceding claims, characterized in that the polymeric particle includes core/shell rubber particles with an average size of 100-200 nm. 23. MATERIAL, according to any one of the preceding claims, characterized in that the polymeric particle is free of agglomerated particles. 24. MATERIAL, according to any of the preceding claims, characterized in that the elastomer in the epoxy/elastomer adduct is selected from polydisulfide polymer, CTBN (carboxyl-terminated butadiene-acrylonitrile), ETBN (butadiene glycidyl ester and butadiene- acrylonitrile), Epoxonic 328 or any combination thereof. 25. MATERIAL according to any one of the preceding claims, characterized in that the material includes a curing accelerator in the range of 0.5% to 5.0% by weight of the material. 26. MATERIAL according to any one of the preceding claims, characterized in that the material includes a curing agent in the range of 2% by weight to 7% by weight of the material. 27. MATERIAL according to any one of the preceding claims, characterized in that the material when cured exhibits a joint shear strength of at least 20 MPa. 28. MATERIAL, according to any one of the preceding claims, characterized in that the material exhibits a resistance to T-peeling when cured of 6 N/mm to 18 N/mm. 29. MATERIAL, according to any one of the preceding claims, characterized in that it includes one or more reinforcing components. 30. MATERIAL according to claim 29, characterized in that one or more reinforcing components are selected from silica, diatomaceous earth, glass, clay (for example, including nanoclay), glass spheres or microspheres, carbon fibers or ceramic, nylon, aramid or polyamide fibers (e.g. Kevlar), pyrophyllite, sauconite, saponite, nontronite, wollastonite or montmorillonite. 31. MATERIAL, according to any one of the preceding claims, characterized in that it includes a reinforcing component based on silica and/or calcium. 32. MATERIAL, according to claim 31, characterized in that the silica-based reinforcement component is fumed silica. 33. MATERIAL according to any of the preceding claims, characterized in that it includes a reinforcing component, wherein the ratio of the epoxy/elastomer adduct to the reinforcing component is 1 to 30 parts of epoxy/elastomer adduct to 1 to 4 parts of reinforcement component. 34. MATERIAL according to any one of the preceding claims, characterized in that it includes a reinforcing component and in which the ratio of the epoxy/elastomer adduct to the reinforcing component is 15 to 30 parts of epoxy/elastomer adduct to 1 to 2 parts of reinforcement component. 35. MATERIAL according to any one of the preceding claims, characterized in that the ratio of the epoxy/elastomer adduct to the epoxy/diacid adduct is 1 to 6 parts of epoxy/elastomer adduct to 1 to 4 parts of epoxy/diacid adduct. 36. MATERIAL according to any of the preceding claims, characterized in that the ratio of the epoxy/elastomer adduct to the epoxy/diacid adduct is 3 to 7 parts of epoxy/elastomer adduct to 1 to 3 parts of epoxy adduct /diacid. 37. MATERIAL according to any of the preceding claims, characterized in that the ratio of epoxy/diacid adduct to amine reaction product is 1 to 12 parts of epoxy/diacid adduct to 1 to 3 parts of amine reaction product. the mine. 38. USE OF THE MATERIAL, as defined in any of the previous claims, characterized by being as an adhesive. 39. USE OF THE MATERIAL, as defined in any of the previous claims, characterized in that it is for adhering members to a transport vehicle. 40. USE OF THE MATERIAL, as defined in any of the previous claims, characterized in that it is for adhering steel to aluminum. 41. USE OF THE MATERIAL, as defined in any of the previous claims, characterized in that it is for adhering steel to the polymer composite. 42. USE OF THE MATERIAL, as defined in any of the previous claims, characterized in that it is for adhering aluminum to the polymer composite. 43. METHOD FOR ADHESION OF A FIRST SUBSTRATE TO A SECOND SUBSTRATE, characterized in that it includes: applying the material, as defined in any one of claims 1 to 37, to the first substrate; then contact of the material with the second substrate before or after activation of the material.