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    • 专利摘要:
    thermosetting adhesive composition, thermosetting adhesive film, process for bonding a first substrate to a second substrate, and method for producing a thermosetting adhesive film are presented here thermosetting adhesive compositions, formed from an epoxy resin containing nano-sized core-carcass particles, one or more thermoplastic curing agents containing an amine-terminated polyether sulfone, and at least one multifunctional epoxy resin, along with at least one amine curing agent, to allow curing total adhesive composition up to 400 ° f (204 ° c). such compositions are useful for forming adhesive films that can bond composite / metallic / honeycomb structures for aerospace application, including the connection of leading and trailing edges on airplanes, acoustic nacelle structures, horizontal and vertical tails, and various other structures, as well as for other high performance industrial applications.
    公开号:BR112012003572B1
    申请号:R112012003572-0
    申请日:2010-08-26
    公开日:2020-03-17
    发明作者:Dalip Kohli
    申请人:Cytec Technology Corp.；
    IPC主号:
    专利说明:

    “THERMOFIXING ADHESIVE COMPOSITION, THERMOFIXING ADHESIVE FILM, PROCESS FOR THE CONNECTION OF A FIRST SUBSTRATE TO A SECOND SUBSTRATE, AND, METHOD FOR THE PRODUCTION OF A THERMOFIXING ADHESIVE FILM” FUNDAMENTALS OF THE INVENTION 1. Field of the Invention [0001] The subject in reference to the current invention it relates to thermosetting epoxy adhesive compositions, useful for bonding various metallic compounds or substrates, and having improved characteristics. More particularly, the subject in question refers to thermosetting compositions containing nano-sized, core-carcass particles, in combination with elastomers and / or thermoplastics, to produce superior synergistic stiffness, high temperature shear properties, high glass transition, and low water absorption. These new compositions are suitable for hostile environments and applications required in various industries, such as structural adhesive and matrix resins for resins previously impregnated with epoxy reinforcement. 2. Description of the Related Art [0002] Many compositions and processes are described in the art for the production and use of a wide variety of compositions based on epoxy and other resins and adhesives, in an effort to improve shear strength, resistance to impact and other important properties of adhesives useful in the adhesion, filling and production of compounds and metallic structures. For example, patents that describe components for the formulation of adhesive compositions and the use of such compositions for the adhesion of various substrates with each other to produce a structural reinforcement, include U.S. patents number 5,028,478; 5,087,657; 5,242,748; 5,278,257; 5,290,857; 5,605,745; 5,686,509; 5,334,654; 6,015,865; 6,037,392; 6,884,854; 6,776,869; and US patent application publications number 2005/0022929; and 2008/0188609.
    [0003] Although adhesive compositions and compound structures with improved stiffness have been presented previously, there has been some sacrifice with respect to other physical properties of the compositions, including, for example, a reduction in glass transition temperatures along with an increase in drag at high temperatures. For example, even today, adhesive compositions suffer from a decrease in high temperature properties (for example, shear properties) when the stiffness (removal) is increased. Other difficulties with such compositions and adhesive compounds may include a loss of rigidity, failure of adhesion that occurs between substrates formed from different materials and / or resins, and deterioration of properties during use due to poor solvent resistance.
    [0004] Therefore, the adhesive compositions and methods currently available for the production of hardened compounds and for the bonding of various compounds and / or metallic substrates require further improvement. Adhesive thermosetting compositions having an improved impact resistance, and having improved rigidity properties at high temperatures would be a useful advance in the technique and could find rapid acceptance in the aerospace and high-performance automobile industries, among others.
    SUMMARY OF THE INVENTION
    [0005] The invention described here is directed, in one aspect, to thermosetting adhesive compositions having a composition that is pre-reacted, which is formed by the reaction of an epoxy resin containing nano-sized particles with a core, one or more thermoplastic modifiers containing an amine-terminated polyethersulfone and / or an amine-terminated polysulfone, and at least one functional epoxy resin, together with at least one amine curing agent, to allow the adhesive composition to fully cure to 400 ° F (204 ° C). Nano-sized core-carcass particles used in conjunction with the indicated thermoplastic, produce the unexpected benefit of high temperature shear properties without loss of rigidity. The unique combination of higher stiffness and higher temperature performance represents a new paradigm shift in properties and a departure from those prior art compositions, which experience a reduction in higher temperature properties when stiffness is increased. [0006] In one embodiment, the prior reaction of the thermosetting adhesive composition may further include a bisphenol and a catalyst for the bisphenol-epoxy reaction, to control the crosslinking density.
    [0007] In another aspect, the invention features thermosetting adhesive films that are suitable for the manufacture of an article, such as by bonding several substrates together, where the film includes a thermosetting adhesive composition as described here, and where the film weight is 0.02 to 0.15 psf.
    [0008] In another aspect, the invention presents methods for the production of adhesive thermosetting films with improved hot / wet properties at high temperature, by coating one of the adhesive thermosetting compositions presented here on a removable paper, at a temperature and enough weight to form a film.
    [0009] In yet another aspect, the invention features processes for bonding a first article and a second article, by producing a thermosetting adhesive composition or a thermosetting adhesive film, as described here, as a point of contact between a surface of the first and second article, and the curing of the thermosetting adhesive composition or adhesive thermosetting film, while in contact with the surface of the first and second articles, thereby bonding the first and second articles.
    [0010] These and other objectives, characteristics and advantages of this invention will become apparent based on the following detailed description of the various aspects of the invention, considered together with the accompanying figures and examples.
    BRIEF DESCRIPTION OF THE DRAWINGS
    [0011] Figure 1 illustrates the removal (or stiffness) as a function of shear strength (shear properties) at high temperatures. As detailed, the curve represents a drop in removal / stiffness when shear properties are increased at elevated temperatures. The compositions according to the invention, as described and claimed here, are detailed beyond the curve, thus showing a paradigm shift in properties, when compared to the compositions of the prior art.
    [0012] Figure 2 illustrates an electron scanning microscope of the fracture surface and morphology of one of the compositions described here. The fractured surface shows that the particle size is less than 100 nm.
    DETAILED DESCRIPTION OF CERTAIN ACCOMPLISHMENTS OF THE INVENTION
    [0013] As summarized above, the discovery relates to adhesive thermosetting compositions containing an epoxy resin with nanoparticles with core-carcass in combination with elastomers and / or thermoplastics, which can be thermally cured with amine curing agents to produce adhesive thermosetting compositions having high rigidity and high temperature shear properties. In addition to the unexpected increase in properties at higher temperatures with better rigidity, these compositions are also characterized by high glass transition temperatures and low water absorption, making the compositions suitable for environments that require high performance, such as for industries aerospace and automotive.
    [0014] Epoxy resins [0015] The preferred formulations of thermoset resins used for the current invention will be based on epoxy resins, which are well known to those of ordinary skill in the art. The epoxy resins that can be used in the current invention are curable epoxy resins having an amount of epoxy groups per molecule. In general, a large number of glycidyl ethers having at least about two epoxy groups per molecule are suitable as epoxy resins for the compositions of this invention. Polypoxides may be composed of saturated, unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic polypoxides. Examples of suitable polypoxides include polyglycidyl ethers, which are prepared by reacting epichlorohydrin or epibromohydrin with a polyphenol, in the presence of an alkali. Suitable polyphenols are, for example, resorcinol, pyrocatechol, hydroquinone, bisphenol A (bis (4-hydroxyphenyl) -2,2-propane, bisphenol F (bis (4-hydroxyphenyl) methane), bisphenol A, bis (4-hydroxyphenyl) -1,1-isobutane, fluorene 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1,1-ethane, bisphenol Z (4,4'-cyclohexylidenobisphenol), and 1,5-hydroxy-naphthalene. In this embodiment, the epoxy resin includes EPON 828. Such resins are commonly used for the production of adhesive materials and / or compounds that are readily available from commercial sources.Other suitable polyphenols as the base for polyglycidyl ethers are the condensation products known to phenol and formaldehyde or acetaldehyde of the novolac resin type.
    [0016] Other polypoxides which, in principle, are suitable, are polyglycidyl ethers of polyalcohols, amino-phenols or aromatic diamines. Special preference is given to liquid epoxy resins derived from the reaction of bisphenol A or bisphenol F and epichlorohydrin. Bisphenol A-based epoxy resins that are liquid at room temperature generally have epoxy equivalent weights of 150 to about 200. Epoxy resins that are solid at room temperature can also, or alternatively, be used and similarly, they are obtainable from polyphenols and epichlorohydrin, and have a melting point of 45 to 130 ° C, preferably 50 to 80 ° C. Typically, the composition may contain about 25 to about 90% by weight (e.g., 25, 30, 35, 40, 45, 50, 55% by weight) of epoxy resin (unless otherwise stated) , all concentrations shown here are expressed in terms of percentage by weight of the component in question, based on the adhesive composition as a whole).
    [0017] Any of these resins can serve as the resin that contains, or is previously dispersed with, core-carcass nanoparticles in the previously reacted component, or as the second epoxy resin of the thermosetting composition. Epoxy resins especially preferred for use as the second epoxy resin, include novolacs (including, but not limited to Hunstsman's Tactix 71756), polyglycidyl derivatives of amines and aminophenols, including, for example, p-aminophenol, aniline, phenylenediamine, and 4 , 4'-methylenedianiline. Commercially available forms of polyglycidyl methylene dianiline ethers include MY 9655 from Huntsman.
    [0018] As described in more detail below, epoxy resins are not used alone, but are combined with suitable curing agents, catalysts, rheology control agents, binders, fillers, elastomeric hardening agents, reactive diluents, soluble and thermoplastics other additives well known to those skilled in the art.
    Core-carcass particles [0019] Particles having a core-carcass structure are an additional component of the compositions of the current invention. Such particles generally have a core made of a polymeric material having elastomeric or rubber properties (ie, a glass transition temperature less than about 0 ° C, for example, less than about -30 ° C) surrounded by a shell consisting of a non-elastomeric polymeric material (ie, a thermoset / crosslinked or thermoplastic polymer having a glass transition temperature greater than the ambient temperature, for example, greater than about 50 ° C). For example, the core may consist of a diene homopolymer or copolymer (for example, a butadiene or isoprene homopolymer, a butadiene or isoprene copolymer with one or more ethylenically unsaturated monomers, such as aromatic vinyl monomers, methacrylonitrile, methacrylates , or the like) while the carcass may consist of a polymer or copolymer of one or more monomers, such as methacrylates (for example, methyl methacrylate), vinyl aromatic monomers (for example, styrene), vinyl cyanides (for example, acrylonitrile ), unsaturated acids and anhydrides (e.g., acrylic acid), methacrylamides, and the like, having a suitably high glass transition temperature. The polymer or copolymer used in the carcass may have acidic groups that are ionically cross-linked through the formation of metallic carboxylate (for example, by the formation of divalent metal cation salts). The polymer or copolymer of the carcass could also be crosslinked covalently through the use of monomers having two or more double bonds per molecule. Other elastomeric polymers may also be used appropriately for the core, including the polybutyl acrylate or polysiloxane elastomer (for example, polydimethyl siloxane, especially cross-linked polydimethyl siloxane). The particle may consist of more than two layers (for example, a central core of an elastomeric material may be surrounded by a second core of different elastomeric material or the core may be surrounded by two carcasses of different composition, or the particle may have a soft core of structure, a rigid housing, a soft housing, a hard housing). The core or shell or both, the core and the shell, may be cross-linked (for example, ionically or covalently), as described, for example, in U.S. Patent No. 5,686,509 (incorporated herein by reference in its entirety). The housing can be grafted onto the core. The polymer constituted by the carcass may contain one or more different types of functional groups (for example, epoxy groups, carboxylic acid groups) that are capable of interacting with other components of the compositions of the current invention. In other embodiments, however, the carcass is free of functional groups capable of reacting with other components present in the composition. Typically, the core will be composed of about 50 to about 95% by weight of the particles, while the carcass is composed of about 5 to about 50% by weight of the particles.
    [0020] Preferably, the elastomeric particles are relatively small in size. For example, the average particle size could be from about 30 nm to about 120 nm. In certain embodiments of the invention, the particles have an average diameter of less than about 80 nm. In other embodiments, the average particle size is less than about 100 nm. For example, the core-carcass particles may have an average diameter within the range of 50 to about 100 nm.
    [0021] Methods of preparing various elastomeric particles having a core-carcass structure are well known, and they are described, for example, in US patents number 3,985,703, 4,180,529, 4,315,085, 4,419,496 , 4,778,851, 5,223,586, 5,290,857, 5,534,594, 5,686,509, 5,789,482, 5,981,659, 6,111,015, 6,147,142, 6,150,693 and 6,331,580 and published American number application 2005-124761, each of which is incorporated here as a reference in its integrity. Elastomeric particles having a core-shell structure are also available from several commercial sources. The following core-shell particles are suitable for use in the current invention, for example: core-shell particles available in powder form from Wacker Chemie under the trademark GENIOPERL, including GENIOPERL P22, P23, P52 and P53, which are described by the supplier as having cross-linked polysiloxane cores, functional epoxy polymethylmethacrylate housings, with a polysiloxane content of about 65% by weight, softening points as measured by DSC / DMTA of about 120 ° C, and a size of primary particle around 100 nm, the core-carcass rubber particles available from Rohm & Haas under the PARALOID brand, especially the PARALOID EXL 2600/3600 series of products, which are grafted polymers containing a polybutadiene core into which they are grafted a styrene / methyl methacrylate copolymer, and having an average particle size of about 0.1 to about 0.3 microns; the rubber core-carcass particles sold under the trademark DEALAN by Rohm GmbH or Rohm America, Inc. (for example, DEGALAN 4899F, which is reported to have a glass transition temperature of about 95 ° C); the rubber core-carcass particles sold by Nippon Zeon under the trademark F351; and particles with rubber core-casings, sold by General Electric under the brand BLENDEX.
    [0022] Elastomeric particles having a core-carcass structure may be prepared as a standard mixture, where the particles are dispersed in one or more epoxy resins, such as diglycidyl ether of bisphenol A. For example, the particles are typically prepared as aqueous dispersions or emulsions. Such dispersions or emulsions may be combined with the desired epoxy resin or mixture of epoxy resins and water, and other volatile substances removed by distillation, or the like. A method of preparing such standard mixtures is described in more detail in European patent application EP 1632533, incorporated herein as a reference in its entirety. For example, an aqueous latex of rubber particles may be brought into contact with an organic medium having a partial solubility in water and then with another organic medium having a lower partial solubility in water than the first organic medium, to separate the water and produce a dispersion of rubber particles in the second organic medium. This dispersion can then be mixed with the desired epoxy resin and the volatile substances removed by distillation or the like to produce the standard mixture. Other methods for the preparation of standard mixtures of elastomeric particles having a core-carcass structure dispersed stably in an epoxy resin matrix are described in U.S. patents 4,778,851 and 6,111,015, each of which is incorporated herein as reference in its integrity. Preferably, the particles are dispersed stably in the epoxy resin matrix, ie, the core-carcass particles remain as separate individual particles with little or no particle agglomeration or precipitation (decantation) of the particles of the standard mixture when the standard mixture is aged and left to stand at room temperature. The substrate of the elastomeric particles can advantageously be functionalized to improve the stability of the standard mixture, although, in another embodiment, the substrate is not functionalized (ie, does not contain any functional group that reacts with any of the other components of the adhesive composition (such as epoxy resin or curing agent) when the composition is cured). Particularly suitable dispersions of particles having a core-carcass structure in an epoxy resin matrix are available from Kaneka Corporation, and include, KANE ACE MX 120®.
    [0023] Elastomeric particles having a core-carcass structure can be produced by any method known in the art, such as emulsion polymerization, suspension polymerization, micro-suspension polymerization and the like. In particular, a process involving emulsion polymerization is preferred. In carrying out the invention where the core-carcass particles are to be introduced into the adhesive composition in the form of a standard mixture in the epoxy resin, the concentration of the rubber particles is not particularly limited. The epoxy resin used for the preparation of the standard mixture may be the same, or different from the epoxy resin introduced separately in the composition. In one embodiment, the entire epoxy resin of the adhesive composition of the current invention is introduced in the form of a standard mixture, together with the core-carcass particles. Considering that the total amount of epoxy resin and rubber particles in the standard mixture is 100% by weight, the content of the core-carcass particles may be, for example, 0.5 to 80%, preferably 1 to 70% by weight, more preferably 3 to 60% by weight, even more preferably 20 to 40% by weight. In one embodiment, the weight percentage of epoxy resin containing, or previously dispersed with, core-carcass nanoparticles, is 40% to 50% of the total weight of the thermosetting composition.
    [0024] In the formulation of the invention, the use of these core-shell rubbers allows stiffening to occur in the formulation, regardless of the temperature or temperatures used to cure the formulation. That is, because of the two-phase separation inherent in the formulation due to core-shell rubber - as contrasted, for example, with a liquid rubber that is miscible or partially miscible or even immiscible in the formulation and can solidify at different temperatures than those used to cure the formulation - there is minimal disruption of the matrix properties, when phase separation in the formulation is often observed to be substantially uniform naturally. In addition, predictable stiffening - in terms of temperature neutrality until curing - can be achieved because of the substantially uniform dispersion.
    [0025] Many of Kaneka's core-carcass rubber structures available in the form of separate phase particles dispersed in epoxy resin are believed to have a core made of a methacrylate-butadiene-styrene copolymer, where butadiene is the main component of the copolymer in the core. Other commercially available standard blends of core-shell rubber particles dispersed in epoxy resins include GENIOPERL M23A (a 30% dispersion of core-shell particles in an aromatic epoxy resin based on a diglycidyl ether bisphenol A; carcass core have an average diameter of approximately 100 nm and contain a crosslinked silicone elastomer core into which an epoxy acrylate copolymer has been grafted; the silicone elastomer core represents about 65% by weight of the core carcass particle) , available from Wacker Chemie GmbH.
    [0026] Typically, the adhesive composition may contain about 5 to about 25% by weight (in one embodiment, about 8 to about 20% by weight) of elastomeric particles having a core-carcass structure. Combinations of different core-shell particles can be used to advantage in the current invention. The core-carcass particles may be different, for example, in particle size, in the glass transition temperatures of their respective cores and / or carcasses, in the polymer compositions used in their respective cores and / or carcasses, in the functionalization of their respective housings, and so on. A portion of the core-carcass particles may be provided for the adhesive composition in the form of a standard mixture, where the particles are dispersed stably in an epoxy resin matrix and another portion may be supplied for the adhesive composition in the form of a dry powder (ie, without any epoxy resin or other matrix material). For example, the adhesive composition may be prepared using both, a first type of core-carcass particles in the form of a dry powder having an average particle diameter of about 0.1 to about 10 microns, more preferably , from about 0.2 to about 2 microns) and a second type of core-carcass particles dispersed stably in a matrix of bisphenol A diglicidyl ether in a concentration of about 5 to about 50% by weight, and having an average particle diameter of about 25 to about 100 nm. The weight ratio between the first type and the second type of core-carcass rubber particles may be, for example, from about 1.5: 1 to about 0.3: 1. Core-shell rubber sold by Nippon Zeon under the trademark F351 may, for example, be used as the first type of core-shell rubber particles and core-shell rubbers sold by Kaneka Corporation under the KANACE trademarks MX120® and KANACE MX156®, could, for example, be used as the source of the second type of rubber core-shell particles.
    Stiffening agents [0027] Suitable stiffening agents may be chosen from a wide variety of substances, but generally speaking, such materials are polymeric or oligomeric in character, and have functional groups, such as epoxy groups, carboxylic acid groups, amino groups and / or hydroxyl groups capable of reacting with the other components of the compositions of the present invention, when the composition is cured by heating (although, alternatively, the curing agents may be free from such reactive functional groups).
    [0028] Epoxy-based prepolymers obtained by reacting one or more amine-terminated polymers, such as amine-terminated polyethers and silane-terminated amino polymers, with one or more epoxy resins, represent an especially preferred class of stiffening agents. Epoxy resins useful for this purpose may be chosen from the epoxy resins described here, with special preference being given to polyphenol diglycidyl ethers, such as bisphenol A and bisphenol F (for example, having epoxy equivalent weights of about 150 to about 1000). Mixtures of solid and liquid epoxy resins can be used appropriately.
    [0029] The preparation of such amine-terminated polyether epoxy prepolymers is well known in the art and is described, for example, in U.S. Patent Nos. 5,084,532 and 6,015,865, each of which is incorporated herein as reference in its integrity. Generally speaking, it will often be desirable to adjust the relationship between the amine-terminated polyester and the epoxy resin that is reacted in such a way that there is an excess of epoxy groups over the amine groups, so that the latter functional groups are completely reacted (ie, the epoxy-based prepolymer essentially contains no free amine groups. Mixtures of di- and trifunctional amine-terminated polyethers may be used.
    [0030] Polyethers with an amine termination containing both oxyethylene and oxypropylene repeating units (eg ethylene oxide and propylene oxide copolymers, with the copolymers having a capped or random block structure) and may also be used as the polyether with amine termination. Preferably, the amine-terminated polyether contains at least two amine groups per molecule. Preferably, the amine groups are primary amine groups.
    [0031] When reacting the epoxy resins with the polyether with an amine termination, an excess of epoxy groups in relation to the amino groups is preferably used, so that the latter react completely with the epoxide groups. Typically, there is a 1.5 to 10-fold excess, for example, a 3.5-fold excess of epoxy groups over the active hydrogen equivalents (AHEW) of the amine-terminated polyether. In preparing the composition according to the present invention, the epoxy-based prepolymer component is preferably initially prepared in a first stage. For this purpose, epoxy resins are preferably reacted with the amine-terminated polyester in the desired proportion. The reaction is preferably carried out at a high temperature, preferably 90 ° to 130 ° C, for example, at approximately 120 ° C, for a period, for example, of 3 hours.
    Other suitable stiffening agents include amorphous polysulfones, i.e., those polymers that contain predominantly ether and sulfone groups interdispersed between arylene residues. Such polysulfones, sometimes called polyethersulfones, may be prepared by the processes taught in US patents number 4,175,175, and especially, for example, 3,647,751. Polysulfones containing ether and alkylene groups, in addition to the sulfone groups are predominantly amorphous, and are suitable candidates for the practice of the invention in reference. Such polysulfones (polyethersulfones) have glass transition temperatures Tg greater than, 150 ° C, preferably greater than 175 ° C, and more preferably, more than 190 ° C. The Tg of an amine-terminated polyethersulfone KM 180 (manufactured by Cytec Industries, Inc., Woodland Park NJ) is approximately 200 ° C.
    [0033] In the preparation of the pre-reacted resin based on epoxy, for example, the following compounds can be used: polyoxyethylene linear ethers with amine termination; polyoxypropylene linear ethers with amine termination; and trifunctional compounds; polymers capped with aminosilane; amine-terminated polyethersulfones; and amine-terminated polysulfones. In the preferred embodiment, the amine-terminated polyethersulfone can be KM 170 and / or KM 180 (available from Cytec Industries, Inc.).
    [0034] In addition to the reacted compounds previously derived from the reaction of polymers terminated in amine or polymers terminated in aminosilane with the aforementioned epoxy resins, other stiffeners or impact modifiers known in the epoxy adhesive technique may be used. Generally speaking, such stiffeners and impact modifiers are characterized by glass transition temperatures ranging from -30 ° C to 300 ° C. Examples of such stiffeners and impact modifiers include, but are not limited to: reaction products of epoxy reactive butadiene copolymers (especially, butadiene epoxy reactive copolymers with relatively polar comonomers, such as methacrylonitrile, methacrylic acid, or alkyl acrylates , for example, carboxyl-terminated butadiene-nitrile rubbers Other examples include polyimides, such as Matrimid 9725 supplied by Huntsman, polyetherimides, such as Ultem supplied by GE, and others.
    [0035] Mixtures of different stiffening agents / auxiliary impact modifiers may be used. The amount of stiffening agent / auxiliary impact modifier in the curable compositions of the current invention may vary substantially, more typically, from about 0.1 to about 20% by weight, for example, from about 5 to about 15 % by weight. In one embodiment, the stiffening agent is considered to be present at about 10% to about 15% by weight of the total.
    [0036] In another embodiment, the thermosetting adhesive compositions shown here include a second stiffening agent chosen from acrylonitrile-butadiene copolymer with carboxyl termination, polyamides, polyimides and starch-amides. The carboxyl-terminated acrylonitrile-butadiene copolymer can include, for example, NIPOL 1472, while the polyamide can include, for example, nylon. Suitable polyimides are known to those of ordinary skill in the art and include, for example, those described in detail in U.S. Patent No. 5,605,745. Especially preferred are those polyimides which, because of the asymmetry of the dianhydride or diamine, especially the latter, have a lower degree of crystallinity or are completely amorphous. BTDA and AATI based polyimides are preferred. Polyimides are commercially available under the trademark MATRIMID® 5218 from Ciba-Geigy Corporation, and have an inherent viscosity of> 0.62 dl / g when measured at a concentration of 0.5% by weight in 25 ° N-methylpyrrolidone Ç. The molecular weight of these most preferred polyimides is greater than 20,000 Daltons, preferably greater than 50,000 Daltons, and more preferably, in the range of about 100,000 Daltons.
    [0037] The cured composition presented by the current invention is capable of exhibiting a high resistance to removal and shear in the temperature range of -55 ° C to + 180 ° C. In the cured state, these adhesives have a performance that is necessary for many end-use applications, especially in the manufacture of high-end aircraft and automobile structures. The stiffness of the resin matrix can be adjusted, for example, the variable functionality of epoxy resins (di- or tri- or tetrafunctional) leading to changes in the crosslink density. The stiffness and shear properties of the cured adhesive can be greatly improved by using a pre-reacted epoxy based resin of this invention, and other stiffeners in combination with nano-particles with core-carcass.
    Curing agents [0038] The term curing agent means a reactive component that is able to react with the functional epoxy group or polymerize the functional epoxy group. Since the compositions of the present invention are preferably compositions of a single part or a single component, and must be cured at an elevated temperature, they also contain one or more curing agents (hardeners) that are capable of carrying out crosslinking or cure of certain of the adhesive components, when the adhesive is heated to a temperature well in excess of the ambient temperature. That is, the hardener is activated by heating. The hardener can function in a catalytic way or, in some embodiments of the invention, participate directly in the curing process, by reacting with one or more of the adhesive components.
    [0039] May be used as thermally activable or latent hardeners for the adhesive compositions of the current invention, for example, guanidines, substituted guanidines, substituted ureas, melamine resins, guanamine derivatives, block amines, aromatic amines and / or mixtures of themselves. The hardeners can be involved stoichiometrically in the hardening reaction; however, they may also be active catalytically. Examples of substituted guanidines are methylguanidine, dimethylisobiguanidine, tetramethylisobiguanidine, hexamethylisobiguanidine, heptamethylisobiguanidine and, more especially, cyanoguanidine (diciandiamide). Representative of suitable guanamine derivatives that could be mentioned are alkylated benzoguanamine resins, benzoguanamine resins or methoxymethylethoxymethylbenzoguanamine. For single-component, thermosetting adhesives, the selection criterion, of course, is that of the low solubility of those substances at room temperature in the resin system, so that finely ground, solid hardeners are preferred; diciandiamide is especially suitable. Therefore, good storage stability of the composition is ensured. The amount of curing agent used will depend on several factors, including whether the curing agent acts as a catalyst or whether it participates directly in the crosslinking of the composition, the concentration of epoxy groups and other reactive groups in the composition, the desired curing rate , and so on. Typically, the composition contains about 0.5 to about 1 equivalent of curing agent per equivalent of epoxy molecule.
    [0040] Generally, such curing agents have relatively low molecular weights and functionalities that are phenolic hydroxyl, amine, amide, or anhydride. The preferred curing agents are the monomeric polyarylenes and amino functional oligomers, where among the arylene groups there are covalent bridges, as in the diaminodiphenyls, or connecting groups chosen from the group consisting of alkylene of 1-8 carbon atoms, ether, sulfone, ketones, carbonate, carboxylate, carboxamide and the like.
    [0041] Aminofunctional polyarylenes where the linking groups are alkylene, ether, sulfone and ketone are especially preferred. Such polyarylenes and synthetic methods for their preparation can be found in US patents number 4,175,175 and 4,656,208, which are incorporated herein by reference. The molecular weights of the preferred curing agents are less than about 800, preferably less than about 600, and more preferably, less than about 450. They are especially preferred as 3.3 'curing agents. -diaminodiphenylsulfone and 4,4'-diaminodiphenylsulfone, especially the latter. Mixtures of these curing agents may also be used. The stoichiometry of the amino-hydrogen / epoxy group is preferably adjusted to a range between 0.5 and 1.1, more preferably between 0.7 and 1.0, and more preferably, about 0.8 to 1.0.
    [0042] In one embodiment, the amine curing agent is a mixture of dicyandiamide (DICY) and bisurea and the composition is cured at 120 ° C. In another embodiment, the amine curing agent is a diaminodiphenylsulfone (DDS) and the curing temperature is 180 ° C. In certain embodiments, the curing agent is a combination of DICY and DDS.
    Other additives [0043] The compositions of the invention may also contain known fillers, such as the various ground or precipitated limestones, quartz powders, alumina, metallic aluminum powder, aluminum oxide, zinc oxide, calcium oxide, silver flakes , dolomite, graphite, granite, carbon fibers, glass fibers, textile fibers, polymeric fibers, titanium dioxide, fused silica, nano grade and hydrophobic silica (eg TS720), sand, carbon black, oxide calcium, calcium and magnesium carbonate, barite and, especially, silicate-like fillers of the type of aluminum and magnesium silicate and calcium, for example, volastonite and chlorite. Typically, compositions of the present invention may contain about 0.5 to about 40% by weight of fillers.
    [0044] In another embodiment, the composition additionally contains one or more laminar fillers, such as mica, talc or clay (for example, kaolin). Adhesive compositions according to the current invention may also contain other common auxiliaries and additives, such as plasticizers, reactive and / or non-reactive diluents, flow aids, coupling agents (for example, silanes), adhesion promoters, humidification, binders, flame retardants, rheology control agents and / or thixotropes (for example, smoked silica, mixed mineral thixotropes) inhibitors of aging and / or corrosion, stabilizers and / or coloring pigments. Depending on the requirements made with regard to the application of adhesive, related to its processing properties, its flexibility, the required stiffening action and the adhesive bonding to the substrates, the relative proportions of the individual components may vary within comparatively wide limits.
    [0045] For some end uses, it may be desirable to include dyes, pigments, stabilizers, thixotropic agents, and the like. These and other additives may be included in the adhesive thermosetting compositions described here, and as needed, at levels commonly practiced in the compounding technique. During curing, the adhesive thermosetting compositions, including any such additives, will form a substantially unique, rigid, continuous phase.
    Films [0046] The compositions of the invention presented here can also be used as adhesive films suitable for bonding two or more substrates chosen from structures of compounds, metals, or honeycombs together. In one embodiment, the thermosetting composition is an adhesive film having a weight of 0.02 to 0.15 psf. Such films may also include a vehicle, such as a woven or sewn blanket, or a random blanket, derived from glass, polyester, nylon, or other suitable polymeric materials. Such vehicles are useful for controlling the thickness at the joining line. The compositions of this invention can also be coated as unsupported films. Unsupported films are generally designed for crosslinking on the honeycomb or a perforated metal or composite sheet used in acoustic applications for aircraft nacelles. Methods [0047] The components of the resin system of the current invention are mixed according to conventional methods known to those trained in the epoxy resin technique. The hardened epoxy resin systems of the present invention can be used as film adhesives, or as matrix resins for the preparation of previously reinforced impregnated resins, for which methods are known to those skilled in the art of compounds.
    [0048] Therefore, in one aspect, the invention presents methods for the production of thermosetting adhesive films having improved hot / wet properties at elevated temperatures, through the reaction of a mixture containing an epoxy resin containing nano-particles with core- carcass with at least one amine-terminated polysulfone or polyethersulfone and sufficient time to form a previous reaction, the addition of at least one other epoxy resin and at least one amine curing agent for the previous reaction, and coating the resulting mixture over a removable paper at a temperature and enough weight to form a film.
    [0049] In one embodiment, the reaction step is performed at 250 - 300 ° F (121 to 149 ° C) for a period of half to two hours. In a specific embodiment, the reaction step is performed at 300 ° F (149 ° C) for one hour. In certain embodiments, the steps can be performed under vacuum.
    The mixing and addition steps can be carried out for a period between 15 and 60 minutes.
    [0050] In one embodiment, the coating step can be performed at 100 - 200 ° F (38 to 93 ° C) and coated with a film weighing 0.02 - 0.15 psf. In a specific embodiment, the coating step is performed at a temperature of 150 ° F (66 ° C) and a film weight of 0.06 psf.
    [0051] In some embodiments, the reaction mixture also includes a bisphenol and a catalyst for the bisphenol-epoxy reaction. At least one other epoxy resin and / or organic filler can be included.
    [0052] The compositions of the invention are suitable for joining together parts made of different materials (metallic or non-metallic), including, for example, wood, metal, coated or pre-treated metal, plastic, charged plastic, thermosetting, such as a sheet and fiberglass molding compound and the like, and honeycomb structures. The substrates to be joined using the adhesive may be the same or different from each other. The compositions of the invention can be applied to the surface of a substrate by any technique known in the art. Generally, the adhesive is applied to one or both of the substrates to be joined. The substrates are contacted in such a way that the adhesive is located between the substrates to be joined. Thereafter, the adhesive composition is subjected to pressure and heating to a temperature and for a time during which the thermosetting or latent curing agent begins to cure the composition containing epoxy resin.
    [0053] Therefore, in another aspect, the invention features processes for bonding a first article and a second article, providing a thermosetting adhesive composition or adhesive film, as described here, as a point of contact between a surface of the first article and a surface of the second article, and the curing of the joined articles at a temperature, pressure, and sufficient time to allow the thermosetting adhesive to fully cure, thereby bonding the first and second articles.
    [0054] In one embodiment, the first and second articles can be metallic, non-metallic, monolithic, or sandwich structures, and are chosen from structures of compounds, metals and honeycombs. Therefore, the joined articles can be of the type compound / compound, metal / metal, compound / metal, honeycomb / metal, honeycomb / compound, and honeycomb / honeycomb. Example metallic honeycomb structures include those made of titanium or aluminum. Example non-metallic honeycomb structures include polyamide (Nomax / Kevlar), gloss phenolic, and polyimide.
    [0055] The curing step can be performed at a temperature of 325 - 400 ° F (163 to 204 ° C), a time of 60 to 120 minutes, and a pressure of 25 -100 psi (172 to 689 kPa). In a specific embodiment, the curing step is performed at a temperature of 350 ° F (177 ° C) and 40 psi (276 kPa) for 90 minutes.
    Other achievements [0056] 1. A thermosetting adhesive composition consisting of: a) a pre-reacted composition formed by the reaction of: i) an epoxy resin containing nanoparticles with core-carcass; ii) at least one stiffening agent chosen from: an amine-terminated polyethersulfone, and an amine-terminated polysulfone; and iii) at least one multifunctional epoxy resin; and b) at least one amine curing agent, to allow total curing of said adhesive composition at temperatures up to 1400 ° F (204 ° C), where said adhesive composition is characterized by high glass transition temperature, rigidity against fracture increased, and increased shear properties at temperatures up to 350 ° F (177 ° C).
    [0057] 2. A thermosetting adhesive composition according to embodiment 1, where the pre-reacted composition further consists of: iv) a bisphenol e; v) and a catalyst for the bisphenol-epoxy reaction. 3. A thermosetting adhesive composition according to embodiment 2, where bisphenol is chosen from bisphenol A, Bis F, Bis S, and fluorene.
    [0058] 4. A thermosetting adhesive composition, according to either of the 2 or 3 embodiments, where the catalyst is triphenyl phosphine.
    [0059] 5. A thermosetting adhesive composition, according to any of embodiments 1 to 4, where the epoxy resin containing nanoparticles with core-carcass is a diglycidyl ether and bisphenol A.
    [0060] 6. A thermosetting adhesive composition, according to any of embodiments 1 to 5, where the size and the nanocapsules of the core-shell are 10 to 100 nm.
    [0061] 7. A thermosetting adhesive composition according to any of the preceding claims, where the core-shell nanoparticle is composed of a butadiene core and a polymethylmethacrylate (PMMA) shell.
    [0062] 8. A thermosetting adhesive composition, according to any of the previous embodiments, where the nanoparticle with core-shell is composed of a butadiene-styrene copolymer core and a PMMA shell.
    [0063] 9. A thermosetting adhesive composition, according to any of the previous embodiments, where the particle with core-carcass consists of a polysiloxane core and a PMMA carcass.
    [0064] 10. A thermosetting adhesive composition according to any of the preceding claims, where the epoxy resin containing the core-carcass nanoparticles is KANE ACE® MX 120.
    [0065] 11. A thermosetting adhesive composition, according to any of the previous embodiments, where the stiffening agent is a polyethersulfone with molecular weight (Mn) from 8,000 to 14,000.
    [0066] 12. A thermosetting adhesive composition, according to any of the previous embodiments, additionally consisting of a second stiffening agent chosen from acrylonitrile-butadiene copolymer terminated in carboxyl, polyamides, polyimides, and an amide-amide.
    [0067] 13. A thermosetting adhesive composition, according to embodiment 12, where the acrylonitrile-butadiene copolymer with carboxyl termination is NIPOL® 1472.
    [0068] 14. A thermosetting adhesive composition, according to embodiment 12, where the polyamide is nylon.
    [0069] 15. A thermosetting adhesive composition, according to embodiment 12, where the polyimide is MATRIMID® 9725.
    [0070] 16. A thermosetting adhesive composition, according to any of the previous embodiments, where the multifunctional epoxy resin is chosen from tetra glycidyl methylene ether dianiline, and a novolac epoxy.
    [0071] 17. A thermosetting adhesive composition according to embodiment 16, where the tetraglycidyl methyl ether dianiline is MY 9655, and where the novolac epoxy is Huntsman Tactic XP® 71756.
    [0072] 18. A thermosetting adhesive composition, according to any of the previous embodiments, where the amine curing agent is chosen from diphenyl sulfone diamine (DDS), diciandiamide (DICY), blocked bisures, amines, and mixtures thereof .
    [0073] 19. A thermosetting adhesive composition, according to embodiment 18, where the amine curing agent is DICY / bisureia, and where the curing temperature is 250 ° F (121 ° C).
    [0074] 20. A thermosetting adhesive composition, according to embodiment 18, where the amine curing agent is DDS or a combination of DICY and DDS, and where the curing temperature is 350 ° F (177 ° C) .
    [0075] 21. A thermosetting adhesive composition, according to any of the previous embodiments, further consisting of one or more inorganic fillers chosen from: aluminum oxide, metallic aluminum powder, nano-hydrophobic grade silica, and calcium oxide or silver flakes.
    [0076] 22. An adhesive thermofixation composition, according to any of the previous embodiments, further comprising one or more flow control agents chosen from: amorphous and hydrophobic silica, and hydrophilic amorphous silica.
    [0077] 23. A thermosetting adhesive composition, according to embodiment 22, where the amorphous and hydrophobic silica is CAB-O-SIL® TS 720.
    [0078] 24. An adhesive thermofixation composition, according to any of the previous realizations, being still constituted by one or more pigments chosen from: TiO2 and ZnO.
    [0079] 25. A thermosetting adhesive composition, according to any of the previous embodiments, where the percentage by weight of the epoxy resin containing core-carcass nanoparticles is 40% to 50% of the total.
    [0080] 26. A thermosetting adhesive composition, according to any of the previous embodiments, where the percentage by weight of the stiffening agent is 1% to 30% of the total.
    [0081] 27. A thermosetting adhesive composition, according to any of the previous embodiments, where the percentage by weight of the multifunctional epoxy resin is 5% to 25% of the total.
    [0082] 28. A thermosetting adhesive film, suitable for bonding a substrate chosen from one or more of: a composite material, a metal, a honeycomb structure, said film being constituted by an adhesive thermosetting composition , according to any of embodiments 1 to 27, where the weight of the film is 0.02 to 0.15 psf.
    [0083] 29. A thermosetting adhesive film, according to embodiment 28, which is still constituted by a polymeric vehicle chosen from one or more of: glass, polyester, and nylon.
    [0084] 30. A thermosetting adhesive film, according to embodiment 28 or embodiment 29, where the film is produced using a hot / melting or solvated process.
    [0085] 31. A method for producing a thermosetting adhesive film having better hot / wet properties at high temperature, the method consisting of: a) reaction of a mixture consisting of an epoxy resin containing nanoparticles with core-carcass , and at least one polysulfone ending with amine or polyethersulfone at a temperature and in a time sufficient to form a pre-reaction; b) adding at least one other epoxy resin and at least one amine curing agent in the previous reaction; c) coating the mixture of step (b) on a removable paper, at a temperature and of sufficient weight to form a film, and thereby producing a thermosetting adhesive film having improved hot / wet properties at high temperatures. 32. The method of claim 31, wherein the reaction step is performed at 250 - 300 ° F (121 to 149 ° C) for a period of 0.5 to 2 hours.
    [0086] 33. A method, according to embodiment 32, where the temperature is 300 ° F (149 ° C) and the time is 1 hour.
    [0087] 34. A method according to any of claims 31 to 33, wherein steps (b) and (c) are performed under vacuum, and where at least one other epoxy resin and an amine curing agent are mixed with the previous reaction over a period of 15 to 60 minutes.
    [0088] 35. A method according to any of claims 31 to 34, wherein step (c) is performed between 100 and 200 ° F (38 and 93 ° C) and the coating is done with a weight of 0, 02 to 0.15 psf.
    [0089] 36. A method, according to embodiment 35, where the temperature is 150 ° F (66 ° C) and the weight of the film is 0.06 psf.
    [0090] 37. A method according to any of claims 31 to 36, wherein the reaction mixture further comprises a bisphenol, a catalyst for the reaction between the bisphenol and the epoxy, and at least one other epoxy resin.
    [0091] 38. A method, according to any of the embodiments 31 to 37, characterized by the fact that step (b) is still constituted by adding at least one inorganic charge to the reaction mixture.
    [0092] 39. A process for bonding a first article with a second article, the process consisting of: a) the production of a thermosetting adhesive composition, according to any of embodiments 1 to 27, or an adhesive film thermosetting, according to any of the embodiments 28 to 30, or a thermosetting adhesive film prepared according to any of the embodiments 31 to 38, as a contact point between the surface of the first and second articles; and b) curing of the thermosetting adhesive composition or adhesive thermosetting film, when the surfaces of the first and second articles are in contact, at a temperature, pressure and time sufficient to allow total curing, thus connecting the first and the second articles.
    [0093] 40. Process, according to realization 39, where the first and second articles (first article / second article) are chosen from compound / compound; metal / metal; compound / metal; metal / compound; honeycomb / compound; honeycomb / metal; and honeycomb / honeycomb.
    [0094] 41. Process, according to realization 40, where the metal is chosen from titanium and / or aluminum.
    [0095] 42. Process, according to embodiment 40, where the compound is chosen from polyamide and / or shiny phenolic polyimide.
    [0096] 43. Process, according to any of the realizations 39 to 42, where step (b) is performed at a temperature of 325 to 400 ° F (163 to 204 ° C), a time of 60 to 120 minutes, and a pressure of 25 to 100 psi (172 to 689 kPa).
    [0097] 44. Process according to claim 43, where the temperature is 350 ° F (177 ° C), the pressure is 40 psi (276 kPa), and the time is 90 minutes.
    Examples [0098] The following examples are presented to assist a person skilled in the art to further understand certain achievements of the current invention. These examples are for illustrative purposes only, and should not be considered as limiting the scope of the various achievements of the current invention.
    Example 1 [0099] A mixture containing 80 g of KANACE MX 120® (supplied by Kaneka - contains 25 wt% rubber with nano-carcass core in EPON 828 epoxy resin), 20 g of tetra bromo bisphenol A (TBBA), 20 g of Paraloid 2691 (Rohm & Hass) and 0.1 g of triphenyl phosphine is reacted at 300 ° F (149 ° C) for 1 hour. The above pre-reacted mixture is cooled to 160 ° F (71 ° C) and 35 g of tetra glycidyl methylene ether dianiline (MY 9655 supplied by Huntsman) is added and mixed under vacuum for 15 minutes. To this mixture, 20 g of diamino diphenyl sulfone DCY 2.5 curing agent and 2 g of amorphous silica flow control agent are added. The mixture is stirred under vacuum for 15 minutes.
    [00100] The above mixture is coated on 150 ° F (66 ° C) removable paper and a film weight of 0.06 psf. The film is evaluated for mechanical performance, by bonding and testing shear, removal and glass transition temperature. The film is cured at 350 ° F (177 ° C) for 90 minutes under a pressure of 40 psi (276 kPa).
    Example 2 [00101] The same procedure as example 1 is followed, except that the KANACE MX 120® is replaced by 60 g of EPON 828® and 25 g of Paraloid 2691®. This pre-reacted mixture is then used with the additional epoxy resin and curing agents, as described in example 1. The mixture is then coated like a film and is tested for mechanical performance, as indicated in example 1.
    [00102] The test results showing the unexpected performance improvement seen with the use of KANACE MX® resin are shown in Table 1.
    Table 1 Example 3 [00103] A mixture of 80 g of KANACE MX 120® and polymer KM 10 (polyethersulfone) is reacted at 250 ° F (121 ° C) for 1 hour. 50 g of novolac epoxy followed by curing agents, as per example 1, and 15 g of KM 180 polymer were added to this previous reaction. The film is coated and tested for mechanical properties on aluminum substrates, as indicated in the example 1. The comparative formulation without KANACE MX 120® resin is shown in example 4.
    Example 4 [00104] The same procedure as example 3 is followed, except that the previous reaction consists of 60 g of EPON 828®, 20 g of Paraloid 2691® (to replace KANACE MX 120® resin) and 10 g of KM 180 The rest of the formulation is the same as in example 3. The film is coated at 0.05 psf and is tested for mechanical properties. The comparative test data between the resin system containing KANACE MX 120® and its replacement (EPON 828® + Paraloid 2691 ®) is shown in table 2.
    Table 2 [00105] As can be seen from the data in table 2, the core-carcass rubber particle containing the formulation (example 3) shows not only greater removal, but also unexpected properties of higher shear strength at elevated temperatures .
    Example 5 [00106] The same procedure as example 3 is followed. The 0.05 psf coated adhesive film with a random blanket vehicle is also used to bond the composite carbon / CYCOM 977-2 substrates. For shear studies in a wide area of simultaneous bonding, a compound film with 8 - 10 layers (adhered) is previously cured at 350 ° F (177 ° C) and the other part with 8 - 10 layers is cured at the same time. , with the adhesive film as shown below: [00107] For secondary adhesion studies, both layers are pre-cured. For simultaneous adhesion studies, the cure cycle consists of 2 hours at 350 ° F (177 ° C) and 85 psi (586 kPa). For secondary adhesion studies, the cure cycle is 90 minutes at 350 ° F (177 ° C) with a pressure of 40 psi (276 kPa). After adhesion, specimens are then tested by ASTM D 3165 before and after 2,000 hours immersed in water at 160 ° F (71 ° C). The results of the shear test are shown in table 3.
    Table 3 [00108] The data in Table 3 shows that the compositions in Example 5 are characterized by high shear strength in both dry and wet conditions, indicating excellent resistance to moisture. The conservation of properties after exposure to humidity is greater than 90% in specimens attached secondarily and greater than 85% in specimens linked simultaneously. These data indicate that the compositions of this invention are unaffected by moisture and retain most of their strength after prolonged exposures under conditions of soaking with water.
    [00109] Reference was made to several patents and / or scientific literature throughout this application. The presentations of these publications and their full content are incorporated herein as references, as if they were written, provided that such presentations are not inconsistent with the invention and for all jurisdictions in which such incorporation is permitted as a reference. In view of the above description and examples, a person of ordinary skill in the art will be able to practice the invention as it is claimed without the need for unnecessary prior experience. [00110] Although the description mentioned above has shown, described, and emphasized the fundamental new characteristics of the present teachings, it will be understood that various omissions, substitutions, and changes in the form of the compositions and processes could be made by those with training in the art , as illustrated and described, without departing from the scope of current teachings. Consequently, the scope of current teachings should not be limited to the description mentioned above, but should be defined by the appended claims.
    权利要求:
    Claims (12)
    [1]
    1. Thermosetting adhesive composition, characterized by the fact that it comprises: a) a pre-reacted formed through the reaction of a mixture comprising: i) an epoxy resin containing nano-sized rubber core-carcass particles, having a size of particle within the range of 10 to 100 nm; ii) an amine-terminated polyether sulfone; iii) at least one multifunctional epoxy resin; iv) a bisphenol; and v) a bisphenol-epoxy reaction catalyst; and b) at least one amine curing agent to allow total curing of said adhesive composition at temperatures up to 400 ° F (204 ° C), wherein, in curing, said adhesive composition has a high glass transition temperature, increased fracture stiffness, and increased shear properties at temperatures up to 350 ° F (177 ° C).
    [2]
    2. Thermosetting adhesive composition according to claim 1, characterized by the fact that the amine-terminated sulfone has a molecular weight (Mn) of 8,000 to 14,000.
    [3]
    Adhesive thermosetting composition according to claim 1, characterized in that it further comprises a second stiffening agent chosen from a group consisting of acrylonitrile-butadiene copolymer with carboxyl termination, polyamides, polyimides, and an amide-amide.
    [4]
    4. Thermosetting adhesive composition according to claim 1, characterized in that the amine curing agent is a mixture of diciandiamide (DICY) and bisurea and in which the curing temperature is 250 ° F (121 ° C).
    [5]
    5. Thermosetting adhesive composition according to claim 1, characterized in that the amine curing agent is diaminodiphenylsulfone (DDS) or a mixture of diciandiamide (DICY) and diaminodiphenylsulfone (DDS), and wherein the curing temperature is 350 ° F (177 ° C).
    [6]
    6. Thermosetting adhesive composition according to claim 1, characterized by the fact that it also comprises one or more of: i) an inorganic load chosen from one or more of: aluminum oxide, metallic aluminum powder, silica, calcium oxide or silver flakes; ii) a flow control agent, chosen from one or more of: hydrophobic amorphous silica, and hydrophilic amorphous silica; and iii) a pigment chosen from one or more of: TiO2 and ZnO.
    [7]
    7. Adhesive thermosetting film, characterized by the fact that it is formed from a thermosetting adhesive composition as defined in claim 1, where the weight of the film is 0.02 to 0.15 psf (9.76 x 103 to 7, 32 x 10-2 g / cm2).
    [8]
    8. Supportive thermosetting adhesive film comprising the thermosetting adhesive film as defined in claim 7, characterized in that it is formed on a polymeric carrier, chosen from one or more glass, polyester or nylon.
    [9]
    9. Method for the production of a thermosetting adhesive film, as defined in claim 1, the method being characterized by the fact that it comprises: a) reacting a mixture comprising (i) an epoxy renin containing rubber particles with a core-carcass dimension nano, having a particle size within the range of 10 to 100 nm; (ii) at least one amine-terminated polyether sulfone; (iii) at least one multifunctional epoxy resin; (iv) a bisphenol; (v) a bisphenol-epoxy reaction catalyst; at a temperature of 250 - 300 ° F (121 to 149 ° C) and in a time of 0.5 to 2 hours, sufficient to form a pre-reagent; b) adding at least one multifunctional epoxy resin, and at least one amine curing agent to the pre-reagent; and c) coat the mixture formed from step (b) on a removable paper at a temperature of 100 to 200 ° F (38 to 93 ° C) and with a weight of 0.02 to 0.15 psf (9.76 x 10-3 to 7.32 x 10-2 g / cm2), sufficient to form a film, thus producing a curable thermosetting adhesive film having improved hot and wet properties at high temperatures when curing.
    [10]
    10. Method according to claim 9, characterized in that step (b) further comprises the addition of at least one inorganic charge to the reaction mixture.
    [11]
    11. Process for joining a first substrate to a second substrate, characterized by the fact that it comprises: a) providing a thermosetting adhesive composition, as defined in claim 1, or the thermosetting adhesive film as defined in claim 7, as a contact between a surface of the first article and a surface of the second article; and b) cure the thermosetting adhesive composition or the thermosetting adhesive film during contact with the surfaces of the first and second articles, at a temperature of 325 to 400 ° F (163 to 204 ° C), a pressure of 25 to 100 psi (172 to 689 kPa) and a time of 60 to 120 minutes, sufficient to allow full curing, thus connecting the first and second substrates.
    [12]
    12. Process according to claim 11, characterized in that the first and the second article (first article / second article) are chosen from composite / composite; metal / metal; composite / metal; metal / composite; honeycomb / composite structure; honeycomb / metal structure; and honeycomb structure / honeycomb structure.
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    同族专利:
    公开号 | 公开日
    US20110048637A1|2011-03-03|
    JP2013503249A|2013-01-31|
    TW201124501A|2011-07-16|
    EP2473573B1|2018-06-13|
    MY156295A|2016-01-29|
    JP5527861B2|2014-06-25|
    CA2772333C|2017-01-17|
    EP2473573A1|2012-07-11|
    CA2772333A1|2011-03-03|
    US8518208B2|2013-08-27|
    CN102498184A|2012-06-13|
    TWI554585B|2016-10-21|
    AU2010286611A1|2012-03-01|
    AU2010286611B2|2013-07-11|
    CN102498184B|2014-09-10|
    WO2011025873A1|2011-03-03|
    BR112012003572A2|2016-03-08|
    KR20120104516A|2012-09-21|
    KR101684721B1|2016-12-20|
    ES2686497T3|2018-10-18|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-02-05| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-08-06| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-03-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-03-17| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/08/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US23856009P| true| 2009-08-31|2009-08-31|
    US61/238560|2009-08-31|
    PCT/US2010/046798|WO2011025873A1|2009-08-31|2010-08-26|High performance adhesive compositions|
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