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    • 专利摘要:
    STRUCTURAL ADHESIVE, AND LAMINATED STRUCTURE. A structural adhesive composition that is suitable for high-strength bonding of metals and aerospace structural materials In one embodiment, the structural adhesive composition is based on a two-part system that is curable at or below 200°F (93° Ç). The two-part system is composed of a resinous part (A) and a catalyst part (B), which can be stored separately at room temperature until ready for use. The resin part (A) includes at least two different multifunctional epoxy resins with different functionalities and selected from bifunctional, trifunctional and tetrafunctional epoxy resins, certain stiffening components and inorganic filler particles as a rheology/thixotropy modifying component. The stiffening components include shell-core rubber particles having different particle sizes and at least one of an elastomeric polymer and a polyethersulfone polymer. The catalyst part (B) includes one or more aliphatic or cyclic amine compounds as curing agents and inorganic filler as a rheology/thixotropy modifying component. The weight ratio of part (A) to part (B) is within the range of 3:2 to 10:2. In another modality, (...).
    公开号:BR112014010798B1
    申请号:R112014010798-0
    申请日:2012-10-19
    公开日:2021-05-04
    发明作者:Junjie Jeffrey Sang；Dalip Kumar Kohli；Kunal Gaurang Shah
    申请人:Cytec Technology Corp；
    IPC主号:
    专利说明:

    FUNDAMENTALS
    [0001] Structural adhesives are conventionally used for structural bonding in the manufacture of structural parts that demand stringent mechanical requirements. such as car body parts and aircraft structure. In general, heat-curable epoxy adhesives are used as structural adhesives. These heat-curable epoxy adhesives often require relatively high curing temperature, eg 120-180°C (248356°F). High temperature curing often requires larger autoclaves, longer production runtime and can cause exothermic concerns. On the other hand, there are conventional adhesives that are curable at a lower temperature, eg room temperature; however, they lack the rigidity and bond strength properties required for structural bonding in aerospace structural part manufacturing. Structural adhesives for aerospace application must be durable to withstand harsh environmental conditions.
    [0002] For structural gluing operations such as rapid assembly of aircraft parts, it is desirable to have an adhesive that allows flexibility in low temperature or room temperature cure, off-autoclave (OOA) processing, and to be able to form strong glue to both composite and metal surfaces with excellent long-term durability under aerospace environmental conditions. SUMMARY
    [0003] The present disclosure provides a structural adhesive composition that is suitable for high strength bonding of metals and aerospace structural materials. In one embodiment, the structural adhesive composition is based on a two-part system, which is curable at or below 200°F (93°C), including room temperature (20-25°C or 68-77°F) . The two-part system is composed of a resinous part (A) and a catalyst part (B), which can be stored separately at room temperature until ready for use. Mixing of part (A) and part (B) is required before application. The resin part (A) includes at least two different multifunctional epoxy resins with different functionalities selected from bifunctional, trifunctional and tetrafunctional epoxy resins, certain stiffening components and inorganic filler particles as a rheology/thixotropy modifying component. The stiffening components include shell-core rubber particles having different particle sizes and at least one of an elastomeric polymer and a polyethersulfone polymer. The catalyst part (B) includes one or more aliphatic or cyclic amine compounds as curing agents and inorganic filler particles as a rheology/thixotropy modifying component. The weight ratio of part (A) to part (B) is within the range of 3:2 to 10:2.
    [0004] In another embodiment, the structural adhesive composition is based on a one-part system that includes the components of the resinous part (A) in the two-part system and a latent amine curing agent. The one-part system may further include an imidazole and/or an aliphatic amine to control the cure kinetics so that further reductions in the cure temperature are possible. The one-piece system is curable within the temperature range of 140-300°F (60-150°C). DETAILED DESCRIPTION
    [0005] For the two part system, a curable paste adhesive is formed by mixing the resinous part (A) with the catalyst part (B) before applying the adhesive to the surface. The mixed paste adhesive can be cured at a low temperature of less than or equal to 93°C (200°F), including room temperature (20-25°C or 68-77°F). The low curing temperature allows adhesive bonding of substrates without the use of an autoclave, ie, out of autoclave (OOA). As such, adhesive sizing and curing can be accomplished by applying low contact pressure of about 1-3 psi (pounds per square inch) (0.007-0.02 MPa) to the bonded substrates with or without external heating. After curing within the range of 65°C-93°C (150°F-200°F), the paste adhesive generates a structural adhesive with a glass transition temperature (Tg) greater than 95°C (203°F). ). In certain embodiments, after curing at 93°C (200°F), the cured adhesive has a Tg greater than 120°C (248°F), eg, 120°C-130°C (248°F-266° F).
    [0006] The resin part (A) includes at least two different multifunctional epoxy resins with different functionalities and selected from bifunctional, trifunctional and tetrafunctional epoxy resins, certain stiffening components and inorganic filler particles as a rheology/thixotropy modifying component. The stiffening components include a first type of shell-core rubber particles (CSR) having particle sizes less than 100 nm, and a second type of shell-core rubber particles having particle sizes greater than 100 nm . The hardening components further include at least one of an elastomeric polymer with a functional group capable of reacting with the multifunctional epoxy resins during curing and a polyethersulfone (PES) polymer. In one embodiment, the elastomeric polymer and polyethersulfone are present in the resinous part (A). The catalyst part (B) includes one or more amine curing agents to react with the epoxy resins and inorganic filler particles as a rheology/thixotropy modifier component. Amine curing agents are aliphatic or cyclic amine compounds. The weight ratio of the resin part (A) to the catalyst part (B) is within the range of 3:2 to 10:2. In a preferred embodiment, the weight ratio of the resin part (A) to the catalyst part (B) is 2:1.
    [0007] The resinous part (A) has a storage viscosity in the range of 500-1000 Poise (50-100 Pa*s) at room temperature (20-25°C or 68-77°F) and a density (weight specific), in the range of 1.0-1.2 g/cm3 and the catalyst part (B) has a storage viscosity in the range of 150-300 Poise (15-30 Pa*s) at room temperature 20-25 °C (68-77°F) and a density in the range of 0.9-1.1 g/cm3. Both parts have a long shelf life and can be stored in separate containers at room temperature for up to one year. When parts (A) and (B) are mixed, the resulting product is a paste adhesive which is curable at or below 200°F (93°C) and has a viscosity of 200-600 Poise (20-60 Pa *s), preferably 300-500 Poise (30-50 Pa*s), at room temperature 2025°C (68-77°F), thus allowing the adhesive to be easily applied to a surface by conventional methods such as bead application or movie. Hereinafter, the terms “ambient temperature” and “ambient temperature” will be used interchangeably to refer to the temperature range of 20-25°C (68-77°F).
    [0008] For the one-part system, the resulting adhesive after mixing its components is a curable paste adhesive that is ready for application and is curable within the temperature range of 140-300°F (60150°C) , or 160-200°F (71-93°C), however, it does not have a long service life at room temperature, typically around 15 days. As such, freezing would be necessary to extend its shelf life. The one-part adhesive has a viscosity of 400-1000 Poise (40-100 Pa*s), preferably 300-500 Poise (30-50 Pa*s), at room temperature. Epoxy resins
    [0009] The multifunctional epoxy resins to be used in the resinous part (A) are polyepoxides that contain an average of two to four epoxy groups (oxirane rings) per molecule with the epoxy groups being the end groups. A bifunctional epoxy resin is an epoxy resin that contains an average of two epoxy groups per molecule, a trifunctional epoxy resin is an epoxy resin that contains an average of three epoxy groups per molecule, and a tetrafunctional epoxy resin contains an average of four epoxy groups per molecule. Bifunctional epoxy resins can have an average epoxy equivalent weight (EEW) in the range of 150-700 g/eq. An epoxy equivalent weight is the molecular weight of the epoxy molecule divided by the number of epoxy groups on the molecule. Thus, for example, a bifunctional epoxy having a molecular weight of 400 would have an epoxy equivalent weight of 200. Trifunctional epoxy resins can have an average EEW in the range of 90-180 g/eq. Tetrafunctional epoxy resins can have an average EEW in the range of 100-200 g/eq.
    [00010] In a preferred embodiment, at least one of the multifunctional epoxy resins is a cycloaliphatic epoxy. In some embodiments, a blend of all three types of multifunctional epoxy resins (bifunctional, trifunctional and tetrafunctional epoxy resins) are present in the resin portion (A) to control the crosslink density of the cured epoxy resin blend and to optimize the Tg and the stiffness of the final cured adhesive. In other embodiments, the resin blend includes a non-cycloaliphatic bifunctional epoxy, or a trifunctional epoxy or a tetrafunctional epoxy and a cycloaliphatic epoxy with more than one epoxy functionality (i.e., a cycloaliphatic multifunctional epoxy). Bifunctional resin makes up the majority of the resin blend (more than 50% by weight of the resin blend) in all cases. When all three multifunctional epoxy resins are used, the following proportions are preferred, based on the total weight of the resin mixture: more than 50% by weight bifunctional epoxy resin, less than 10% by weight tetrafunctional epoxy resin and epoxy resin trifunctional make up the balance.
    [00011] In general, multifunctional resins suitable for the resinous part (A) can be saturated, unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic polyepoxides. Examples of suitable polyepoxides include polyglycidyl ethers, which are prepared by reacting epichlorohydrin or epibromidrine with a polyphenol in the presence of alkalis. Suitable polyphenols, therefore, are, for example, resorcinol, polycatechol, hydroquinone, bisphenol A (bis(4-hydroxyphenyl)-2,2-propane), bisphenol F (bis(4-hydroxyphenyl)methane), bisphenol S, bis( 4-hydroxyphenyl)-1,1-isobutane, fluorene, 4,4'-dihydroxybenzophenone, bis(4-hydroxyphenyl)-1,1-ethane, bisphenol Z (4,4'-Cyclohexylidenebisphenol) and 1,5-hydroxynaphthalene. Also suitable are polyglycidyl ethers of polyalcohols, aminophenols or aromatic diamines.
    [00012] Other types of polyepoxides that can be used are glycidyl polyester resins prepared by the reaction of an epihalohydrin with an aromatic or aliphatic polycarboxylic acid. Another type of polyepoxy resin is a glycidyl amine that is prepared by reacting a polyamine with an epichlorohydrin. Other suitable multifunctional epoxy resins include novolac multifunctional epoxy resins with two to four epoxy groups. Epoxy novolac resins that are useful include epoxy cresol novolacs and epoxy phenol novolacs. Additional suitable multifunctional epoxy resins include aliphatic multifunctional epoxy such as polyglycidyl ether type epoxy and sorbitol glycidyl ether type.
    [00013] Multifunctional liquid epoxy resins or a combination of solid and liquid multifunctional epoxy resins can be used to form the resin mixture. Particularly suitable are liquid epoxy resins having relatively low molecular weight derived by the reaction of bisphenol A or bisphenol F and epichlorohydrin. Bisphenol-based epoxy resins that are liquid at room temperature generally have an epoxy equivalent weight of about 150 to about 350 g/eq. Epoxy resins that are solid at room temperature are obtainable from polyphenols and epichlorohydrin and have epoxy equivalent weights greater than 400 g/eq. Solid epoxy resins differ from liquid epoxy resins in that they are solid at room temperature and have a melting point of 45°C to 130°C.
    [00014] Examples of bifunctional epoxy resins include diglycidyl ethers of bisphenol A based materials (eg Epon™ 828 (liquid epoxy resin) from Hexion, DER 331, DER 661 (solid epoxy resin) supplied by Dow Chemical Co.,, Tactix 123 and Araldite® 184 supplied by Huntsman Advanced Materials).
    [00015] Examples of trifunctional epoxy resins include aminophenol triglycidyl ether, e.g. Araldite® MY 0510, MY 0500, MY 0600, MY 0610 supplied by Huntsman Advanced Materials.
    [00016] Examples of tetrafunctional epoxy resins include methylene dianiline tetraglycidyl ether (for example Araldite® MY 9655 supplied by Huntsman Advanced Materials), tetraglycidyl diaminodiphenyl methane (for example Araldite® MY-721, MY-720, 725, MY 9663 , 9634, 9655 from Huntsman Advanced Materials), EJ-190 from JSI Co., Ltd., and ERISYS GE-60 from CVC Chemical, Inc.
    [00017] Suitable cycloaliphatic epoxies include compounds containing at least one cycloaliphatic group and at least two oxirane rings per molecule. Specific examples include cycloaliphatic alcohol diepoxide, hydrogenated Bisphenol A (Epalloy™ 5000, 5001 supplied by CVC Thermoset Specialties) represented by the following structure:

    [00018] Other examples of cycloaliphatic epoxies include: EPONEX cycloaliphatic epoxy resins (eg EPONEX Resin 1510) supplied by Momentive Specialty Chemicals; Epotec® cycloaliphatic epoxy resins (eg YDH 184, YDH 3000) supplied by Aditya Birla Chemicals; ERL-4221 (3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate) from Dow Chemicals; and Araldite® CY 179 MA supplied by Huntsman Advanced Materials. hardening agents
    [00019] Two different types of shell-core rubber particles (CSR) are incorporated in the resinous part (A) to create a bimodal particle size distribution with different domains of hardening morphology. These CSR particles act as hardening agents that allow the adhesive to harden after curing. Smaller particles may have an average particle size of less than or equal to 100 nm, preferably 50-90 nm and larger particles may have an average size greater than 100 nm, preferably 150-300 nm. The weight ratio of smaller CSR particles to larger CSR particles can be in the range of 3:1 to 5:1. The CSR particles, in total, can be present in the resinous part (A) in an amount of 5% - 30% by weight, based on the total weight of the part (A). With different particle sizes, you can control the balance of key properties such as the shear strength, peel strength and fracture toughness of the resin.
    [00020] Shell-core rubber particles may have a soft core, composed of a polymeric material containing elastomeric or rubber properties (i.e., a glass transition temperature less than 0°C, for example, less than about -30°C.), surrounded by a hard shell, composed of a non-elastomeric polymeric material (ie, a thermoplastic or thermosetting/crosslinked polymer containing a glass transition temperature greater than ambient temperature, e.g., greater than about 50°C.). For example, the core can be composed of, for example, a homopolymer or copolymer of diene (for example, a homopolymer of butadiene or isoprene, a copolymer of butadiene or isoprene with one or more ethylenically unsaturated monomers such as vinyl aromatic monomers, ( meth)acrylonitrile, (meth)acrylate or the like), while the shell can be comprised of a polymer or copolymer of one or more monomers such as (meth)acrylates (eg methyl methacrylate), vinyl aromatic monomers (eg styrene ), vinyl cyanides (eg acrylonitrile), unsaturated acids and anhydrides (eg acrylic acid), (meth)acrylamides and the like having an appropriately high glass transition temperature. The polymer or copolymer used in the shell may have acidic groups that are ionically cross-linked through metal carboxylate formation (eg, forming salts of divalent metal cations). The shell polymer or copolymer could also be covalently cross-linked through the use of monomers containing two or more double bonds per molecule. Other elastomeric polymers may also be suitably used for the core, including polybutylacrylate or polysiloxane elastomer (for example, polydimethylsiloxane, particularly cross-linked polydimethylsiloxane). The particle can be comprised of more than two layers (for example, a central core of an elastomeric material can be surrounded by a second core of a different elastomeric material or the core can be surrounded by two shells of different composition or the particle can have the soft core/hard shell/soft shell/hard shell structure). Typically, the core comprises from about 50 to about 95 percent by weight of the particle while the shell comprises from about 5 to about 50 percent by weight of the particle.
    [00021] The shell-core rubber particles can be pre-dispersed in a liquid resin matrix system such as those available from Kaneka Texas Corporation under the Kane Ace MX brand names. It is preferred that the shell-core rubber particles are pre-dispersed in one of bifunctional, trifunctional and tetrafunctional epoxy resins to be used in the resinous part (A). As examples, suitable resin matrix systems containing CSR particles include MX 120 (liquid Bisphenol A epoxy with about 25 wt% CSR), MX 125 (liquid Bisphenol A epoxy with about 25 wt% CSR), MX 153 (liquid Bisphenol A epoxy with about 33% by weight CSR), MX 156 (liquid Bisphenol A epoxy with about 25% by weight CSR), MX 130 (liquid Bisphenol F epoxy with about 25% by weight CSR ), MX 136 (liquid Bisphenol F epoxy with about 25% by weight of CSR), MX 257 (liquid Bisphenol A epoxy with about 37% by weight of CSR), MX 416 and MX 451 (liquid multifunctional epoxy with about 25 wt% CSR), MX 215 (Novolac Epoxidized Phenol, with about 25 wt% CSR) and MX 551 (cycloaliphatic epoxy with about 25 wt% CSR).
    [00022] In addition to CSR particles, thermoplastic and/or elastomeric stiffening agents are added to the epoxy resin blend to further increase the stiffness of the finally cured adhesive. Particularly preferred are elastomeric polymers having functional groups capable of reacting with the multifunctional epoxy resins during curing and a polyether sulfone (PES) polymer having an average molecular weight in the range of 8,000-14,000.
    [00023] Elastomeric polymers with epoxy functional groups are particularly suitable. Specific examples include epoxy elastomer adduct formed by the reaction of epoxy resin with carboxyl terminated butyl nitrile elastomer or amine terminated butadiene acrylonitrile elastomer (ATBN). A specific example is Epon 58005, which is an elastomer-modified epoxy-functional adduct formed from the reaction of the diglycidyl ether of Bisphenol A and a carboxyl-terminated butadiene acrylonitrile elastomer. Additional elastomer-modified epoxy resins include Epon 58006, Epon 58042, Epon 58120, Epon 58091 from Hexion Specialty Chemicals, Inc.
    [00024] Other suitable elastomeric polymers include carboxyl terminated butadiene acrylonitrile polymer (CTBN) and amine terminated butadiene acrylonitrile elastomer (ATBN) or similar reactive liquid polymer chemicals. In addition, CTBN and/or ATBN can also be added to part (A) or part (B) of the two-part system or to the one-part system to further improve the rigidity and resilience of the adhesive.
    [00025] Polyether sulfone (PES) polymer includes polyethersulfone-polyetherethersulfone (PES-PEES) copolymer having Tg above 190°C, for example, KM 170 and KM 180, which have Tg of about 200°C, available from Cytec Industries Inc.
    [00026] Other suitable stiffening agents include phenoxy resins, which are long chain linear polyhydroxy ethers with different molecular weights, such as phenol,4,4'-(1-methylethylidene) bispolymer with (chloromethyl)oxirane. Commercial examples include Phenoxy PKHP-200 and PKHB-100 available from InChem Corp.
    [00027] A significant challenge for a resin-based adhesive composition is maintaining the rheology performance of the adhesive between the time it is manufactured and the time it is applied. Inorganic fillers act as a thixotropy or rheology modifying component in the two-part or one-part system. Suitable inorganic fillers are those in particulate form and include silica, alumina, calcium oxide, talc and kaolin. Colloidal silica, with surface area in the range of 90-380 m2/g has been shown to be suitable for the two-part system or the one-part system. For the two-part system, the percent inorganic filler weight in the resinous part (A) is within the range of 1-6% by weight based on the total weight of part (A). For catalyst part (B), the percent inorganic filler weight is within the range of 3-10% by weight based on the total weight of part (B). For the one-part system, the percent inorganic filler weight is within the range of 0.5 to 2.5% by weight. Inorganic fillers
    [00028] In an embodiment of the two-part system, the inorganic filler in the resinous part (A) is the hydrophobic colloidal silica, such as CAB-O-SIL TS-720 available from Cabot Corporation, and the inorganic filler in the catalyst part ( B) is hydrophilic colloidal silica such as CAB-O-SIL M-5 available from Cabot Corporation. In one embodiment of the one-part system, the inorganic filler is hydrophobic colloidal silica, such as CAB-O-SIL TS-720. Other examples of colloidal silica-based rheological modifiers include Aerosil R202 and VPR 2935 supplied by Evonik Degussa Corp. The presence of colloidal silica helps maintain the desired viscosity of the adhesive and also improves the adhesive's sagging resistance during application and curing. Sagging or dropping strength is desirable when the adhesive is applied to vertical or high-angle surfaces. Amine Curing Agents for Two-Part System
    [00029] One or more amine curing agents can be used in the catalyst part (B) of the two-part system. The amine curing agents for catalyst part (B) are compounds of aliphatic or cyclic amines capable of reacting with the multifunctional epoxy resins in part (A) to form highly crosslinked resin matrix. In a preferred embodiment, the amine compounds are selected from the group consisting of cycloaliphatic amines, polyethylene polyamines, amine terminated piperazines, imidazoles and combinations thereof. The weight percent of the amine curing agents is within the range of 80-95% by weight based on the total weight of part (B).
    [00030] Suitable cycloaliphatic amines include dicyclohexylamines such as bis-(paminocyclohexyl)methane (PACM), containing the following structure:

    [00031] and dimethyl PACM containing the following structure:

    [00032] Suitable polyethylene polyamines include tetraethylene pentamine (linear C-8 pentamine), containing the following chemical structure:

    [00033] Other suitable examples of polyethylene polyamines include diethylenetriamine (C-4 linear diamine), triethylenetetramine (C-6 linear triamine), and pentaethylenehexamine (C-10 linear hexamine).
    [00034] An example of an amine terminated piperazine is 1,4 Bisaminopropyl piperazine containing the following structure:

    [00035] Another example is aminoethyl piperazine containing the following structure:

    [00036] Suitable imidazoles include 2-ethyl-4-methyl imidazole having the following structure:

    [00037] This type of imidazole is commercially available as Imicure EMI-2.4 from Air Products.
    [00038] Additional examples of amine curing agents include tris-(dimethylaminomethyl)phenol (available as Ancamine K54 from Air Products) and diethylene glycol, di(3-aminopropyl) ether (available as Ancamine 1922A). Amine Curing Agents for One-Part System
    [00039] Curing agents for the one-part system include latent amine-based curing agents, which can be used in combination with at least one of an imidazole and an aliphatic amine. The inclusion of imidazole and/or aliphatic amine further lowers the curing temperature of the adhesive composition. Latent amine based curing agents that can be activated at a temperature greater than 160°F (71°C) are suitable for the one-part system. Examples of suitable latent amine-based curing agents include dicyandiamide (DICY), guanamine, guanidine, aminoguanidine and derivatives thereof. A particularly suitable latent amine-based curing agent is dicyandiamide. The latent amine-based curing agent may be present in an amount within the range of 2-6% by weight.
    [00040] A curing accelerator can be used in conjunction with the latent amine based curing agent to promote the curing reaction between the epoxy resins and the amine based curing agent. Suitable cure accelerators can include alkyl and aryl substituted ureas (including aromatic or alicyclic dimethyl urea); bisureas based on toluenediamine or methylene dianiline. An example of bisurea is 2,4-toluene bis(dimethyl urea) (commercially available as Omicure U-24 or CA 150 from CVC Chemicals). Another example is 4,4'-methylene bis(phenyl dimethyl urea) (commercially available as Omicure U-52 or CA 152 from CVC Chemicals), which is a suitable accelerator for dicyandiamide. The cure accelerator may be present in an amount within the range of 1-6% by weight. In one modality, dicyandiamide is used in combination with a substituted bisurea as a healing accelerator.
    [00041] Suitable imidazoles include 2-ethyl-4-methyl imidazole, eg Imicure® EMI-24 as described above for the two-part system.
    [00042] Suitable aliphatic amines are those with amine value (mg KOH/g) in the range of 180-300, and equivalent weight (H) in the range of 35-90. Examples of suitable aliphatic amines include Ancamine 2014AS (modified aliphatic amine) and Ancamine 2037S available from Air Products. Other examples of aliphatic amines are Aradur™ 956-4, 943, 42 from Huntsman and EPICURE™ 3202, 3223, 3234 from Momentive Specialty Chemicals.
    [00043] In a one-part adhesive modality, an amine encapsulated in the matrix, such as Intelimer® 7004 (2-ethyl-4-methyl-imidazole covalently bonded to Intelimer® polymer) and Intelimer® 7024 (Intelimer® polymer encapsulated 2- ethyl-4-methyl-imidazole) from Air Products, is used as a latent curing agent. These materials are composed of imidazole-based catalyst encapsulated within Intelimer® polymer through matrix encapsulation. Intelimer® polymers are crystalline polyacrylate polymers in which crystallinity results from side chains that are attached to the polymer backbone. These crystalline polymers have a very sharp and well-defined melting point. Encapsulation can be done by physical mixing or deliberate covalent bonding (ie covalently modified polymer). By this encapsulation arrangement, the activity of the amine catalyst is blocked by a polymer network until thermal activation, eg cure. The inclusion of these matrix-encapsulated amines in the adhesive increases the stability of the adhesive at room temperature. Additional Additives
    [00044] Additives such as dyes or coloring pigments can be added to the two-part system (part A or part B) and the one-part system to adjust the color of the adhesive. Adhesive bonding application
    [00045] The one-part and two-part adhesives of the present disclosure are suitable for bonding various aerospace structural materials to form a laminated structure, including metal to metal, metal to composite material, composite material to composite material. Composite materials include fiber-reinforced resin composites such as prepegs or pre-peg arranged to prepare composite plane structures. The term "pre-peg" as used herein refers to a sheet or sheet of fibers that has been impregnated with a matrix resin. The matrix resin can be present in a cured or partially cured state. The term “laid pre-peg” as used herein refers to a plurality of layers of pre-pegs that are placed adjacent to each other in a stack. Pre-peg layers within the stock can be positioned in a selected orientation relative to each other. For example, pre-peg arrays can comprise pre-peg layers containing unidirectional fiber architectures, with the fibers oriented at 0°, 90°, a selected angle θ, and combinations thereof, with respect to the largest largest dimension of the stock, like the length. It should further be understood that, in certain embodiments, pre-pegs can have any combination of fiber architectures, such as unidirectional and multidimensional.
    [00046] After mixing, the two-part adhesive composition generates a paste adhesive that can be applied by conventional means of distribution such as bead or film application on one or more surfaces to be glued. For structural bonding of metals and aerospace composite materials, the adhesive can be applied in a thickness of 10-80 mils (0.254mm - 2.032mm). The surfaces are then joined to form a laminate with an adhesive film between the substrates. Thereafter, the resulting laminate can be cured at or below 93°C (or 200°F), including room temperature. This low-temperature curing method allows for curing the laminate outside the autoclave (OOA). The two-part system cured adhesive is a structural adhesive with improved mechanical properties: an overlay shear strength of 33-37 MPa at 20°C-25°C and 24-27 MPa at 82°C, 15-18 MPa at 121 °C according to ASTM D3165, a peel strength of 250-350 Nm/m (or 50-75 lbs/in) at 20OC-25OC according to ASTM D3167. In addition, when the two-part adhesive is used for bonding resin fiber reinforced composite substrates, it exhibits fracture stiffness (or interlaminar stiffness, G1c) greater than 650 J/m2, eg 651-1500 J/m2 per ASTM 5528. The Tg and overlap shear strength remain substantially unchanged (over 90% retention) after aging by exposure to air containing 100% relative humidity at 71OC for 14 days or at 49OC per 30 days.
    [00047] For the one-part adhesive, the cured adhesive film has the following properties: a glass transition temperature (Tg) greater than 100OC (212OF) after curing in the temperature range of 65-93OC (150OF-200OF), a overlap shear strength of 28-40 MPa at 20OC-25OC and 25-28 MPa at 82OC, 17-21 MPa at 121°C, as per ASTM D3165 tests, a peel strength of 150-250 Nm/m ( or 30-50 lbs/in) at 20OC-25OC in accordance with ASTM D3167.
    [00048] ASTM D3165 refers to a Standard Test Method for Tensile Loading Shear Strength Properties of Adhesives in Single Lay Joint Laminate Assemblies. Lap shear determines the shear strength of adhesives for bonding materials when tested on a single lapped joint sample.
    [00049] ASTM D3167 refers to a Standard Test Method for Detachment Resistance of Floating Roll of Adhesives. This test method encompasses the determination of the relative peel strength of adhesive bondings between a rigid and a flexible adhesive when tested under specific preparation and testing conditions. Adhesion is measured by detaching the flexible adhesive from the rigid substrate. Detachment force is a measure of fracture energy.
    [00050] ASTM D5528 refers to a Standard Test Method for Mode I Interlaminar Fracture Stiffness of Fiber Reinforced Polymer Matrix Composites.
    [00051] The paste adhesive disclosed here has film-like properties that allow for automated distribution of the adhesive - this is particularly useful in quick assembly aerospace structural bonding applications. In addition, the advantages of the two-part adhesive disclosed here include: - Low temperature cured glue with film-like properties of structural adhesives - High strength/high stiffness and excellent hot/wet properties for bonding metal and composite - Schedule of flexible low temperature cure - Stable properties - Long packaged life/Long assembly time - No bagging, OOA Structural Bonding - Thixotropic, drop resistant and easy to use - Automation positioning capability - Room temperature storage for up to 1 year ( 1 year validity) - Lower manufacturing cost. EXAMPLES
    [00052] The following examples are provided for purposes of illustrating the various embodiments, but are not intended to limit the scope of the present disclosure. Example 1 Two Part System
    [00053] For the two-part adhesive system, Tables 1A and 1B show exemplary formulations for the resinous part (A). A-1 through A-7 represent the most preferred formulations, and A-8 and A-9 are comparative formulations. Table 2 shows exemplary formulations for the catalyst part (B). To form a paste adhesive, any one of A-1 through A-9 can be mixed with any one of B-1 through B-7. Unless otherwise noted, quantities in the tables are expressed in parts. TABLE 1A - Resin Part (A)
    TABLE 1B - Resin Part (A)
    TABLE 2 - Catalyst Part (B)

    [00054] The resinous part and the catalyst part based on the above formulations were prepared separately by weighing and adding the necessary components in different steps for a double planetary mixer with heating and cooling capacity. The epoxy and CSR components of the resinous part were first mixed under high temperature (between 65.5 °C (150 °F) and 93.3 °C (200 °F)) to obtain a homogeneous, resinous mixture. The mixture was cooled to 65.5 °C (150 °F) and Epon 58005 was added to the mixture. EPON 58005 has been preheated to 120°F before adding to the mix for ease of handling. The mixture was cooled to 90°F and colloidal silica then added. Mixing continued during the application of a vacuum to remove air from the mixture. The resulting resin base was then removed from the blender when the temperature was below 80°F. For the catalyst part, the amine curing agents and colloidal silica were added to the mixer and mixed at room temperature until the silica was evenly dispersed. Example 2
    [00055] A two-part sticker based on Part A-1 and Part B-1 (disclosed in Example 1) and a two-part sticker based on Part A-2 and Part B-3 (disclosed in Example 1), have the properties shown in Table 3. Mixed density (ie, specific mass) was determined after mixing the resin part with the catalyst part at room temperature and after curing at 93°C (200°F). TABLE 3 - Two-Part Adhesive Properties
    Example 3 Glue Performance
    [00056] The metal bonding performance and composite bonding performance of various two-part adhesives based on the formulations disclosed in Example 1 were measured. Al-2024-T3 aluminum sheets from Alcoa Inc. were used as the substrates for the metal-to-metal bonding. The aluminum metal was first cleaned with a solvent, followed by alkaline degreasing, FPL (chromium sulfur corrosion) corrosion, and phosphoric acid (PAA) anodizing by ASTM 3933. Cytec Industries Inc. BR®127 solvent-based initiator was sprayed. on aluminum metal with a thickness of 0.00015 inches. The initiator was air dried for 15 minutes and then cured at 121°C (250°F) for 60 minutes. Two aluminum sheets were glued together by applying the paste adhesive between the sheets. The glue line thickness is controlled with glass beads to about 10 mils (254 microns). All bonded samples were cured in a hot press at temperatures between 71°C (160°F) and 93°C (200°F) for the time indicated. Contact pressure of 0.021 to 0.035 MPa (3 to 5 psi) was applied throughout the cure. The properties of metal-to-metal adhesion strength (Wide Area Overlap Shear - WALS) and stiffness (floating roller shell -FRP, or climbing drum shell - CDP) of the paste adhesive were tested at different temperatures. Test results are reported as the average of five samples for each test group. The glass transition temperature (Tg onset) of the cured paste adhesive was determined using a thermal mechanical analyzer (TMA 2940) from TA Instruments.
    [00057] Composite sizing was performed using fiber reinforced pre-pegs as test substrates. The pre-pegs used were precured Torayca® T800H/3900-2 prepegs from Toray Composites, Inc. A dry polyester peel layer or resin-rich peel layer was used as a surface treatment on the composite substrates. Curing was performed under non-autoclave (OOA) conditions.
    [00058] For gluing performance tests, the following test methods were used: a) Wide Area Overlap Shear (WALS) - ASTM D3165 b) Floating Roll Detachment (FR Detachment) - ASTM D3167 c) Double Cantilever Bundle (DCB, G1C) for composite bonding - ASTM D5528
    [00059] Table 4 shows the metal bonding properties of a paste adhesive formed by mixing Part A-2 and Part B-1 at a mixing ratio (A:B) of 2:1 by weight. TABLE 4

    [00060] Table 5 shows the composite-composite sizing properties of a paste adhesive formed by mixing Part A-1 and Part B-1 at a mixing ratio (A:B) of 2:1 by weight. TABLE 5

    [00061] Table 6 shows the metal-to-metal bonding properties of a paste adhesive formed by mixing Part A-2 and Part B-3 at a mixing ratio (A:B) of 2:1 by weight. TABLE 6

    [00062] Table 7 shows the metal-to-metal bonding properties of a paste adhesive formed by mixing Part A-1 and Part B-4 or B-5 in mixing ratios (by weight). TABLE 7

    [00063] Room temperature curable two-part adhesive based on Part A-1 combined with Part B-4 (4:1 A:B weight ratio) has been tested for composite bonding. The results show a G1c value of 4.5 in-lb/in2 (788 J/m2) and cohesive failure mode. Comparative Examples
    [00064] For comparison, each of Part A-8 and Part A-9 disclosed in Table 1B was mixed with the formulation of Part B-1 disclosed in Table 2 to form a paste adhesive. The resulting adhesives were then tested for metal-to-metal bonding properties as described above. The results are shown in Table 8. TABLE 8

    [00065] Table 8 shows that the temperature floating roll detachment resistance of the comparative adhesives is lower than that of the more preferred adhesives at the same curing temperature. Example 4
    [00066] Effect of Bonding Line Thickness on Paste Adhesive Bonding Performance
    [00067] The effect of bond line thickness on the metal-to-metal bonding performance of the paste adhesive was measured using bonded aluminum samples, where bonding the adhesive was done using a two-part adhesive composed of the formulations of Part A-1 and Part B-1 disclosed in Example 1, at a mixing ratio of 2:1. Curing was performed under OOA curing at 93°C for 2 hours. The results for WALS and FRP tests with different bond line thicknesses are shown in Table 9. Paste adhesive showed decreases in overlap shear and peel strength with increasing bond line thickness. However, the detachment strength was much more tolerant to the variation of the glue line thickness. At high bond line thicknesses (40-80 mm), the paste adhesive showed very high peel strength and mainly cohesive failure mode. At high bond line thicknesses, it also retained more than 50% of its original large-area overlap shear strength. The paste adhesive's good tolerance for bond line thickness variation reflects its inherently high stiffness. The tolerance for high glue line thickness makes it very attractive for structural gluing applications where high or non-uniform glue line thickness occurs. TABLE 9
    Example 5 Effect of Moisture Exposure on Adhesive Bonding Performance
    [00068] To ensure the durability of bonded composite-composite or composite-metal structures, a hard, moisture resistant, flow-controlled epoxy-based adhesive is required. Hardened adhesives must have good durability performance under hot/wet conditions and other environmental exposure conditions. The effect of post-gluing moisture on the paste adhesive was evaluated by exposing individually cut large area overlap shear samples to air at 71°C and 100% relative humidity (RH) for 14 days, or by exposing them at 49° C and 100% HR for 30 days. Table 10 shows the results for bonded metal samples, which were formed using a two-part adhesive composed of Part A-1 and Part B-1, 2:1 mixing ratio. As shown in Table 10, the paste adhesive demonstrates excellent shear strength retention after post-gluing moisture exposures. Failure modes for samples exposed to hot/wet were mainly cohesive or slightly cohesive reflecting the good moisture resistance of the material. TABLE 10

    [00069] The bonding performance of the composite of the same two-part adhesive (Part A-1/Part B-1, 2:1 mixing ratio) was determined using WALS test and double beam cantilever (G1C) as described in Example 3. Cure was performed at 93.3°C (200°F) for 2 hours. Results after aging exposure to moisture are shown in Table 11. TABLE 11
    Example 6 One-Part System
    [00070] Table 12 shows exemplary one-part adhesive formulations 1A-1E. All quantities are expressed in parts. TABLE 12

    [00071] The metal bonding properties of Formulations 1A-1E were measured as described in Example 3. The results are shown in Table 13. TABLE 13


    [00072] The sizing properties of Formulation 1A composites were measured as described in Example 3. For measurement of WALS, the polyester peel layer was used for surface treatment before sizing, and for measurement of G1c, the surface of the compound was plasma treated before bonding. The results are shown in Table 14. TABLE 14

    [00073] The ranges disclosed herein are inclusive and independently combinable (for example, ranges of "up to approximately 25% by weight, or more specifically approximately 5% by weight to approximately 20% by weight", are inclusive of the endpoints and of all intermediate values in the ranges of "approximately 5% by weight to approximately 25% by weight", etc.).
    [00074] Although various embodiments are described herein, it will be appreciated from the specification that various combinations of elements, variations of embodiments disclosed herein can be made by those skilled in the art and are within the scope of the present disclosure. Furthermore, many modifications can be made to adapt a particular situation or material to the teachings of the modalities disclosed here without departing from the essential scope of the same. Therefore, it is intended that the claimed invention not be limited to the particular embodiments disclosed herein, but that the claimed invention include all embodiments falling within the scope of the appended claims.
    权利要求:
    Claims (15)
    [0001]
    1. Two-part system for forming a structural adhesive, characterized in that it comprises a resinous part (A) with a separate catalyst part (B), the resinous part (A) comprising: at least two different multifunctional epoxy resins with different epoxy functionality selected from bifunctional, trifunctional and tetrafunctional epoxy resins; smaller shell-core rubber particles having average particle size less than or equal to 100 nm and larger shell-core rubber particles having average particle size greater than 100 nm, the weight ratio of shell-core rubber particles smaller for larger shell-core rubber particles being in the 3:1 to 5:1 range; at least one of (i) an elastomeric polymer having a functional group capable of reacting with multifunctional epoxy resins and (ii) a polyethersulfone polymer having an average molecular weight in the range of 8,000-14,000, wherein said elastomeric polymer is selected from the group consisting of carboxyl-terminated butadiene acrylonitrile (CTBN), amine-terminated acrylonitrile butadiene (ATBN) and epoxy-elastomer adducts formed by the reaction of an epoxy resin with a carboxyl-terminated butyl acrylonitrile elastomer or an ATBN elastomer; and inorganic filler particles; the catalyst part (B) comprising: at least one amine curing agent selected from the group consisting of: dicyclohexylamine, amine terminated piperazine, polyethylene polyamine, and combinations thereof; and inorganic filler particles; where the weight ratio of part (A) to part (B) is within the range of 3:2 to 10:2, and where when part (A) and part (B) are mixed and then cured in a temperature range of 65 °C - 93 °C (150-200 °F), the resulting structural adhesive has a glass transition temperature (Tg) greater than 95 °C (203 °F), an overlap shear strength 33 MPa - 37 MPa at a temperature of 20 °C-25 °C and 24 MPa -27 MPa at 82 °C, and 15 MPa -18 MPa at 121 °C according to ASTM D3165, a resistance to detachment 250 N Nm/m -350 N^m/m at a temperature of 20°C - 25°C according to ASTM D3167.
    [0002]
    2. Two-part system according to claim 1, characterized in that the weight ratio of part (A) to part (B) is 2:1.
    [0003]
    3. Two-part system according to claim 1, characterized in that the amine curing agent is dicyclohexylamine selected from the following:
    [0004]
    4. Two-part system according to any one of claims 1 to 3, characterized in that the curing agent is a combination tetraethylene pentamine (TEPA) and amine-terminated piperazine.
    [0005]
    5. Two-part system according to any one of claims 1 to 4, characterized in that the resinous part (A) comprises a combination of non-cycloaliphatic bifunctional epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin and multifunctional cycloaliphatic epoxy resin .
    [0006]
    6. Two-part system according to any one of claims 1 to 5, characterized in that the at least two different multifunctional epoxy resins comprise at least one cycloaliphatic epoxy.
    [0007]
    7. Two-part system according to claim 1, characterized in that the polyethersulfone polymer is a copolymer of polyethersulfone-polyetherethersulfone (PES-PEES).
    [0008]
    8. Two-part system according to any one of claims 1 to 7, characterized in that the smaller shell-core rubber particles have particle sizes within the range of 50 nm - 90 nm and the rubber particles of Larger shell-cores have particle sizes within the range of 150 nm - 300 nm.
    [0009]
    9. Laminated structure, characterized in that it comprises a first substrate bonded to a second substrate and a cured structural adhesive film between the first and second substrates, wherein the cured structural adhesive film is formed by the two-phase system as defined in claim 1; and wherein the structural adhesive film has a thickness of 254 µm to 2032 µm (10-80 mils), a glass transition temperature Tg greater than 95 °C (203 °F) after curing in the 65 °C temperature range at 93 °C (150200 °F), an overlap shear strength of 33 MPa at 37 MPa at a temperature of 20 °C at 25 °C and 24 MPa at 27 MPa at a temperature of 82 °C, and 15 MPa to 18 MPa at a temperature of 121 °C according to ASTM D3165 test, a peel strength of 250 Nmi/m to 350 N^m/m (or 50-75 lbs/in) at a temperature of 20 ° C to 25°C according to ASTM D3167.
    [0010]
    10. Laminated structure according to claim 9, characterized in that the first substrate is a metal substrate and the second substrate is a metal substrate or a fiber-reinforced resin composite.
    [0011]
    11. Laminated structure according to claim 9 or 10, characterized in that the adhesive film has a fracture stiffness in the range of 651 J/m2 -1500 J/m2 (3.5 to 8.1 in-lb/ in2) as determined by ASTM D5528.
    [0012]
    12. Laminated structure, characterized in that it comprises a first substrate bonded to a second substrate and a cured adhesive film formed therebetween, the adhesive film being formed from an adhesive composition comprising: at least two selected different multifunctional epoxy resin bifunctional, trifunctional and tetrafunctional resins; smaller shell-core rubber particles having average particle size less than or equal to 100 nm and larger shell-core rubber particles having average particle size greater than 100 nm, the weight ratio of the smaller particles to the larger particles being in the range of 3:1 to 5:1; at least one of an elastomeric polymer having an epoxy functional group and a polyethersulfone polymer having an average molecular weight in the range of 8,000-14,000; inorganic filler particles; and a latent amine-based curing agent selected from dicyandiamide (DICY), guanamine, guanidine, aminoguanidine and their derivatives, and an imidazole-based catalyst encapsulated within a crystalline polymer network, in which the cured adhesive film has the following properties: a glass transition temperature (Tg) greater than 100 °C (212 °F) upon curing in the temperature range of 65 °C-93 °C (150 °F-200 °F), a shear strength of overlap of 28 MPa - 40 MPa at 20 °C -25 °C and 25 MPa - 28 MPa at a temperature of 82 °C, and 17 MPa - 21 MPa at a temperature of 121 °C according to ASTM D3165, a resistance to detachment of 150 N^m/m -250 Nm/m (30-50 lbs/in) at a temperature of 20°C -25°C according to ASTM D3167.
    [0013]
    13. Laminated structure according to claim 12, characterized in that the imidazole-based catalyst is 2-ethyl-4-methyl-imidazole covalently bonded to or encapsulated in a crystalline polymer network.
    [0014]
    14. Laminated structure according to claim 12 or 13, characterized in that at least one of the multifunctional epoxy resins is a cycloaliphatic multifunctional epoxy resin.
    [0015]
    15. Laminated structure according to any one of claims 12 to 14, characterized in that the adhesive composition further comprises an aliphatic amine having an amine value in the range of 180 mg/g to 300 mg/g, and an equivalent weight (H) in the range of 35 g/mol to 90 g/mol.
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    同族专利:
    公开号 | 公开日
    TW201323556A|2013-06-16|
    CA2854825C|2019-11-12|
    CA3052816A1|2013-05-16|
    CA2854825A1|2013-05-16|
    IN2014CN03459A|2015-10-09|
    US20150030844A1|2015-01-29|
    WO2013070415A1|2013-05-16|
    KR102052389B1|2019-12-05|
    MX362835B|2019-02-19|
    EP2776487A1|2014-09-17|
    US20130115442A1|2013-05-09|
    CA3052816C|2020-07-07|
    MY168074A|2018-10-11|
    JP2015501853A|2015-01-19|
    CN103797043B|2016-09-07|
    MX2014005116A|2014-05-28|
    US8895148B2|2014-11-25|
    AU2012336202A1|2014-02-06|
    BR112014010798A2|2017-04-25|
    TWI576404B|2017-04-01|
    JP5964980B2|2016-08-03|
    RU2014123295A|2015-12-20|
    CN103797043A|2014-05-14|
    AU2012336202B2|2015-12-03|
    KR20140100463A|2014-08-14|
    RU2592274C2|2016-07-20|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-29| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-04-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161557538P| true| 2011-11-09|2011-11-09|
    US61/557,538|2011-11-09|
    PCT/US2012/060975|WO2013070415A1|2011-11-09|2012-10-19|Structural adhesive and bonding application thereof|
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