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    • 专利摘要:
    COMPOSITION OF LIQUID BINDER, FIBROUS MATERIAL, AND INFUSIBLE RESIN PREMOLD. A liquid binder composition for binding fibrous materials in infusible resin preform fabrication is disclosed. The binder composition is an aqueous dispersion containing (a) one or more multifunctional epoxy resins, (b) at least one thermoplastic polymer, (c) one or more surfactants selected from anionic surfactants, nonionic surfactants, and combination thereof, (d) ) water, and is essentially free of organic solvents. A de-emulsification process for producing the liquid binder composition is also disclosed.
    公开号:BR112015014780B1
    申请号:R112015014780-1
    申请日:2013-08-29
    公开日:2021-05-11
    发明作者:Carmelo Luca Restuccia；William Jacobs；Gerald Hobisch；Dominique Ponsolle
    申请人:Cytec Technology Corp；
    IPC主号:
    专利说明:

    FUNDAMENTALS
    [001] Fiber-reinforced polymer composites have been used in the construction of load-bearing articles, typically in the marine, automotive, aerospace and construction industries. These composites typically contain fibrous reinforcement such as glass fibers and carbon fibers, embedded in a cured matrix resin.
    [002] Fiber-reinforced polymer composites are traditionally produced from pre-impregnated sheets of resin-impregnated fibers, which are laid, molded and cured. The resin content in the prepreg is high, typically 20%-50% by weight. The properties and quality of the prepreg are controlled by strength, strength, flexibility and the like. Pre-impregnated sheets can be cut to smaller sizes for laying in the construction of a given article.
    [003] In recent years, resin infusion technologies have been used to fabricate complex shaped structures that are otherwise difficult to fabricate using conventional prepreg technology. Resin infusion technologies include Resin Transfer Molding (RTM), Liquid Resin Infusion (LRI), Vacuum Assisted Resin Transfer Molding (VARTM), Resin Over Mold Infusion (RIFT), Resin Infusion Vacuum Assisted (VARI), Resin Film Infusion (RFI), Resin Infusion with Controlled Atmospheric Pressure (CAPRI), VAP (Vacuum Assisted Process) and Single Line Injection (SLI). Resin infusion differs from conventional prepreg technology in that the dry structural reinforcing fibers are laid out in a mold as a preform, then the preform is injected or infused directly in situ with the matrix. of resin. After resin infusion, the resin infused preform is cured to form a hardened composite part. The preform typically consists of a plurality of layers of fibrous materials, such as unidirectional fibers or fabrics, which are assembled through a lay-up molding process to form a predetermined shape and hold in place by stitching, stapling or gluing with the use of binders. Preform fabrication often requires cutting (or slitting) dry fabrics or fibers of a certain size and/or shape. The limitations of these conventional fiber products lie in the inability to cut and apply these products through an automated laminating process without deforming and fraying the edges.
    [004] Binders have been used in the manufacture of dry preforms for various purposes, such as to provide cohesion to the reinforcing fibers, to bond the layers of reinforcing fibers, and to provide tackiness so that the fibrous material remains in a stationary position during the lay-up process. While there are commercially available binders such as solvent based binders and powder form binders, there are disadvantages associated with each type. As such, there continues to be a need for a binder composition that can be applied in an environmentally friendly manner, and that can improve the handling, cutting and shaping of the fibrous materials that are used to manufacture dry preforms. SUMMARY
    [005] Described herein is a liquid binder composition that is suitable for fibrous materials that are for use in the manufacture of dry preforms. The liquid binder composition is an aqueous dispersion containing (a) one or more multifunctional epoxy resins, (b) at least one thermoplastic polymer, (c) one or more surfactants selected from anionic surfactants, nonionic surfactants, and combinations of the themselves, and (d) water, and is essentially free of organic solvents. In addition, the binder composition is formulated to have a solids content and a viscosity level that allows application of dip or spray coating at room temperature (20°C-25°C). It has been found that the presence of the binder composition in the fibrous materials improves the handling, cutting and shaping of the fibrous materials. Furthermore, the binder composition is particularly suitable for treating fibrous materials for use in automated lamination processes. Also described herein is the method of preparing the binder composition. BRIEF DESCRIPTION OF THE DRAWINGS
    [006] FIG. 1 is a micrograph showing a bond-coated carbon web prepared according to an example. DETAILED DESCRIPTION
    [007] The present invention provides a liquid binder composition to be introduced into the fibrous materials that make up the preform. The binder composition can be applied in an eco-friendly way, and can improve the handling, cutting and forming of the fibrous materials that are used for making dry preforms. In the case of preforms with complex shapes, the binder composition in the fibrous materials allows the preform to maintain its shape during injection of the preform with a liquid resin matrix. It is desirable that the binder composition does not impede the lay-up modeling operation or composite fabrication and, in particular, the resin injection process. Furthermore, the binder composition generally should not affect the mechanical performance of the resulting composite derived from such a preform nor considerably lower the composite's glass transition temperature (Tg). To that end, the liquid binder composition of the present disclosure is formulated so as to be chemically compatible with the resin matrix, particularly the epoxy base resin, which is to be injected into the preform.
    [008] The binder composition of the present invention is an aqueous dispersion containing (a) one or more multifunctional epoxy resins, (b) at least one thermoplastic polymer, (c) one or more surfactants selected from anionic surfactants, non-anionic surfactants. ionic, and combinations thereof, (d) water, and is essentially free of organic solvents. Optional additives such as organic or inorganic fillers and an anti-foaming agent can also be included in the binder composition.
    [009] The liquid binder composition is preferably produced by a high shear emulsification process and may have the following properties: solids content in the range of 45%-70% based on the total weight of the composition, and the particle size distribution in the range of 50 nm -10000 nm;
    [0010] The binder emulsion produced from the emulsification process has been shown to be stable for several weeks in the above solid content, and can produce a stable emulsion of low solids, eg 0.1% to 10%, by dilution with deionized water. As such, the binder emulsion can be applied to fibrous materials used in preform fabrication when the emulsion has been sufficiently diluted to achieve a low solids content that is suitable for preform fabrication.
    [0011] Generally, the quantity and type of multifunctional epoxy resins is sufficient amount to achieve the viscosity level that is compatible for high shear emulsification and to produce tack-free binder treated fibrous material at room temperature g pixgku uul'kekgptgu fg rgicjqukfcfg c VgorgtcVwtcu cekoc fg 92üEo C pctwtgzc thermoplastic, the number average molecular weight, content, type and content of the chain end or pendant groups are sufficient to harden the binder composition without disrupting the ionic balance of the emulsion, and are selected to maintain the desired viscosity level. The amount of surfactant(s) is the amount sufficient to emulsify the thermoplastic/epoxy mixture and to stabilize the binder emulsion.
    [0012] In one embodiment, the relative amounts of the components in the binder composition, in percentages by weight based on the total weight of the composition, are as follows: 0.1-70% of one or more multifunctional epoxy resins 0.01-30% of one or more thermoplastic polymers 0.01-15% of one or more surfactants 0.001-10% of optional additive(s) water for equilibrium, wherein the optional additives include an anti-foaming agent such as a polysiloxane, a fluorocarbon, mineral oils, or an acetylene-based defoamer, however, other compounds can also be used that can reduce surface tension and/or decompose the foam by other means.
    [0013] To prepare the binder composition, the thermoplastic polymer(s) and multifunctional epoxy resin(s) are usually mixed first, optionally with heating to disperse and/or dissolve (the) thermoplastic polymer in the resin(s) (s) epoxy. The surfactant(s) and, optionally, additives are added and completely dispersed in the resin mixture to form a resin mixture. Then the resin mixture is poured into a mixing device, eg high shear mixer equipped with an open vessel connected to a recirculating heating system. Mixing is then carried out at a relatively high temperature, while gradually adding water to emulsify the resin mixture. Alternatively, resins are added (with or without surfactant) to the water phase (often containing the surfactant) under shear conditions. This is called the direct method for producing emulsion. Additives can also be added to the binder composition, during or after the emulsification or dilution steps prior to application to the fibrous substrate.
    [0014] In one embodiment, the temperature inside the high shear mixer during emulsification is 90°C-110°C. The temperature should be sufficient to ensure that the binder composition is capable of being uniformly stirred under shear, so as to allow water to be incorporated, but not so high as to cause the water to rapidly evaporate at a given pressure in the reactor. . The temperature must also not be so high that the components of the composition undergo undesirable side reactions, such as hydrolysis or advancing. The shear rate of the mixer is initially set to a low value, then at the inversion point (when the solid-in-liquid mixture becomes more of a homogeneous phase), the high shear rate is applied to reduce the particle size and ensure optimal homogenization and emulsion stability. Sufficient amount of water is added to the mixer during emulsification to achieve the desired solids content and viscosity. Additional additives, such as anti-foaming agents, can be added to the binder composition, prior to application to the fibrous product.
    [0015] The liquid binder composition of the present invention provides several advantages, including: (i) Dispersibility in water, thus the composition is ecologically correct; (ii) Ability to homogeneously coat the fibrous cables in woven fabrics, thus enhancing the integrity of the fiber cables; (iii) Suitability for existing textile manufacturing processes; (iv) Providing an adequate level of adhesion and/or compatibility with the conventional epoxy-based resin matrix that has been used for resin infusion; (v) Ability to minimize/eliminate variability in binding capacity normally observed in powder coated textiles; (vi) Limited or no impact on the thermo-mechanical performance of the composite portion produced from a fibrous preform that has been treated with the liquid binder.
    [0016] Furthermore, the liquid binder composition of the present invention provides several advantages over conventionally shaped powdered binders. Binder in solid form not only requires expensive milling and sieving equipment to produce the necessary uniform fine powders, but it also requires expensive powder coating equipment in order to effectively apply it to fibrous materials or fabrics. In addition, application of a powder provides an uneven, non-uniform application to fibrous materials or fabrics that may not provide the ideal bonding properties desired for styling. Powders also tend to be easily peeled from the fibrous substrate when subjected to friction during handling and depositing, especially in automated processes, resulting in additional variation and defects due to lack of tack at specific points. In contrast, the emulsified aqueous liquid binder compositions of the present disclosure provide the ability to incorporate solid components, such as high Tg solid thermoplastics, into an organic solvent free, low viscosity aqueous composition. This low-viscosity, solvent-free aqueous composition can now be easily applied homogeneously by conventional dipping, spraying or lamination-coating processes, thus providing additional benefits including ease of processing, increased automation and cost savings. .Multifunctional epoxy resins
    [0017] The one or more multifunctional epoxy resins in the binder composition are polyepoxides that contain an average of two or more epoxy groups (oxirane rings) per molecule with the epoxy groups being the end groups. A difunctional epoxy resin is an epoxy resin that contains, on average, 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 groups epoxy per molecule. In a preferred embodiment, the multifunctional epoxy resin has an average epoxy equivalent weight (EEW) in the range of 90-240 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 difunctional epoxy having a molecular weight of 400 would have an epoxy equivalent weight of 200. In one embodiment, the binder composition contains a plurality of multifunctional epoxy resins, including one or more trifunctional epoxy resins.
    [0018] In general, multifunctional epoxy resins that are suitable for the binder composition 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 epibromohydrin with a polyphenol in the presence of an alkali. Suitable polyphenols are, therefore, for example, resorcinol, pyrocatechol, hydroquinone, bisphenol A (bis(4-hydroxy-phenyl)-2,2-propane), bisphenol F (bis(4-hydroxy-phenyl)methane), bisphenol S, bis(4-hydroxy-phenyl)-1,1-kuqdwVcpq. flwqtgpq 6.6'-dihydroxy-benzophenone, bis(4-hydroxy-phenyl)-1,1-gVcpq. dkufgpql ¥ *6.6'-Cyclohexylidenebisphenol), and 1,5-hydroxy-naphthalene. Polyglycidyl ethers of polyalcohols, aminophenols or aromatic diamines are also suitable.
    [0019] Other types of polyepoxides that can be used are glycidyl polyester resins prepared by the reaction of an epichlorohydrin with an aliphatic or aromatic polycarboxylic acid. Another type of polyepoxide resin is a glycidyl amine, which is prepared by reacting a polyamine with an epichlorohydrin. Other suitable multifunctional epoxy resins include multifunctional novolac epoxy resins with two or more epoxy groups. Epoxy novolac resins that are useful include cresol epoxy novolacs and phenol epoxy novolacs. Suitable multifunctional epoxy resins include multifunctional aliphatic epoxies such as epoxy-type polyglycidyl ether, and sorbitol glycidyl ether.
    Examples of difunctional epoxy resins include fkinkekfínkequ ethers fg bisl'gnol C. eqoq c Grqp™ :4: fg OqogpVkxg. FGT® 331, DER® 661, available from Dow Chemical Co., Tactix® 123 from Huntsman Advanced Materials, epoxy bisphenol F diglycidyl ethers such as PY306 available from Huntsman Advanced Materials and diglycidyl 1,2-phthalate (eg, GLY CEL A-100);
    [0021] Examples of trifunctional epoxy resins include aminophenol diglycidyl ether, eg Araldite® MY 0510, MY 0500, MY 0600, MY 0610, all available from Huntsman Advanced Materials, tris-(p-hydroxy) based epoxy -phenyl) Ethane such as Epalloy® 9000 from Emerald Performance Materials or Epon 1031 from Momentive.
    [0022] Examples of epoxy novolacs include DEN 354, 431, 438 and 439 from Dow Chemical Co., resorcinol modified phenol novolacs such as Erisys RN3650 from Emerald Performance Materials, dicyclopentadiene based phenolic novolacs such as Tactix 556 and 756 from Huntsman Advanced Materials and 1050, SU-3 and SU-8 from Momentive. Examples of tetrafunctional epoxy resins include Tetrad-X from Mitsubushi gas Company, Erisys® GA-240 from Emerald materials and Araldite® MY721 from Huntsman Advanced Materials. Other epoxy resin precursors include cycloaliphatic such as 3',4'-epoxy-cyclohexyl-3,4-epoxy-cyclohexane carboxylate (eg, CY 179 from Huntsman). thermoplastic polymer
    [0023] In a preferred embodiment, the thermoplastic polymer in the binder composition is a polymer that is substantially insoluble in a thermosetting resin system curable at room temperature (i.e., 20°C - 25°C) or under conditions not sufficient to the complete cure of the thermoset resin, but is capable of at least a partial phase transition to a fluid phase during the thermoset resin cure cycle. In other words, the thermoplastic polymer is a material that has no solubility (or negligible solubility) in the thermoset resin at room temperature or under conditions not sufficient for complete cure of the thermoset resin, while its solubility is substantial (i.e., more than 50% dissolves) or total (ie completely dissolves) during the thermoset resin cure cycle. The "thermosetting resin system" refers to the multifunctional epoxy resins in the binder composition or the liquid matrix resin to be injected or introduced into the preform after manufacturing the preform. The matrix resin for preform injection contains one or more thermosetting resins as the main component and small amounts of additives such as curing agents, catalysts, rheology control agents, tackifiers, inorganic or organic fillers, agents elastomeric hardeners, hardener particles, stabilizers, inhibitors, pigments/dyes, flame retardants, reactive diluents and other additives well known to those skilled in the art to modify the properties of the resin system before or after curing. Thermosetting resins for resin infusion include epoxy resins, bismaleimide, vinyl ester resins, cyanate ester resins, isocyanate modified epoxy resins, phenolic resins, benzoxazine, condensed formaldehyde resins (such as with urea, melamine or phenol) , polyesters, acrylics and combinations thereof. In one embodiment, the thermoplastic polymer in the binder composition is soluble in an epoxy-based resin matrix after the matrix resin has cured.
    [0024] For use herein, the term "cure" refers to the hardening of a matrix resin by crosslinking polymer chains, caused by chemical additives, ultraviolet radiation, microwave radiation, by electron beams, gamma radiation or other suitable thermal or non-thermal radiation.
    [0025] The solubility property of thermoplastic polymer in a curable thermosetting resin system, as discussed in this context, can be determined by several known methods, including optical microscopy, spectroscopy, and the like.
    [0026] For a material to be soluble in another material, the difference in its solubility parameters (Δh+ fgxg ugt v«q rgswgpc as possible. The solubility parameter of a polymer can be determined by a calculation based on the method of group contribution described by Van Krevelen (see DW Van Krevelen, Properties of Polymers, 3rd Revised Edition, Elsevier Scientific Publishing, Amsterdam, 1990, Chapter 7, pp 189-224).
    [0027] The solubility parameter of a polymer can also be determined using the Hansen Solubility Parameters (HSP), as a way to predict whether one material will dissolve into the other to form a solution. Hansen's parameters are based on the idea that "like dissolves like", where one molecule is defined as being "like" to another if it binds itself in a similar way.
    [0028] Examples of resin-soluble thermoplastic polymers include, but are not limited to members of the group consisting of cellulose derivatives, polyester, polyamide, polyimide, polycarbonate, polyurethane, poly(methyl methacrylate), polystyrene, polyesteramide, polyamideimide, polyetherimide, polyaramid, polyarylate, polyacrylate, poly(ester) carbonate, poly(methyl methacrylate/butyl acrylate), polyarylether; polyarylsulfone; polyarylether ketone (PAEK) including polyether ketone (PEKK) and polyether ether ketone (PEEK); combinations and copolymers the same.
    A particularly preferred thermoplastic polymer is a polyarylsulfone comprised of ether-linked repeating units and, optionally, thioether-linked repeating units, the units being selected from:—(Ph-A-Ph)—and optionally— (Ph)a —where A is CO or SO2, Ph is phenylene, n = 1 to 2 and may be fractional, a = 1 to 4 and may be fractional, with the proviso that when a exceeds 1, the phenylenes are linked linearly through a simple chemical bond or a divalent group other than —CO— or —SO2—, or are fused together directly or through a cyclic moiety selected from the group consisting of an acidic alkyl group, a (hetero ) aromatic, a cyclic ketone, a cyclic amide, an imide, a cyclic imine and combinations thereof.
    [0030] Furthermore, the polyarylsulfone may have pendant and/or reactive end groups. The pendant and/or end-reactive group is a group reactive with epoxide groups or with a curing agent. Examples of reactive groups are those that provide active hydrogen, such as OH, NH2, NHR' or -SH, where R' is a hydrocarbon group containing up to 8 carbon atoms, or groups that provide crosslinking activity, such as epoxy , (meth)acrylate, (iso)cyanate, isocyanate ester, acetylene or ethylene as in vinyl or allyl, maleimide, anhydride, and oxazoline.
    [0031] In one embodiment, the polyarylsulfone contains repeating units of —(PhSO2Ph)—, wherein the unit —(PhSO2Ph)— is present in the polyarylsulfone in such a proportion that, on average, at least two of said units of —( PhSO2Ph)n— are in sequence on each polymer chain present, and also contain pendant or reactive end groups, as discussed above.
    [0032] In one embodiment, polyarylsulfone is a copolymer containing the following units: X-PhSO2Ph-X-PhSO2Ph ("PES") and (I)X-(Ph)a-X-PhSO2Ph ("PEES") (II)
    [0033] where X is O or S and may differ from unit to unit, and a is 1-4. In some embodiments, the molar ratio of I to II is about 10:90 and 80:20, about 10:90 and 55:45, about 25:75 and 50:50, about 20: 80 and 70:30, from about 30:70 and 70:30, or from about 35:65 and 65:35. In another embodiment, the PES:PEES copolymer has reactive amine end groups.
    [0034] The number average molecular weight of the polyarylsulfone polymer discussed above is preferably in the range of 2,000 to 30,000, especially in the range of 3000 to 15,000, or 3,000 to 13,000. In certain embodiments, the polyarylsulfone polymer has a glass transition temperature (Tg) greater than 150°C as measured by Differential Scanning Calorimetry (DSC). The particular Tg is dependent on the molecular weight of the polymer. Surfactants
    [0035] The surfactant(s) for the binder composition can be selected from nonionic and anionic surfactants or combination of both types.
    [0036] Suitable nonionic surfactants are monoblock or multifunctional block or graft block copolymers comprising hydrophilic and hydrophobic blocks. The non-ionic surfactant may comprise a main chain fraction, hydrophobic blocks and hydrophilic blocks which may be part of the main chain or which protrude substantially or in their entirety from the main chain fraction to form grafts, or a mixture of the two.
    [0037] Suitable hydrophilic blocks are typically derived from polyvalent hydrophilic block precursors. Suitably, hydrophilic blocks are derived from hydrophilic block precursor molecules which are polyols or polyamines. Preferred hydrophilic polymers are polyethylene oxides. Alternatively, poly(ethylene oxide-propylene) or poly(ethylene oxide-butylene) can be used as long as they meet the desired water solubility criteria.
    [0038] Particularly suitable nonionic surfactants are block copolymers such as polyoxamers represented by the following formula: (EO)x - (PO)y - (EO)ze where x, y, z = integers or fractions provided that the ratio of (x+z) for y is 1.32 or greater, or polyoxamines represented by the formula:
    where (a, b, c, d, e, f, g, h = integers or fractions).
    [0039] The nonionic surfactant is characterized by ethylene oxide content that is in the range of 20%-99% by weight, and by having a number average molecular weight in the range of 1000 g/mol -100000 g/mol.
    A suitable anionic surfactant is characterized by the following formula:A—Rem wherein R is an alkyl, or an aryl, or aryl-alkyl, or an alkylene chain having 4-50 carbon atoms (C4 to C50); and A is lithium, sodium, potassium, ammonium, quaternary ammonium or the amine salt of a carboxylic, or sulfonic, or phosphoric acid group.
    [0041] More specific examples of anionic surfactants include, but are not limited to: alkylaryl sulfonate; Dioctyl sulfosuccinate sodium salt; lauryl sulfonate; fatty acid salts; fatty alcohol such as ethoxylate phosphate; and in the Secondary Alkyl Sulphonates (SAS) category - these surfactants contain secondary sulfonate group and show low foaming properties. Optional additives
    [0042] The binder composition may further include additional crosslinking agents, such as aminoplastic, phenolic compounds, azlactones, aziridines, blocked isocyanates and optional additives, such as defoamers, fungicidal rheology control agents, tackifiers, micro or nanofillers inorganic or organic, elastomeric or thermoplastic hardening agents, hardening particles, stabilizers, inhibitors, pigments/dyes, flame retardants, reactive thinners and other additives well known to those skilled in the art to modify the properties of the binder, before and during emulsification, application to the fibrous substrate, infusion and curing of matrix resin. Suitable defoaming agents include, but are not limited to, acetylene diols, silicones and mineral oils. Examples of nanofillers include, but are not limited to, components referred to in the art as nanosilica, oligomeric polyhedral silsesquioxane (POSS), carbon nanotubes (CNTs), boron nitride nanotubes, carbon nanoparticles, carbon nanofibers, nitride nanofibers boron, carbon nanocords, boron nitride nanostrings, carbon nanoribbons, boron nitride nanoribbons, carbon nanofibers, boron nitride nanofibers, carbon nanoneedles, boron nitride nanofibers, carbon nanoblades, nanorods carbon, boron nitride nanorods, carbon nanocones, boron nitride nanocones, carbon nanorolls, boron nitride nanorolls, carbon nanoohms, boron nitride nanoohms, nanoplatelets or nanodots graphite, graphenes, cut/short carbon fibers, carbon black or a combination thereof with or without a partial or full metallic coating or other fullerene materials and combinations thereof.
    [0043] Optional additives, when present, constitute less than 15% based on the total weight of the composition. Fibrous Materials and Preform Fabrication
    [0044] A fibrous material containing from 1% to 190% by weight of the binder composition distributed thereon or coated thereon is contemplated herein.
    [0045] In making a preform, the fiber layers or fabric plies are laid dry in a stacking arrangement. Cutting or slitting the fibrous layers to certain sizes is sometimes necessary prior to the lay-up shaping operation. Thereafter, the molding material is infused with matrix resin in a liquid infusion process, such as RTM, and the infused preform is cured to form a hardened composite part.
    [0046] The liquid binder composition disclosed herein may be distributed as desired throughout the fibrous materials or provided as a surface coating before or during preform molding. The surface coating can be applied to one or both sides of the fibrous layer (eg fabric layer) that is used for laying above the preform. The method of administration may be spraying, liquid immersion, lamination coating, or electrocoating. Electro-coating is possible when the fibrous material is made of conductive fibers, eg carbon fibers. Preferably, the liquid binder composition is provided to the fibrous material as a surface coating. The binder content in the preform is about 20% or less, in some embodiments, 2% - 10% by weight based on the total weight of the preform. The preform is configured to receive liquid resin through resin infusion due to its permeability. This is in contrast to the resin impregnated prepreg layers used in the conventional lay-up type prepreg process, which typically contain 20% - 50% by weight matrix resin.
    [0047] In some cases, higher binder content can be applied to very light weight and highly permeable fibrous products to achieve specific binding performance. For example, fiber products that have an areal weight of less than 5 gsm (grams per square meter) and air permeability value > 200 cm3/cm2/s can contain up to 70% by weight of binder, while products with a areal weight from 5 gsm to 20 gsm may have up to 50% by weight of binder.
    [0048] Binder-containing fibrous layers are dry, flexible, preformable fibrous products that can provide significant advantages over standard prepreg materials due to their longer shelf life and applicability to more complex geometries and flexibility around narrow radius . The presence of the binder ensures the cohesion of the fibers and the integrity of the fibrous material during the cutting/slitting and molding steps. During cutting or slitting, the binder coating or distribution on the fibrous layer prevents the creation of distorted edges that can drastically affect process speed and productivity.
    [0049] The fibrous materials for the formation of the preform can take the form of directional or non-directional continuous or cut aligned fibers, woven or non-woven textiles, knitted fabrics, non-woven mats, cotton fabric, knits, braids, wires, or cables. Non-woven textiles include non-crimped fabric (NCF), which contains unidirectional cords that are sewn together. The cables may or may not touch each other in such a way that gaps are present between the cables, thus providing permeations in the material. The "cable" is a bundle of fiber filaments, the number of which could be thousands. Non-woven mats are formed from randomly arranged fibers that are held together by a binder, i.e., the liquid binder disclosed herein. The fibers in the non-woven mat can be chopped fibers or vortex of continuous fiber strands.
    [0050] Commercial woven or non-woven fiber fabrics or products with areal weight in the range of 1-2000 gsm are suitable. The fibers in the fabric can be any organic or inorganic fibers and mixtures thereof. Organic fibers include aramid fibers, metallized polymer fibers (where the polymer may be soluble or insoluble in the resin matrix), polyparaphenylene terephthalamide or inorganic fibers or a combination thereof. Inorganic fibers include glass fibers such as "E", "A", "E-CR", "C", "D", "R", "S" or quartz fibers, or fibers made from alumina , zirconia, silicon carbide, metallized glass, other ceramic materials or metals. Particularly suitable as reinforcing fibers are carbon-based fibres, including graphite fibres. Graphite or carbon fibers can also be metallized (with discontinuous or continuous metal layers). Examples of commercially available graphite fibers include those supplied by Cytec under the tradenames T650-35, T650-42 and T300; those supplied by Toray under the tradenames T1000 and T800-H; those supplied by Hexcel under the trade names AS4, AU4, IM9, IM8 and IM 7; and those supplied by Toho Tenax under the trade name IM60.
    [0051] The simplest lay-up modeling method is the manual lay-up, but this is quite cumbersome. Thus, it would be more efficient to manufacture the dry preform through an automated lay-up process, such as automated lamination through tape (ATL) or automated fiber placement (AFP). Automated Lamination Through Tape (ATL) and Automated Fiber Placement (AFP) are processes that use computer-guided robotics to attach one or several layers of fiber ribbons or cables to a mold surface to create a part or structure.
    [0052] Automated fiber placement (AFP) involves laminating fibers in the form of "cables" onto the surface of a molding tool that defines the shape of the portion of the composite to be fabricated. Cables are composed of fiber filaments and are usually wound on a spool. Cable is defined as a series of adjacent strips on the surface of the molding tool by a fiber placement head that moves relative to the tool under computer control to form a laminate as it accumulates layers of cables on the tool. The cable is fed through a laminator over the fiber laying head to compress the cable against the mold tool as it is placed. The laying head may include heating means to effect the connection in situ as the cable is laminated.
    [0053] Automated Laminating Through Tapes (ATL) is an even faster automated process in which tape, rather than individual cables, is continuously laminated to form parts. Tape is an elongated strip of fibrous materials with a narrow width, for example a width ranging from about several inches wide to as low as % of an inch. The ribbon laminating head may include a ribbon spool or spools, a winder, winder guides, a compaction shoe, a position sensor, and a ribbon cutter or cutter. The head can be located at the end of a multi-axis articulating robot that moves around the chuck or tool to which material is being applied, or the head can be located in a gantry suspended above the tool. Alternatively, the tool or chuck can be moved or rotated to provide head access to different sections of the tool. Tape is applied to a running tool that consists of a line of material of any length, at any angle. Several courses are generally applied together over an area or pattern and are defined and controlled by machine control software.
    [0054] ATL is generally used for manufacturing flat parts or parts that have a smooth curvature, while AFP is used for manufacturing parts with a more complex surface geometry. Automated procedures such as those described above tend to be more accurate and more efficient than traditional manual lay-up modeling techniques.
    [0055] A technological challenge associated with such automated processes is the need for a binder composition that can provide integrity and cohesion to the fiber layers during the cutting, handling and laminating stages. The liquid binder composition described herein is believed to meet the physical, thermomechanical and process requirements for ATL and AFP.
    [0056] To form a preform through the processes of ATL and AFP, the fibrous materials are dried in the form of tapes and cables, respectively. An application of the liquid binder composition is described herein, to form binder coated tapes for ATL or binder coated cables for AFP. To make tapes for ATL, liquid binder can be applied to one or both surfaces of a dry fabric blanket (eg, by spraying) to form a coated fabric, and then the binder coated fabric is cut into elongated ribbons. The presence of the binder helps maintain the cohesion of the fabric material during the cutting process and prevents wear. To form a preform through AFP, the fibrous filament tows are individually coated with the liquid binder composition prior to the lamination process. The binder coating provides tackiness so that the tapes and cables remain in a stationary position during the lamination process. As such, the bonding coating promotes the adhesion of the first laminated tape or cable to the surface of the tool, as well as facilitating the attachment of a previously laminated tape or cable.
    [0057] In summary, the advantages associated with fibrous materials or fabrics that have been coated with the liquid binder composition of the present invention include: (i) self-bonding ability (or tackiness) over a wide temperature range (e.g., 70°C °C -210°C) and pressure levels (eg 10 N -1500 N); (ii) Coated fibrous materials free from tackiness at room temperature; (iii) Good in plane and through resin/air permeability for thickness ;(iv) Not limited to any shrinkage;(v) Anti-wear behavior (ie, no excessive pile on the edges) during the cutting and rolling process steps. EXAMPLES
    [0058] The following examples are presented to further illustrate the exemplifying binder compositions and methods of preparation, but are not to be construed as limiting the invention which is outlined in the appended claims. Example 1
    The liquid binder compositions were prepared based on the compositions shown in Table 1. All values are percentages by weight, (% by weight).

    [0060] The anionic surfactant, alkyl aryl sulfonate, is based on the natural ethoxylated chain extended fatty acid. Polyoxamer nonionic surfactant is an AB-type block copolymer of Polyethylene Oxide (PEO) and Polypropylene Oxide (PPO) with an average molecular weight in the range of 8000-18000 Da. Polyoxamine nonionic surfactant is an alkoxylated aliphatic diamine with an average molecular weight of about 18000-25000 Da.
    [0061] With regard to nonionic surfactants, while polyethylene oxide blocks have a hydrophilic behavior, polypropylene oxide blocks ensure a strong hydrophobic behavior and better affinity for the binder composition, thus improving the stability of the dispersion .
    [0062] Liquid binder compositions were prepared by dissolving the thermoplastic polymer in the epoxy resins by applying heat to form a homogeneous molten mixture. A mixture of surfactants was then added to the molten mixture, and the resulting mixture was poured into the container of a Dispermat VMA CN30 high shear mixing device equipped with an open vessel connected to a recirculating heating system and operating at a range of shear rate of 3005,500 rpm. The blends were then emulsified in the blender according to the process conditions shown in Table 2.

    [0063] Initially, the mixture was set at a relatively low speed while gradually adding deionized water. Water dispersibility within the resulting mixture was continuously monitored up to the point of inversion, when a higher shear rate was applied to reduce particle size and to ensure optimal emulsion homogenization and stability. A sufficient amount of deionized water was then added to the emulsion to reach the target solids content. Typical physical properties of the emulsion are shown in Table 3.

    [0064] Dynamic viscosity was measured according to the standard method DIN EN ISO 3219 using a Bohlin viscometer at a shear rate of 25 s-1 at room temperature. The particle size distribution was measured using a Malvern Nanosizer S, which operates in the 0.6 nm - 6000 nm range. Example 2
    The binder compositions described in Example 1 were used for dipping-coating a unidirectional uncorrugated fabric sewn with polyester of approximately 200 gsm (Saertex, Germany).
    [0066] For comparison purposes, a number of commercially available binders were also used to dip coated sheets of the same unidirectional uncrimped fabric. FILCO 8004 (EP1) and 345HP (EP2) are two epoxy-in-water emulsions having 63% and 53% solids content respectively (available from COIM Italy). HYDROSIZE PA845 (PA1) and U2022 (PU1) are respectively water dispersions of polyamide 4.6 at 23% solids and polyurethane at 59% solids (available from Michelman, USA). NEOXIL NX962D (EP3) is a bisphenol-A based epoxy emulsion in water with 54% solids (available from DSM).
    [0067] All fabrics coated with binders were dried for 3 minutes at 100°C and for a further 4 minutes at 130°C in an oven.
    [0068] Binder coated fabrics were evaluated for drape ability, anti-wear behavior, shrinkage, and self-bonding ability.
    [0069] Draping was determined by hot draping at 145°C (temperature ramp rate of 3°C/min from room temperature) for 1 minute on a coated fabric 350x350 mm over a conical tool (height = 86 mm, inner diameter = 120 mm, outer diameter = 310 mm) under vacuum (60 mmHg vacuum during the test) and fgVgtmkpc>«q fq puogtq fg xipeqUo Qu ocVgriciu eqo 0 8 xipequ fotcm considered excellent (E), the resulting materials in 7-12 creases were considered acceptable (A), while materials that produced more than 12 creases were considered unacceptable (U). The anti-wear behavior was determined in a developmental tension-controlled pile test having four sections (unwinder, friction rollers, catch plate and reel) running at a speed of 20 m/min. The amount of fluff accumulated on the capture plate over a 5 minute period was weighed and the materials sorted accordingly. Fluff is the debris released by cables that rub against the friction laminators and is collected by the capture plate. Materials resulting in more than 500 mg of fluff were considered unacceptable (U), materials between 200 and 500 mg were considered acceptable (A), while materials creating less than 200 mg of fluff were considered excellent (E). Shrinkage was determined by measuring the width of the pristine coated fabric and bound after a heat treatment (3 minutes at 100°C + 4 minutes at 130°C). Materials resulting in less than 1% shrinkage were considered excellent (A), materials yielding 12% shrinkage were considered acceptable (B), while materials yielding more than 2% shrinkage were considered unacceptable (C). Self-bonding capability was determined by applying a pressure of 10N using a compaction laminator at a temperature of 100°C for 5 seconds. The results are shown in Table 4.

    [0070] None of the commercial binders based on epoxy (EP1, EP2 and EP3) and binders based on thermoplastics (PA1 and PU1) proved to be effective in maximizing the physical parameters of tissue evaluated. Although a good level of drape and a limited level of shrinkage were measured for most fabrics coated with commercial binders, no significant effect on rope integrity and corresponding pile levels was observed. Only PU1 and EP3 showed a very limited self-binding ability when applied at 3% by weight.
    [0071] In contrast, when the binder compositions (1a-1h) described in Example 1 were applied to the dry unidirectional fabric, excellent anti-fluff behavior and drapeability, good self-bonding performance, and no shrinkage were observed. Furthermore, it has been found that the self-bonding performance can be improved by increasing the binder content up to 10% by weight. Example 3 Comparative example - Effect of binder composition on the binding ability of different fiber products
    [0072] The binder composition (1d) described in Example 1 was used for dipping-coating a non-woven carbon-fiber veil in film weight of 3 gsm (grams per square meter). The binder coated with binder was dried and stabilized in an oven for four minutes at 130°C. It was found that application of 3 gsm of the disclosed binder composition produced a homogeneous coating on each carbon fiber and created microsized resin-rich pockets at the intersection between two or more fibers. FIG. 1 shows a micrograph of the coated carbon fiber web. The homogeneous coating, as indicated by the gloss coating and films between the fibers, can be seen in FIG. 1.
    [0073] A plurality of unidirectional Toho Tenax IMS65 carbon fibers were held unidirectionally in position over the coated web, and the assembly was subjected to a pressure of approximately 10N when passing through a laminator nip at a temperature of approximately 90-100°C for a few seconds to assess the binding capacity and stability of the product. It was found that the set showed excellent stability and showed the ability to maintain its structure, even at narrower angles and when subjected to a low compression force.
    [0074] For comparison, samples of the same carbon-fiber veil were coated using the commercial binders (EP1, EP2, EP3, PA1, PU1) from Example 2 at similar binder contents (about 4-10 gsm). A plurality of strands of carbon filaments were held unidirectionally in position over each of the coated webs, and the assemblies were subjected to the same test discussed above. None of the assemblies evaluated on the basis of commercial binders reached the sufficient level of binding capacity. Example 4
    [0075] Each of the binder compositions (1a-1h) described in Example 1 was used for dipping-coating the same unidirectional uncorrugated fabric described in Example 2, at room temperature. The coated fabrics were then dried for 3 minutes at 100°C and then for a further 4 minutes at 130°C in an oven.
    [0076] Each of the binder coated non-corrugated fabrics was then cut into smaller layers, and the layers were laminated in a stacking sequence to form a mold. The mold was then precast in an oven at 130°C for 30 minutes and infused with Prism® EP2400 (hardened epoxy system available from Cytec Engineered Materials). Panels (5a-5h) having a Vf (fiber volume fraction) in the range of 55% - 57% were produced after curing the infused preforms at 180°C for 2h.
    [0077] For comparison purposes, the same pristine unidirectional uncurled fabric (uncoated) was used to prepare an identical test panel (Control 1). A variety of mechanical tests including 0 compression modulus of steering (0 CM) and force (0 CS) and interlaminar shear strength (ILSS) were performed on all panels and the results are shown below in Table 5.

    [0078] The application of the binder compositions (1a-1h) described in Example 1 proved to be substantially neutral, and, in some cases, advantageous for the mechanical performance of the composite. Small reductions in glass transition temperature (Tg) compared to the unmodified baseline (Control 1) were also observed.
    权利要求:
    Claims (12)
    [0001]
    1. Liquid binder composition for binding fibrous materials, characterized in that it comprises: a) one or more multifunctional epoxy resins; b) a polyarylsulfone polymer; c) one or more surfactants selected from: (i) surfactant nonionic, which is monoblock or multifunctional block or graft copolymers comprising hydrophilic and hydrophobic blocks; (ii) anionic surfactant, which is represented by the following formula: A-Rem wherein R is an alkyl, aryl, aryl group -alkyl, or an alkylene chain having 4-50 carbon atoms (C4 to C50); and A is lithium, sodium, potassium, ammonium, quaternary ammonium amine salt of a carboxylic, or sulfonic, or phosphoric acid group; and(iii) a combination of nonionic surfactant and anionic surfactant; and d) water, wherein said composition is free of organic solvents, and wherein said polyarylsulfone polymer is composed of ether linked repeating units and optionally thioether linked repeating units, the units being selected from: e) -PH-A-PH)-e optionally f) PH)a-where A is CO or SO2, PH is a phenylene group, A = 1 to 4 and may be fractional, provided that when A exceeds 1, the phenylenes are linearly linked through a simple chemical bond or a divalent group other than -CO- or -SO2-, or are fused together directly or through a cyclic moiety selected from the group consisting of an acidic alkyl group, a aromatic (hetero) group, a cyclic ketone, a cyclic amide, an imide, a cyclic imine and combinations thereof.
    [0002]
    2. Liquid binder composition according to claim 1, characterized in that said polyarylsulfone further comprises one or more pendant or reactive end groups selected from: OH, NH2, NHR' or -SH, where R' is a hydrocarbon group containing up to 8 carbon atoms, epoxy, (meth)acrylate, (iso)cyanate, isocyanate ester, acetylene, ethylene, maleimide, anhydride, and oxazoline.
    [0003]
    3. Liquid binder composition according to claim 2, characterized in that said polyarylsulfone contains repeating units of —(PhSO2Ph)—, wherein the unit —(PhSO2Ph)— is present in the polyarylsulfone in such a proportion that On average, at least two of said units of —(PhSO2Ph)— are in sequence in each polymer chain present.
    [0004]
    4. Liquid binder composition according to claim 1, characterized in that the polyarylsulfone is a copolymer containing the following units: X-PhSO2Ph-X-PhSO2Ph ("PES") and (I)X-(Ph)aX -PhSO2Ph ("PEES") (II)where X is O or S and may differ from unit to unit, and A is 1-4.
    [0005]
    5. Liquid binder composition according to any one of claims 1 to 4, characterized in that said polyarylsulfone polymer has a glass transition temperature (Tg) greater than 150°C, as measured by Differential Scanning Calorimetry ( DSC).
    [0006]
    6. Liquid binder composition according to any one of claims 1 to 5, characterized in that the nonionic surfactant comprises a main chain fraction, and the hydrophobic and hydrophilic blocks are part of the main chain or substantially project from the fraction of main chain to form grafts, or combinations thereof.
    [0007]
    7. Fibrous material, characterized in that it comprises a binder composition distributed thereon or coated thereon, wherein said fibrous material is selected from: a woven or non-woven textile; a non-woven layer of randomly arranged fibers, fiber cables, yarns, braids, textile tape suitable for automated fiber placement (AFP) and/or automated lamination through tapes (ATL), and wherein said binder composition comprises a composition as defined in claim 1.
    [0008]
    8. Fibrous material according to claim 7, characterized in that the non-ionic surfactant comprises a main chain fraction, and the hydrophobic and hydrophilic blocks are part of the main chain or substantially protrude from the main chain fraction to form grafts , or combination thereof.
    [0009]
    9. Fibrous material according to claim 7 or 8, characterized in that the fibrous material is a non-corrugated fabric and said binder composition is coated on at least one surface of the fabric.
    [0010]
    10. Fibrous material according to any one of claims 7 to 9, characterized in that the binder composition is present in an amount within the range of 1% to 20% by weight based on the total weight of the material, and the material is permeable to liquid resin.
    [0011]
    11. Infusible resin preform, characterized in that it comprises a set of fibrous materials, wherein the fibrous materials are held together by the binder composition of any one of claims 1 to 6, wherein the amount of binder composition in the preform is up to 10% by weight based on the total weight of the preform.
    [0012]
    12. Infusible resin preform according to claim 11, characterized in that the fibrous materials are selected from: a woven or non-woven textile; a non-woven layer of randomly arranged fibers, fiber tows, yarns, braids, textile tape suitable for automated fiber placement (AFP) and/or automated lamination through tapes (ATL), and combinations thereof.
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    同族专利:
    公开号 | 公开日
    MX364967B|2019-05-16|
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    CN104870558A|2015-08-26|
    EP2906631A1|2015-08-19|
    AU2013364261C1|2017-03-23|
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    EP3219759B1|2020-11-25|
    TW201425513A|2014-07-01|
    US20180155542A1|2018-06-07|
    JP2016506455A|2016-03-03|
    WO2014099050A1|2014-06-26|
    EP3219759A1|2017-09-20|
    CA2895682C|2020-03-31|
    CN104870558B|2018-03-23|
    AU2013364261A1|2015-05-07|
    KR20150097474A|2015-08-26|
    ES2640717T3|2017-11-06|
    JP6485975B2|2019-03-20|
    US20140179187A1|2014-06-26|
    CA2895682A1|2014-06-26|
    TWI579359B|2017-04-21|
    AU2013364261B2|2016-11-24|
    JP2017197901A|2017-11-02|
    BR112015014780A2|2017-07-11|
    MY169941A|2019-06-18|
    RU2621764C2|2017-06-07|
    EP2906631B1|2017-06-21|
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    法律状态:
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    2021-04-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-11| 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 29/08/2013, OBSERVADAS AS CONDICOES LEGAIS. |
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    US201261739748P| true| 2012-12-20|2012-12-20|
    US61/739,748|2012-12-20|
    PCT/US2013/057197|WO2014099050A1|2012-12-20|2013-08-29|Liquid binder composition for binding fibrous materials|
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