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    • 专利摘要:
    COMPOSITE RESIN AND FIBER SHEET, COMPOSITE ARTICLE, FOLDED CORE STRUCTURE AND STRUCTURAL SANDWICH PANEL. The present invention relates to a composite sheet of resin and fiber comprising a fibrous reinforcing substrate and a resin coated on or within the substrate, the resin comprising a first thermoplastic polymer and a second thermoplastic polymer, where (i) the first and the second polymer form a mixture of two phases, (ii) the first polymer which is thermoplastic, has a melting point of 75 to 400 ° (degree) C and forms a continuous or co-continuous phase with the second polymer, ( iii) the second polymer is dispersed in the continuous or co-continuous phase of the first polymer, which has an effective diameter from 0.01 to 15 micrometers and has a melting point of 25 to 350 ° (degree) C, (iv ) the first polymer comprises from 35 to 99% by weight of the combined weight of the first and the second polymer in the mixture, (v) the second polymer has a melting point of at least 5 ° (degree) C lower than the melting point of the first polymer, and (vi) the substrate reinforcing fibers are fibers which have a toughness of 3 and 60 grams per dtex (...).
    公开号:BR112014021166B1
    申请号:R112014021166-3
    申请日:2013-02-22
    公开日:2021-01-26
    发明作者:Olivier Rozant；Louis Boogh；Olivier Magnin
    申请人:E.I. Du Pont De Nemours And Company；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention relates to a high strength core structure produced from a fibrous substrate. The core structure can be in the form of a honeycomb core or a folded core. BACKGROUND OF THE INVENTION
    [002] The core structures for sandwich panels produced from fibrous substrates of paper or high-resistance fabric, mostly in the form of honeycomb, are used in different applications, but mainly in the aerospace and transport industries of mass, in which the proportions of resistance to weight or stiffness to weight have high values. For example, US patent 5,137,768 to Lin describes a honeycomb core produced from a fibrous, high density, nonwoven wet deposition substrate comprising 50% by weight of p-aramid fibers with the rest of the composition being a binder and other additives. An example of such a honeycomb core is the Kevlar® core. Similar cores can also be produced using the m-aramid fiber in place of the p-aramid fiber. An example of this type of honeycomb core is the Nomex® core.
    [003] US patent 5,527,584 to Darfler et al., Describes the honeycomb nuclei, in which the cell walls comprise the tissues. The specific weaving pattern, filament size and trailer size can be varied widely, depending on the structural strength and weight required for the honeycomb structure. A simple weave is a suitable weave style.
    [004] US patent 6,245,407 to Wang et al., Describes the resins, which are a combination of phenolic polymers and polyamide, which are used as immersion resins for the coating honeycomb structures.
    [005] The thermoplastic honeycomb can be produced using techniques such as heat generation or ultrasonic. These methods are described in US patents 5,039,567; 5,421,935 and 5,217,556. This type of process is more efficient than the expansion or corrugation processes used to manufacture the honeycomb from paper or fabric substrates.
    [006] There is a continuing need to improve the effectiveness of core structures produced from paper or fabric substrates, without adversely affecting the mechanical properties of the structure. This is particularly true for structures used in airplanes, trains and boats. Laser welding of a core structure is an approach to increase production efficiency. BRIEF DESCRIPTION OF THE INVENTION
    [007] The present invention relates to a composite sheet of resin and fiber comprising a fibrous reinforcing substrate and a resin coated on or within the substrate, the resin comprising a first thermoplastic polymer and a second thermoplastic polymer, wherein, ( i) the first and the second polymer form a mixture of two phases, (ii) the first polymer which is thermoplastic, has a melting point of 75 to 400 ° C and forms a continuous or co-continuous phase with the second polymer. (iii) the second polymer is dispersed in the continuous or co-continuous phase of the first polymer, which has an effective diameter from 0.01 to 15 micrometers and has a melting point of 25 to 350 ° C, (iv) the first polymer comprises from 35 to 99% by weight of the combined weight of the first and the second polymer in the mixture, (v) the second polymer has a melting point of at least 5 ° C lower than the melting point of the first polymer, and ( vi) the substrate reinforcing fibers are fibers that have a toughness of 3 and 60 grams per dtex and a filament diameter of 5 to 200 micrometers.
    [008] The present invention also relates to a composite article comprising a composite sheet of resin and fiber. BRIEF DESCRIPTION OF THE FIGURES
    [009] Figures 1A and 1B are representations of the views of a honeycomb in hexagonal shape.
    [010] Figure 2 is a representation of another view of a honeycomb in a hexagonal cellular format.
    [011] Figure 3 is an illustration of honeycomb with face sheets (s).
    [012] Figure 4 is an illustration of a bent-core structure.
    [013] Figure 5 is a sectional view of an article, comprising a plurality of substrates and an energy absorbing layer. DETAILED DESCRIPTION OF THE INVENTION COMPOSITE SHEET
    [014] The present invention relates to a composite sheet of resin and fiber comprising a fibrous reinforcing substrate and a coated resin on or within the substrate. The substrate can be in the form of a paper or fabric. SUBSTRATE
    [015] Preferably, the substrate reinforcing fibers have a filament toughness of 3 and 60 grams per dtex and a filament diameter of 5 to 200 micrometers. In some embodiments, fibers with filament diameters from 7 to 32 micrometers are preferred. In other embodiments, the filament toughness is from 8 and 60 grams per dtex. In some embodiments, the substrate is a paper.
    [016] A preferred paper contains high strength fibers and a binder. In one embodiment, the paper comprises from 10 to 100% by weight of fibers and, correspondingly, from 0 to 90% by weight of binder. In another embodiment, the paper comprises from 10 to 85% by weight of fibers and from 15 to 90% by weight of binder. In yet another embodiment, the paper comprises from 50 to 100% by weight fibers and from 0 to 50% by weight of binder.
    [017] The high strength fibers of the paper have an initial Young's modulus of at least 180 grams per dtex (200 grams per denier) and a tenacity of 11 grams per dtex (10 grams per denier) at 56 grams per dtex (50 grams per denier). In one embodiment, the length of the fibers in the paper is from 0.5 to 26 mm. In another embodiment, the length of the fibers is from 1 to 8 mm, and in yet another embodiment, the length of the fibers varies from 1.5 mm to 6 mm.
    [018] The reinforcement substrate may also include the lower strength fibers and the module mixed with the upper modulus fibers. The amount of lower strength fibers in the mix will vary from case to case, depending on the desired strength of the core structure. The greater the amount of lower strength fiber, the lower the strength of the core structure. In a preferred embodiment, the amount of fibers of lower strength should not exceed 30%. An example of such lower strength fibers is poly (ethylene terephthalamide) fiber or cellulose.
    [019] The reinforcement substrate may contain small amounts of inorganic particles and representative particles include mica, vermiculite, and the like; the addition of these performance-enhancing additives can provide properties such as improved fire resistance, thermal conductivity, dimensional stability and the like for the substrate and therefore for the final core structure.
    [020] In some embodiments, the thickness of the paper is from 12 to 1,270 micrometers (0.5 to 50 mils), and the base weight of the paper is from 10 to 900 grams per square meter (0.29 to 230 ounces per square yard). The paper can be a single sheet or a plurality of sheets, which have been laminated together.
    [021] The fibers that comprise the paper can be in the form of cut fiber (flakes) or paper pulp, used alone or in combination.
    [022] Flake, in general, is produced by cutting continuous spun filaments into pieces of specific lengths. If the length of the flake is less than 0.5 mm, in general, it is too short to provide paper with adequate strength. If the flake length is greater than mm, it will be very difficult to form uniform wet deposition substrates. A flake that has a diameter of less than 5 μm and, in particular, less than 3 μm, is difficult to produce with cross-sectional uniformity and adequate reproducibility. If the flake diameter is greater than 20 micrometers, it will be very difficult to form uniform articles of light to medium base weights.
    [023] The term "pulp", as used herein, means particles of fibrous material that have a stem and fibrils that, in general, extend from there, in which the stem, in general, is columnar, and about 10 to 50 micrometers in diameter and the fibrils are hair-like members, thin, in general, attached to the stem measuring only a fraction of a micrometer or just a few micrometers in diameter and about 10 to 100 micrometers in length . A possible illustrative process for the manufacture of aramid pulp is described in US patent 5,084,136.
    [024] A preferred linker is fibrids. The term "fibrids", as used herein, means a very finely divided polymer product of small, membranous particles, essentially in two dimensions with a length and width in the range of 100 to 1,000 μm and a thickness only in the range of 0, 1 to 1 μm. Fibrids are normally produced by continuously flowing a polymer solution in a coagulating liquid bath that is immiscible with the solution's solvent. The flow of the polymeric solution is subjected to intense shear forces and turbulence as the polymer is coagulated. The preparation of fibrids is taught in US patent 3,756,908, with a general discussion of the processes that can be found in US patent 2,999,788. Fibrids must be refined in accordance with the teachings of US patent 3,756,908, only to the extent necessary to allow the densification and permanent saturability of the final paper.
    [025] Preferred polymers for fibrids in the present invention include aramides (poly (m-phenylene isophthalamide) and poly (p-phenylene terephthalamide)). Other binders include polysulfonamide (PSA), polyphenylene sulfide (PPS) and polyamides. Other binder materials, in general, are in the general form of resins and can be epoxy resins, phenolic resins, polyureas, polyurethanes, melamine-formaldehyde resins, polyesters, polyvinyl acetates, polyacrylonitriles, alkyd resins, and the like. Preferred resins are water-dispersible and thermoset. Most preferably resin binders comprise water-dispersible epoxy resins. The binder can also be derived from a biological source. An example of such a polymer is that based on 1,3-propanediol, the diol component being manufactured through a corn sugar fermentation process. Soy is another source of biological binding material.
    [026] The composition of fibers and fibrids may vary. Preferred types of fibers include aromatic polyamide, liquid crystal polyester, polybenzazole, polypyridazole, polysulfonamide, polyphenylene sulfide, polyolefins, carbon, glass, ceramics, basalt and other inorganic fibers or mixtures thereof.
    [027] Preferred types of fibrids include aromatic polyamide, aliphatic polyamide, polysulfonamide (PSA), polyphenylene sulfide (PPS), polyimide and mixtures thereof.
    [028] Suitable aromatic polyamides are meta-aramid and para-aramid. A suitable meta-aramid polymer is poly (m-phenylene isophthalamide) and a suitable para-aramid polymer is poly (p-phenylene terephthalamide).
    [029] Papers manufactured using fibrids and short fibers have been described in US patent 3,756,908, to Gross and US patent 5,137,768 to Lin.
    [030] A commercially available high modulus p-aramid high strength fiber-reinforced paper substrate for the production of core structures is Kevlar N636® paper marketed by E.I. DuPont from Nemours and Company, Wilmington, DE. The core structures can also be produced from the non-woven substrate of m-aramid fiber also available from DuPont under the trade name NOMEX®.
    [031] A paper substrate can also comprise cellulose, as exemplified by Kraft paper. Cellulose can also be present in a paper that comprises a mixture of cellulosic fibers of p-aramide and / or m-aramide. A paper can also comprise polyester or glass fibers, alone or in combination with other fibers.
    [032] Once the paper is formed, it is calendered to the desired density or left uncalendered depending on the target's final density.
    [033] In some embodiments, the fiber reinforcing substrate is a fabric material that comprises continuous filament yarns. The term "fabric" means the structures that can be woven, unidirectional, can be multiaxial, 3-dimensional or a randomly oriented non-woven staple fiber blanket. Each of these styles of fabric is well known in the art. A number of different fabric weave patterns including plain, twill, satin, short satin, single derivative, simulated and simulated handkerchief can be used. Simple weave patterns are preferred. Carbon, ceramic, glass or basalt fibers are the preferred fibers for fabrics. In some embodiments, the fabric filaments are made of aromatic polyamide or aromatic copolyamide. The wires can be connected and / or twisted. For the purposes of the present invention, the term "fiber" refers to a relatively flexible, macroscopically homogeneous body that has a high ratio of length to width over its entire cross-sectional area perpendicular to its length. The filament cross section can be of any shape, but in general it is circular or bean shaped. At present, the term "fiber" is used interchangeably with the term "filament". A "thread" is a plurality of filaments. The filaments can be of any length. The multifilament yarn spun on a bobbin in a bundle contains a plurality of continuous filaments. The multifilament yarn can be cut into staple fibers and transformed into a spun yarn suitable for use in the present invention. The staple fiber may have a length of about 3.8 cm to about 12.7 cm (1.5 to about 5 inches). The staple fiber can be linear (that is, without pleats) or with pleats to have a sawtooth-like pleat along its length, with a pleat frequency (or repeated fold) of about 1.4 to about of folds by 7.1 cm (about 3.5 to about 18 folds per inch).
    [034] Other fiber formats suitable for some of the fabrics include broken or mixed stretch yarns.
    [035] In other embodiments, the fabric is a non-woven blanket that comprises randomly oriented discontinuous filaments, in which the filaments are linked or interconnected. An example of a nonwoven blanket includes felts and hydroentangled or continuous spinning sheets. POLYMERIC RESIN COATING
    [036] A polymer resin is coated on or inside the reinforcement substrate. In some embodiments, the resin only partially impregnates the substrate. The coating resin comprises a first thermoplastic polymer and a second thermoplastic polymer. The first and second polymers form a mixture of two phases. The first polymer comprises from 35 to 99% by weight of the mixture of the first and the second polymer. In some embodiments, the first polymer comprises from 45 to 85% by weight or even from 45 to 70% by weight of the mixture of the first and the second polymer. The composite sheet may optionally comprise a third polymer.
    [037] In addition, the first or second polymers, optionally, may comprise alone or in combination, reactive or non-reactive additives, such as dyes, diluents, processing agents, UV additives, fire retardants, mineral excipients, excipients organic, binding additives, surfactants, pulp, antioxidants, antistatic agents, gliding agents and adherents. The suitable pulp is aramid pulp. The methods for incorporating these additives into the polymer are well known.
    [038] Suitable flame retardants include brominated flame retardants, red phosphorus, asbestos, antimony trioxide, borates, metal hydrates, metal hydroxides, tetrakis (hydroxymethyl) phosphonium salts, fluorocarbons or combinations thereof.
    [039] At least one plasticizer can optionally be added to the polymer, preferably to the second polymer. Suitable examples include phthalate-based plasticizers, trimellate-based plasticizers, adipate-based plasticizers, sebacate-based plasticizers, maleate-based plasticizers, organophosphate-based plasticizers, sulphonamide-based plasticizers benzoate, epoxidized vegetable oils, poly (ethylene oxide) or their combinations. In some embodiments at least one plasticizer is a plasticizer with a reactive group, such as an epoxidized vegetable oil. Examples of epoxidized vegetable oils are epoxidized soybean oil (ESO), epoxidized linseed oil (ELO), epoxidized talate, or combinations thereof.
    [040] The polymeric resin coating, as described herein, provides a coated substrate that is amenable to processing through laser welding techniques. FIRST POLYMER
    [041] The first and second polymers belong to a group of polymers with good mechanical properties and good chemical resistance. These resins are often referred to in the trade as High Performance Polymers or Engineering Thermoplastics. Some rubbers and elastomers also fall into this category of material.
    [042] The first polymer is a thermoplastic polymer that has a melting point of 75 to 400 ° C. In some embodiments, the first polymer has a melting point of 110 ° C to 300 ° C or even from 140 ° C to 230 ° C. The first polymer forms a continuous or co-continuous phase with the second polymer. The continuous phase, as defined by the International Union of Pure and Applied Chemistry (IUPAC), refers to a matrix, in which the second phase is dispersed in the form of particles. The co-continuous phase, as described by IUPAC, is a matrix that is a semi-penetrating polymer network (SIPN) or a polymer interpenetrating network (IPN). A semi-penetrating polymer network is a polymer comprising one or more polymer network (s) and one or more linear or branched polymer (s) characterized by penetration on a molecular scale of at least one of the networks through at least some of the straight or branched chains. An interpenetrating polymer network is a polymer comprising two or more networks, which are at least partially interlaced on a molecular scale, but are not covalently linked together and cannot be separated unless the chemical bonds are broken. The second polymer forms a dispersion within the first polymer, or a co-continuous network within the first polymer. The first polymer provides the greatest contribution to the thermal and mechanical performance of the composite. Preferably, the first polymer should have a melting point that is higher than the peak operating temperature of the article comprising the composite sheet. The peak operating temperature is defined as the maximum temperature to which the article is exposed when in service. The peak operating temperature varies depending on the particular application for which the polymer is used. Other factors that affect the peak operating temperature are the climatic situation, geographical area and / or seasonal fluctuations encountered, as well as the proximity to a heat source. In some embodiments, the first polymer must have a melting point that is at least 5 ° C higher than the peak operating temperature. In other embodiments, the first polymer must have a melting point that is at least 10 ° C higher than the peak operating temperature.
    [043] Preferably, the first polymer is polyolefin, polycondensate, or an elastomeric block copolymer.
    [044] Examples of elastomeric block copolymers are acrylonitrile-butadiene-styrene, polyisopropene-polyethylene-butylene-polystyrene or polystyrene-polyisoprene-polystyrene block copolymers, or combinations thereof.
    [045] Other suitable polymers include polyamides, polyamide copolymers, polyimides, polyesters, polyurethanes, polyurethane copolymers, polyacrylics, polyacrylonitriles, polysulfones, silicone copolymers.
    [046] In some embodiments, preferably, the first polymer is polyamide, polyester, polyester copolymers or combinations thereof. A preferred polyolefin is polypropylene.
    [047] In some other embodiments, preferably, the first polymer is a polyamide such as an aliphatic polyamide or a semi-aromatic polyamide. Preferred polyamides are those that have a final amine content of at least 30%, more preferably at least 50%, most preferably at least 70%. Preferably, suitable aliphatic polyamides are nylon 6, nylon 66, nylon 6/66, nylon 11, nylon 12, nylon 612, nylon 13, nylon 1010, or combinations thereof. Most preferably, suitable aliphatic polyamides are nylon 6, nylon 11, nylon 12, nylon 612, nylon 13, nylon 1010, or combinations thereof.
    [048] Preferred semi-aromatic polyamides are Nylon 6T, Nylon 6 / 6T, Nylon 3T, Nylon 6 / 3T, 66 / 6T Nylon, Nylon 10 / 6T, 12 / 6T Nylon, Nylon 10 / 3T, 12 / 3T Nylon, and / or their combinations.
    [049] Amorphous polyamides can preferably be used in a range of up to 10% by weight based on the total weight of the polyamides. Preferably, it is the use of crystalline, semi-crystalline polyamides or their combinations. SECOND POLYMER
    [050] The second polymer is dispersed in the continuous or co-continuous phase of the first polymer and has an effective diameter of 0.01 to 15 micrometers.
    [051] When the second dispersed thermoplastic polymer is present as spherical particles, the effective diameter is the diameter of the particle. When the second dispersed thermoplastic polymer is present as non-spherical particles, such as elongated shapes of spheroids, ellipsoids, or a network of structures similar to branched filaments, the effective diameter is the diameter that can be traced around a plane of the smallest cross-sectional area of the particle.
    [052] The second polymer has a melting point of 25 to 350 ° C. In some embodiments, the melting point of the second polymer is from 50 to 200 ° C. Preferably, the second polymer has a melting point at least 5 ° C below the melting point of the first polymer. In some embodiments, the second polymer has a melting point of at least 10 ° C, 20 ° C, or even 30, 50, 75,100 or 120 ° C lower than the melting point of the first polymer. The second polymer facilitates processing and speed malleability when the composite sheet is being formed into a composite article, for example, during laser welding of a core structure. The second polymer also increases the bond strength between successive fibrous substrates.
    [053] In some embodiments, the largest dimension of the particles is of the same order of magnitude as the smallest dimension of the filaments that comprise the reinforcement substrate.
    [054] In other embodiments, the larger particle size is less than the smallest size of the filaments that comprise the reinforcement substrate. The effective particle diameter of the second polymer is from 0.01 to 15 micrometers. In some embodiments, the diameter is from 0.01 to 5 micrometers, or even 0.01 to 1 micrometer. The term "effective diameter" means the smallest circular diameter that can be circumscribed around the particle's cross section.
    [055] Preferably, the second polymer is polyolefin, polycondensate, or an elastomeric block copolymer.
    [056] Examples of polyolefin polymers are polyethylene, polyethylene copolymers, polypropylene, polypropylene, polybutylene copolymers and polybutylene copolymers.
    [057] Suitable polyethylene polymers include low density polyethylene, very low density polyethylene, metallocene polyethylene and polyethylene copolymers such as ethylene / α, β-unsaturated C3-C8 copolymers and copolymers of ethylene / α, β-unsaturated C3-C8 carboxylic acids partially neutralized with the metal salts.
    [058] When the second polymer is a copolymer of ethylene / α, β-unsaturated C3-C8 carboxylic acid, α, β-unsaturated C3-C8 carboxylic acid can be selected from acrylic acid or methacrylic acid.
    [059] The ethylene / α, β-unsaturated C3-C8 carboxylic acid copolymer is preferably a terylene polymer of ethylene, α, β-unsaturated C3-C8 and α, β-unsaturated C3- C8.
    [060] α, β-unsaturated C3-C8 dicarboxylic acid can be maleic acid, maleic anhydride, maleic acid C1-C4 alkyl esters, fumaric acid, itaconic acid and itaconic anhydride. Preferably, α, β-unsaturated C3-C8 dicarboxylic acid is maleic anhydride, hydrogen maleate acetate and methyl hydrogen maleate. Most preferably, α, β-unsaturated C3-C8 dicarboxylic acid is maleic anhydride, hydrogen maleate or methyl combinations.
    [061] The ethylene dicarboxylic acid / α, β-unsaturated C3-C8 / α, β-unsaturated C3-C8 carboxylic acid can still comprise up to 40% by weight of a C1C8 alkyl acrylate softening comonomer that, preferably, it is selected from methyl (meth) acrylate, ethyl (meth) acrylate or n-butyl (meth) acrylate, most preferably from n-butyl acrylate or ethyl (meth) acrylate.
    [062] The term softening comonomer is well known to those skilled in the art and refers to comonomers, such as C1-C8 alkyl acrylate. The term (meth) acrylate encompasses acrylate and methacrylate.
    [063] In the ethylene / α, β-unsaturated C3-C8 / α dicarboxylic acid, C3-C8 dicarboxylic acid polymer, the C3-C8 α, β-unsaturated carboxylic acid may be present in a range from 2 and 25% by weight and α, β-unsaturated C3-C8 dicarboxylic acid can be present in a range from 0.1 to 15% by weight, with the proviso that α, β-unsaturated carboxylic acid C3-C8 and α, β-unsaturated C3-C8 dicarboxylic acid are present from 4 to 26% by weight, and with the proviso that the total comonomer content, including the C1 alkyl acrylate softening comonomer -C8, does not exceed 50% by weight.
    [064] In other embodiments, the second polymer is a copolymer of ethylene / α, β-unsaturated C3-C8 carboxylic acid partially neutralized with the metal ions, which is usually called an "ionomer". The percentage of total neutralization is from 5 to 90%, preferably from 10 to 70% and, most preferably, between 25 and 60% of the ionomer.
    [065] In the case where the second thermoplastic polymer is a copolymer of ethylene / α, β-unsaturated C3-C8 carboxylic acid partially neutralized with the metal ions, the α, β-unsaturated C3-C8 carboxylic acid may be the acrylic acid or methacrylic acid. The ethylene / α, β-unsaturated C3-C8 carboxylic acid copolymer partially neutralized with the metal ions is preferably a terpolymer of ethylene carboxylic acid, α, β-unsaturated C3-C8 and α dicarboxylic acid , β-unsaturated C3-C8 partially neutralized with the metal ions. The dicarboxylic acid α, β-unsaturated C3-C8 can be selected from the same components, as described above.
    [066] The ethylene carboxylic acid / α, β-unsaturated C3-C8 / α, dicarboxylic acid C3-C8 partially neutralized with metal ions can still comprise up to 40% by weight of a softening comonomer of C1-C8 alkyl acrylate which is preferably selected from the same components, as described above.
    [067] In the polymer of ethylene carboxylic acid / α, β-unsaturated C3-C8 / dicarboxylic acid α, β-unsaturated C3-C8 partially neutralized with metal ions, from 5 to 90% of the total number of units of α, β-unsaturated C3-C8 carboxylic acids in the polymer were neutralized with metal ions, and α, β-unsaturated C3-C8 carboxylic acid and α, β-unsaturated C3-C8 acid may be present in the same quantities, as described above, with the same condition in relation to α, β-unsaturated C3-C8 carboxylic acid and α, β-unsaturated C3-C8 acid and in the same additional condition in relation to the total comonomer content, including the C1-C8 alkyl acrylate softening comonomer, as described above.
    [068] The ethylene / α, β-unsaturated C3-C8 carboxylic acid copolymer is partially neutralized with the metal ions that can be any group I or group II metal ions in the periodic table. Preferred metal ions are sodium, zinc, lithium, magnesium, calcium or a mixture of any of these. Most preferably, the ions are sodium, zinc, lithium or magnesium. Most preferably, the ion is zinc, lithium or their combinations.
    [069] Copolymers of partially neutralized ethylene / α, β-unsaturated C3-C8 carboxylic acids can be prepared using conventional neutralization techniques, as described in US patent 3,264,272. The resulting ionomers have a melt index (MI) from 0.01 to 100 grams / 10 minutes or higher, preferably from 0.1 to 30 grams / 10 minutes, as measured using the ASTM D- standard 1238, condition E (190 ° C, 2,160 grams by weight).
    [070] The above ionomers can be prepared using free radical copolymerization methods, using high pressure, which operate in a continuous manner as described in US patents 4,351,931; 5,028,674; 5,057,593 and 5,859,137. Exemplary examples of ionomeric materials include products available from DuPont under the tradename SURLYN, from Exxon under the tradename IOTEK and Dow under the tradename AMPLFY IO.
    [071] Examples of elastomeric block copolymers are acrylonitrile-butadiene-styrene, polyisopropene-polyethylene-butylene-polystyrene or polystyrene-polyisoprene-polystyrene block copolymers, polyether ester block copolymers, or combinations thereof.
    [072] Other suitable polymers are polyamides, polyamide copolymers, polyimides, polyesters, polyurethanes, polyurethane copolymers, polyacrylics, polyacrylonitriles, polysulfones, silicone copolymers.
    [073] In some embodiments, the second polymer is preferably a thermoplastic elastomeric block copolymer such as polyisopropene-polyethylene-butylene-polystyrene or a polystyrene-polyisoprene-polystyrene block copolymer.
    [074] The first and second polymers can be mixed together and produced in various forms, such as pellets, fibers, sheets, films, fabrics, hot melt adhesives, powders, liquids or combinations thereof. As examples, the mixture can be produced using a kneader, a single or double screw extruder or a melt mixer heated to a temperature between 80 ° C and 420 ° C. The first polymer forms a continuous or co-continuous phase with the second polymer after adding the second polymer. THIRD POLYMER
    [075] In some embodiments, a third polymer can be present in an amount from 0 to 99.7% by weight based on the total weight of the first, second and third polymers. The third polymer can also be a bimodal component of the first and second polymers. The third polymer can be polyetheretherketone (PEEK), polyetherketone (PEK), polyetheretherketone (PEKK), polyphenylene sulfide (PPS), polyetherimide (PEI), polysulfone (PSU), polyimide (PI) and polyphenylene oxide (PPO). The third polymer can be present as a separate layer on the substrate, or it can replace the first polymer. In another embodiment, the third polymer is mixed with the first polymer. An example of such a mixture is a first polyamide polymer, and a third polyimide polymer. COMPOSITE ARTICLE
    [076] The resin-coated substrate described above can be incorporated into a composite article, such as a structural core, an impact resistant article or a laminate.
    [077] The use of a first and second resin, as described above, has been found to provide a number of advantages of a composite article.
    [078] When subjected to a shear test or butt joint, laminates show a cohesive failure. Similar laminate tests that comprise an aliphatic polyamide resin, such as nylon 6 or nylon 12, show an adhesive failure. This result is indicative of a mixture of the first and second resin delivering (a) the improved bending performance in a sandwich structure comprising the incorporation of the core and (b) the ease of expansion, during the manufacture of a honeycomb core. honey.
    [079] Substrates coated with a first and a second resin show improved shape retention when compared to similar substrates coated with nylon based resins. This can be demonstrated by placing a sample of coated substrate between two aluminum plates in a right angle format, placing the plate set for one minute in an oven in a range from 50 to 325 ° C, removing the plate set from the oven, cooling for 10 minutes, and then removing the coated substrate from the plate set. The plates must be preheated to the required temperature before the substrate is positioned between the plates. After 24 hours of storage under environmental conditions, the angle formed by the two sides of the substrate is measured. This is known as the retained angle. The closer to 90 degrees the retained angle is, the better the retention property of the shape will be. Ambient conditions mean a temperature of 23 +/- 1 ° C and a humidity of 50 +/- 10%.
    [080] The first and second resins allow a wider range of operating temperatures from about 175 to 300 ° C when compared to a range of about 185 to 275 ° C, for a nylon resin.
    [081] The first and second resins are capable of laser welding the substrates to form a laminate, as well as the conventional connection in a press, oven or hot autoclave. Such versatility is not possible in all resin systems.
    [082] The structure of the nucleus can be in the shape of a honeycomb or a folded nucleus.
    [083] Figure 1A is an illustration of the plan view of a honeycomb (1), which comprises a coated substrate and shows the cells (2) formed by cell walls (3). Figure 1B is an elevation view of the honeycomb shown in Figure 1A and shows the two outer surfaces, or the faces (4) formed at both ends of the cell walls. The core also has edges (5). Figure 2 is a three-dimensional view of the honeycomb. It is shown in honeycomb (1) which has hexagonal cells (2) and cell walls (3). The thickness of the honeycomb is shown in (10) in Figure 2. The hexagonal cells are shown; however, other geometric arrangements are possible with the square cells of the flex core, overexpanded being among the most common arrangements possible. These cell types are well known in the art and reference can be made to Honeycomb Tecnology, pages 14 to 20 by T. Bitzer (Chapman & Hall, editors, 1997) for additional information on possible cell types geometric shapes.
    [084] Figure 3 shows a structural sandwich panel (5) assembled from a honeycomb core (6) with face sheets (7 and 8), connected to the two outer surfaces of the core. The preferred face sheet material is a pre-impregnated fibrous sheet, impregnated with thermoplastic or thermoset resin, although face sheets of another material can also be used. Examples of other types of cover sheet include wood, metal, ceramic and fiber-reinforced plastic. In some circumstances, an adhesive film (9) is also used to intensify the bonding of the face sheet to the core. There are usually at least two pre-impregnated films on both sides of the core.
    [085] Figure 4 shows a folded core structure, which is a three-dimensional structure of the folded geometric pattern from a relatively thin, flat sheet material. Such folded sheet or mosaic structures are discussed in US patents 6,935,997 and 6,800,351 B1 B2. Chevron is a common standard for three-dimensional folded sheet or mosaic core structures. Such structures are different from honeycomb structures. The preferred folded or mosaic sheet structure is of the type described in US patent 6,913,570 B2 and US patent publication 2010 / 0.048,078. A sheet of corrugated cardboard is another form of a folded core structure.
    [086] The core structure can optionally be coated with a fourth polymeric resin. Such a resin can provide flame resistance and additional mechanical strength for the core. Suitable fourth resins include phenolic flame retardant (FR) epoxy, FR polyester, polyamide, and polyimide resins. Phenolic resins typically comply with United States Military Specification MIL-R-9299C. Preferably, the resin is a phenol-formaldehyde resin and can be a resol or novolac resin. Other aldehydes, for example, furfural, can be used, and other phenols, for example, hydroquinone and p-cresol, can also be used. The preparation of p-cresol and the properties of these resins are described in “Phenolic Resins”, authors A. Knop and LA Pilato, Springer-Verlag, Berlin, 1985. A resol resin is cured simply by applying heat while a novolac resin requires, for its cure, the additional presence of a substance that generates formaldehyde, for example, hexamethylenetetramine, also known as hexamine. Resins of the resol type are preferred. Suitable phenolic resins are available from companies such as Hexion Specialty Chemicals, Columbus, OH or Durez Corporation, Detroit, MI. When the coating of the substrate by the fourth resin is carried out before forming the core, the resin is preferably partially cured. Such a partial curing process, known as B-stage, is well known in the composite materials industry. By B-stage is meant an intermediate stage in the polymerization reaction in which the resin softens with heat and is plastic and fuse, but does not completely dissolve or melt. The B-stage reinforcement substrate is still capable of further processing in the desired core shape.
    [087] When resin impregnation is carried out after the core has been formed, it is usually produced in a sequence of repetitive immersion steps, followed by removal of the solvent and curing of the resin. Preferred final core densities (non-woven sheet, plus resin) are in the range from 5 to 500 kg / m3. In some embodiments, the range is from 10 to 300 kg / m3, while in other embodiments it is from 15 to 200 kg / m3. During the resin impregnation process, the resin is absorbed and coated on the reinforcement substrate. The coating resin is applied to the core according to known substrate coating or block dipping procedures.
    [088] Resins can be used as solutions or dispersions in solvents or dispersion media, for example, water, acetone, propan-2-ol, butanone, ethyl acetate, ethanol, and toluene. Mixtures of these solvents can be used to achieve acceptable evaporation rates of the solvent from the core. The amount of solvent used will vary widely, depending on a number of factors, including the type of core material to be used. In general, the solvents must be added in conventional amounts, to provide a resin solution, which can be easily applied, according to known processes.
    [089] The amount of resin coating that is applied can vary depending on a number of factors. For example, non-woven materials, which are relatively porous, will need more resin in order to achieve sufficient moisture in the honeycomb walls. For relatively non-porous core materials, preferably, a sufficient amount of resin is applied to the material to provide the coating thicknesses in the range of 0.0025 to 0.125 mm (from 0.1 to 5 mils).
    [090] When the reinforcement substrate is manufactured in a honeycomb core structure, there are two main methods of fabrication, expansion or curling. Expansion methods are typically used for paper substrates and curling methods for fabric substrates. Both methods are well known in the prior art and are further detailed on page 721 of the Engineered Materials Handbook, Volume 1 - Composites, ASM International, 1988.
    [091] In some embodiments, prior to the expansion of the honeycomb or curling processes, the substrate can be coated with a first amount of the fourth coating resin with the remainder to be applied in a second amount after the formation of the honeycomb. honey.
    [092] When the reinforcement substrate is manufactured in a bent-core structure, several production techniques are required. The processes for converting the substrates to the folded core structures are described in US patents 6,913,570 and 7,115,089 B2 B2, as well as US patent application 2007/0141376. In some embodiments, the entire fourth coating resin is applied after forming the folded core, while in other embodiments, the substrate is coated with a first amount of the fourth coating resin before forming the core, with the remainder being applied in a second amount after the formation of the nucleus.
    [093] Methods for coating substrates, before and after core formation are well known in the art.
    [094] The thickness of the reinforcement substrate depends on the end use, or the desired properties of the honeycomb core and in some embodiments it is usually from 75 to 500 micrometers (from 3 to 20 mils) thick. In some embodiments, the base weight of the substrate is from 15 to 200 grams per square meter (0.5 to 6 ounces per square yard).
    [095] The core structures of the present invention above can be used to manufacture composite panels that have face sheets attached to at least one outer surface of the core structure. The material of the face sheet can be a plastic sheet or a plate, a fiber-reinforced plastic (pre-impregnated) or metal. The face sheets are attached to the core structure, under pressure and, usually, with heat by an adhesive film, or from the resin in the pre-impregnation. Curing is carried out in a press, an oven or an autoclave. Such techniques are well understood by those skilled in the art.
    [096] The resin-coated substrate described above can also be incorporated into an impact resistant article in order to provide impact resistance at low and high speed. Suitable items include covers, bumpers and other accident-resistant structures.
    [097] The resin-coated substrate described above can be incorporated into a composite laminate. This laminate is a metal fiber laminate that comprises several thin layers of metal bonded to the layers of the resin-coated substrate. The metal fiber laminate may also comprise other reinforcement fibers. Other laminated composite materials can be constructed without the metal layers.
    [098] During the construction of the articles referred to above, it may be advantageous to include at least one energy absorbing layer, as a component of the article. The selective positioning of the energy-absorbing layer will allow the targeted connection of specific regions within a layer, when subjected to a high energy source, such as a laser beam. As an example, such a process can be used to form the knot line welds between successive layers of the coated substrate in a honeycomb block. A suitable energy-absorbing layer is a polymeric layer comprising carbon black. This effect is shown in Figure 5, in which a multilayer stack (50) comprises a first plurality of resin-coated substrates (51) and a second plurality of resin-coated substrates (53) separated by an energy-absorbing layer (52). A high energy beam (54), such as a laser, is shown directed towards the outer surface of the first plurality of resin coated substrates. The beam causes the polymer coating of the substrate to melt in the region under the laser beam path, thereby fusing the adjacent layers (55) in the region of the laser beam path. The substrate layers (53) that are below the energy absorbing layer are not fused together. The laser beam can move and trace any desired path, such as a straight line, a discontinuous line, a zigzag, a circle, an ellipse, a square, a cross, a star or a spiral. The bonding zone between adjacent layers will be bonded in a correspondingly similar pattern. TEST METHODS
    [099] The density of the honeycomb core has been determined according to ASTM C271-61.
    [0100] The compressive strength of the core was determined according to the ASTM C365-57 standard.
    [0101] The specific compression strength of the core was calculated by dividing the values of the compression strength by the density of the core.
    [0102] The tensile strength of adhesive-bonded butt joints was determined in accordance with ISO 6922: 1987 - EN 26922: 1993.
    [0103] The resistance of the shear connections of the plastic circuit, rigidly bonded in a shear way through the stress loading was measured according to the ASTM D3163-01 standard (again approved in 2008).
    [0104] The apparent shear strength properties of overlapping joints have been determined in accordance with ASTMD7616-11. EXAMPLES EXAMPLE 1
    [0105] In the following examples, fabric F was a single weave fabric comprising the commercially available p-aramid yarns under the trademark Kevlar® 49 from EI DuPont de Nemours and Company, Wilmington, DE, the yarns had a density linear of 1,580 dtex. The fabric had 6.7 ends per cm in warp and 6.7 ends per cm in the filling (weft). The weight of the fabric was 220 gsm.
    [0106] In the following examples, R1 resin exclusively comprises BASF nylon 6 commercially available under the trade name Ultramid® B27E. The resin was subjected to extrusion to form a sheet with a thickness of 50 micrometers.
    [0107] In the following examples, resin R2 was a mixture of 60% by weight of nylon 6 (Ultramid® B27E) and 40% by weight of a zinc ionomer resin. The ionomeric resin comprised 83% by weight of ethylene, 1% by weight of methacrylic acid and 6% by weight of maleic acid anhydride. The ionomeric resin was neutralized to 60%. The resin was subjected to extrusion to form a sheet with a thickness of 50 micrometers.
    [0108] In the following examples, fabric S was a hydroentangled fabric comprising 1.7 denier per filament (dpf) of commercially available p-aramid fiber under the trade name Kevlar 970 blend 1F894 from EI DuPont de Nemours and Company, Wilmington , IN. The weight of the fabric was 64 gsm. The fiber had a nominal cut length of 38 mm.
    [0109] In the following examples, paper P was a commercially available para-aramid sheet under the trade name Kevlar® aramid paper from E.I. DuPont de Nemours and Company, Wilmington, DE. The sheet of paper had a base weight of 61 gsm and a thickness of 0.07 mm (2.8 mil).
    [0110] In the following examples, resin R3 is a mixture of 70% by weight of nylon 12, commercially available from Arkema Inc., King of Prussia, PA under the trade name Rilsan® AESNO and 30% by weight of nylon 12 Rilsan ® Amno. The resin was subjected to extrusion to form a sheet with a thickness of 50 micrometers.
    [0111] In the following examples, resin R4 was a mixture of 55% by weight of resin R1 and 45% by weight of a zinc ionomer resin. The ionomeric resin comprised 83% by weight of ethylene, 11% by weight of methacrylic acid and 6% by weight of maleic acid anhydride. The ionomeric resin was neutralized to 60%. The R4 resin was extruded into a sheet that has a thickness of 50 micrometers. COMPARATIVE EXAMPLE A
    [0112] A composite set has been produced which comprises a layer of fabric F with a layer of resin sheet R1 extruded on both sides of fabric F.
    [0113] The resulting composite assembly was then molded by compression in an automated parallel plate press under a pressure of 20 bar, while heating from 100 ° C to 250 ° C at a rate of 5 ° C / min . The pressure and temperature conditions were maintained for 15 minutes and then the whole was cooled to 50 ° C at a rate of 5 ° C / min, still under pressure.
    [0114] The overlapping joint specimens were prepared from the cured composite and tested using a stress load according to the test method ASTM D3163-01 (2008). The test results were compared according to the recommendations provided in the ASTM D4896-01-2008 standard. The shear specimens of the circuit had a length of 105 mm, a width of 25 mm and an overlap of 15 mm. The specimens were bonded in the overlap region with a commercially available epoxy film adhesive from Cytec Engineered Materials, Tempe, AZ under the trade name FM 300U. The weight of the adhesive was 150 gsm. Specimen binding was performed on a parallel automated flat plate using a pressure of 20 bar, while heating from 100 ° C to 175 ° C at a rate of 5 ° C / min. The pressure and temperature conditions were maintained for 60 minutes and then the press was cooled to 50 ° C at a rate of 5 ° C / min, still under pressure. EXAMPLE 1
    [0115] A composite set was produced that comprises a layer of fabric F with a layer of extruded resin sheet R2 on both sides of fabric F. The resulting composite set was then molded by compression in an automated parallel plate press. according to Comparative Example A. The resulting laminate was then conditioned for 24 hours at 25 ° C in 50% RH, before being cut for the circuit shear test. The overlapping joint specimens were prepared as in Example A, except that instead of using an adhesive film to bond the overlapping region, the circuit shear specimens were fused together by compression welding in an automated plate press. parallel using a pressure of 20 bar, while heating from 100 ° C to 250 ° C at a rate of 5 ° C / min and maintaining the temperature and pressure conditions for 15 minutes. The mold and contents were then cooled to 50 ° C at a rate of 5 ° C / min, before the pressure was released.
    [0116] After the test, the samples were visually examined to observe the failure mode. The sample failed outside the overlap connection region. That is, the bond overlap is stronger than the composite laminate. COMPARATIVE EXAMPLE B
    [0117] This example was prepared and tested in a manner identical to that of Example 1, except that the extruded resin sheet R1 was used in place of R2. Examination of the tested samples showed the adhesive failure. That is, that the test coupons failed in the region of the cast (welded) joint. This leads to the conclusion that a resin sheet R2 used in Example 1 provides a stronger compound than the resin sheet R1 used in Comparative Example B. COMPARATIVE EXAMPLE C
    [0118] A composite set was produced which comprises a layer of paper P with a layer of resin sheet R3 extruded on both sides of the paper sheet. The resulting composite assembly was then molded by compression in an automated parallel plate press under a pressure of 20 bar, while heating from 100 ° C to 220 ° C at a rate of 5 ° C / min. The pressure and temperature conditions were maintained for 15 minutes and then the whole was cooled to 50 ° C at a rate of 5 ° C / min, still under pressure. EXAMPLE 2
    [0119] A composite set has been produced which comprises a layer of paper P with a layer of extruded resin sheet R4 on both sides of the paper sheet. The same processing conditions were used as for the manufacture of Comparative Example C. COMPARATIVE EXAMPLE D
    [0120] A composite set was produced which comprises a layer of fabric S with a layer of resin sheet R3 extruded on both sides of the fabric. The same processing conditions were used as for the manufacture of Comparative Example C. EXAMPLE 3
    [0121] A composite set has been produced which comprises a layer of fabric S with a layer of extruded resin sheet R4 on both sides of the fabric. The same processing conditions were used as for manufacturing Comparative Example C. COMPARATIVE EXAMPLE E
    [0122] A composite set was produced comprising a layer of fabric F with a layer of resin sheet R1 extruded on both sides of fabric F. The same processing conditions were used as for the manufacture of Comparative Example C. EXAMPLE 4
    [0123] A composite set has been produced which comprises a layer of fabric F with a layer of extruded resin sheet R4 on both sides of the fabric. The same processing conditions were used as for the manufacture of Comparative Example C. EXAMPLE 5
    [0124] A composite set has been produced which comprises a layer of fabric F with a layer of extruded resin sheet R2 on both sides of the fabric. The same processing conditions were used as for the manufacture of Comparative Example A. COMPARATIVE EXAMPLE F
    [0125] In this Comparative Example, two laminates of Comparative Example A were joined using a 150 gsm structural epoxy bonding adhesive that was commercially available from Cytec Engineered Materials, Tempe, AZ under the trade name FM 300U. The connection was carried out on a parallel automated flat plate using a pressure of 10 bar, while heating from 100 ° C to 175 ° C at a rate of 5 ° C / min. The pressure and temperature conditions were maintained for 60 minutes and the press was then cooled to 50 ° C at a rate of 15 ° C / min, still under pressure. THERMOFORMATION ASSESSMENT
    [0126] The individual composite laminated reinforced layers manufactured from each of Comparative Examples A, D and Examples 2 and 3 were subjected to a thermoforming test. The dimensions of the test samples were 75 mm x 25 mm. The samples were placed in a training tool. The forming tool comprises two aluminum plates, each plate being 150 mm x 200 mm folded in the width direction to form an L shape, with a 90 degree angle between the two sides. The two plates of the tool were heated to the formation temperature. Formation temperatures were 50 ° C, 100 ° C, 150 ° C, 175 ° C, 185 ° C, 200 ° C, 225 ° C, 250 ° C, 275 ° C, 300 ° C and 325 ° C. Test coupons that were kept at room temperature (room temperature) were placed between the two heated plates and kept for 1 minute inside an oven before being removed from the oven and cooled to room temperature. The molding tool containing the molded laminate was kept at room temperature for 24 hours before the outer plate was removed. At least three laminated composite materials were tested for each temperature condition. The purpose of the measurements was to observe how the laminate maintained its shape after removing the external component from the molding tool. Figure 6 shows in (61), the internal L-shaped component of the molding tool. The laminate is shown in (62). The first angle A1 is measured at a distance of 5 mm from the tip of the tool component (61). The second angle, A2 is measured 35 mm away from the tip of the tool component (61). If the molded laminate retained 100% of the "as molded" shape when removed from the mold, therefore, the angles A1 and A2 would be the same. Any tendency for the molded laminate to return to its original, flat pre-molding shape will result in the A2 angle being greater than the A1. Constructions of composite laminate that have the smallest difference between A2 and A1 will have the best retention of post-molding and thermoformability. The results are summarized in Table 1 for a molding temperature of 150 ° C, which is close to, but below the melting point temperature of resins R3 and R4. TABLE 1
    Mean difference between angle A2 and A1 (°) 7.0 3.3 23.0 2.3 Improvement of relative thermoforming for each pair 0% 52% 0% 90%
    [0127] Table 1 shows the thermoforming performance for Comparative Examples A and D and Examples 2 and 3. As can be seen, the laminate comprising the thermoplastic compositions of the present invention has a better thermoforming behavior and, when compared to the compositions of the Comparative Examples. These thermoforming improvements are considered to be significant. At higher temperatures above the melting point of thermoplastic polymers, the processing window is wider, the retention of the shape is better and the robustness of the process is significantly improved. T-EXFOLIATION TESTS
    [0128] The individual composite laminated reinforced layers manufactured in accordance with Comparative Examples A, E and Examples 4 and 5 were tested by a T-Exfoliation test, according to the ASTM D1876-08 standard. The test specimens consisted of two laminates from each example thermally fused together without any additional adhesive. The dimensions of the test samples were 150 mm x 25 mm, and the bonded length was 100 mm. The fusion of the specimen was performed in a parallel automated flat plate using a pressure of 10 bar at 220 ° C or 250 ° C, respectively, for the thermoplastic laminates produced with, respectively, the R3 or R4 resin system. The temperature was maintained for 5 minutes at 10 bar, then cooled to 50 ° C at a rate of 50 ° C / min, still under pressure.
    [0129] Exfoliation tests were performed seven days after the bonding (fusion) process. The ends of each specimen were attached to the test jaws of a Zwick® 1445 strain test machine model with a 1kN load cell and 0.1 N resolution. This equipment is available from Zwick GmbH & Co. KG, Ulm, Germany.
    [0130] The load was applied at a constant main speed of 50 mm / min. At least five samples for each bond or fusion condition were tested. All test coupons failed in a cohesive manner in the region of the cast (welded) joint. The results are summarized in Table 2. TABLE 2

    [0131] Table 2 shows the melting strength or adhesive bonds for Comparative Examples A, E and F, and Examples 4 and 5. The resistance to exfoliation of thermally fused samples is as good or better than that of bonded laminate. , the latter being an example of what is normally used in industry.
    [0132] The above data confirms that a composite of resin and fiber, as described herein, has sufficient bond strength and thermoforming capacity to be a suitable material honeycomb and other core structures through production methods, such as expansion, curling or other folding processes. The application in other scanning areas of the fiber reinforced composite is also considered.
    [0133] A honeycomb structure comprising a paper or fabric core coated with R2 or R4 resin will exhibit greater shear strength when compared to a similar core structure that only comprises a nylon resin coating. No deterioration in tensile strength is expected when resins R2 and R4 are used. When compared to a core structure comprising paper or fabric coated with a thermoset resin, the core comprising resin R2 or R4 will inherently increase the properties of toughness, good fatigue, improved malleability and gains in production efficiency.
    权利要求:
    Claims (13)
    [0001]
    1. COMPOSITE RESIN AND FIBER SHEET, characterized by comprising a fibrous reinforcing substrate and a resin coated on or inside the substrate, the resin comprising a first thermoplastic polymer and a second thermoplastic polymer, in which: (i) the first and the second polymer form a mixture of two phases, (ii) the first polymer is thermoplastic, has a melting point of 75 to 400 ° C and forms a continuous or co-continuous phase with the second polymer, (iii) the second polymer is dispersed in the continuous or co-continuous phase of the first polymer, has an effective diameter of 0.01 to 15 micrometers and has a melting point of 25 to 350 ° C, (iv) the first polymer comprises 35 to 99% by weight of the combined weight of the first and the second polymer in the mixture, (v) the second polymer has a melting point of at least 5 ° C less than the melting point of the first polymer, and (vi) the substrate reinforcing fibers are of fibers that have a toughness of 3 to 60 grams per dtex and a filament diameter of 5 to 200 micrometers.
    [0002]
    2. COMPOSITE SHEET according to claim 1, characterized in that the first and the second polymer are polyolefin, polycondensate or an elastomeric block copolymer.
    [0003]
    COMPOSITE SHEET, according to claim 2, characterized in that the polyolefin is polypropylene.
    [0004]
    COMPOSITE SHEET according to any one of claims 1 to 3, characterized in that the fibrous substrate is a paper or a fabric.
    [0005]
    COMPOSITE SHEET according to claim 4, characterized in that the paper comprises from 10 to 100% by weight of aramid fibers and from 0 to 90% by weight of the aramid binder.
    [0006]
    6. COMPOSITE SHEET, according to claim 4, characterized in that the paper comprises fibers of p-aramid, m-aramid, cellulose, polyester, fiberglass, ceramic, carbon, basalt or mixtures thereof.
    [0007]
    7. COMPOSITE SHEET, according to claim 4, characterized in that the fabric is woven, unidirectional, multiaxial, three-dimensional or non-woven and comprises filaments that have a toughness of 8 to 60 grams per dtex and a filament diameter of 7 to 32 micrometers .
    [0008]
    COMPOSITE SHEET according to claim 7, characterized in that the fabric comprises filaments of aromatic polyamide, aromatic copolyamide, glass, ceramics, carbon, basalt or mixtures thereof.
    [0009]
    COMPOSITE SHEET according to claim 7, characterized in that the nonwoven is a felt, a hydroentangled sheet or a continuous spinning sheet.
    [0010]
    10. COMPOSITE ARTICLE, characterized by comprising the composite sheet, as defined in any one of claims 1 to 9.
    [0011]
    11. ARTICLE according to claim 10, characterized in that the article is a honeycomb structure, a folded core structure, an impact resistant article or a composite laminate.
    [0012]
    12. STRUCTURE OF FOLDED CORE or honeycomb, as defined in claim 11, characterized in that it comprises a fourth resin.
    [0013]
    13. STRUCTURAL SANDWICH PANEL, characterized by comprising a folded or honeycomb core, as defined in claim 11, having at least one face sheet connected to both outer surfaces of the core.
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    同族专利:
    公开号 | 公开日
    EP2817451A1|2014-12-31|
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    JP2015511194A|2015-04-16|
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    CA2864826C|2020-02-18|
    WO2013126739A1|2013-08-29|
    US20140113104A1|2014-04-24|
    CN104114768B|2017-06-27|
    CA2864826A1|2013-08-29|
    EP2817451B1|2016-01-13|
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    法律状态:
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-26| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-02-09| B16C| Correction of notification of the grant|Free format text: REF. RPI 2612 DE 26/01/2021 QUANTO AO ENDERECO. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261602199P| true| 2012-02-23|2012-02-23|
    US61/602,199|2012-02-23|
    PCT/US2013/027375|WO2013126739A1|2012-02-23|2013-02-22|A fiber-resin composite sheet and article comprising the same|
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