JP6221150B2 - High performance thermoplastic composite laminate and composite structure produced therefrom - Google Patents

Description

  The following disclosure relates generally to composite laminates and composite structures produced therefrom, and more specifically, high performance thermoplastic composite laminates and composite structures produced therefrom, and methods for producing the same About.

  Composite applications are often limited to components with low or moderate structural loads. However, there is a need for composite materials that are lightweight, relatively low cost, and have high performance. Such composite materials can meet the needs of the aerospace industry and the general transportation industry, such as the requirements regarding corrosion resistance, fire resistance, smoke or toxicity. In addition to protective clothing, bulletproof materials, etc., in industries related to power generation, construction, land transportation or maritime transportation, for example, for vehicles and personal use products that require flame resistance, There is a need for composite materials.

  Embodiments of the present invention solve the above problems and meet the above industrial needs.

  As an embodiment of the present invention, a refractory composite laminate comprising a thermoplastic matrix material, wherein the thermoplastic matrix material is reinforced by fibers embedded in the matrix of the composite laminate. The body is provided. The thermoplastic matrix material of the refractory composite laminate comprises polyvinylidene fluoride (PVDF).

  In another embodiment of the present invention, there is provided a refractory composite laminate including a polymer matrix material, wherein the polymer matrix material is reinforced by fibers embedded in the matrix of the composite laminate. A functional composite laminate is provided. The polymeric matrix material of the refractory composite laminate includes one or more of polyvinylidene fluoride (PVDF), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), and polyetheramide (PEI).

  As still another embodiment of the present invention, a fireproof bulletproof panel provided with a fireproof composite laminate is provided. The refractory composite laminate includes a refractory polymer matrix material reinforced by fibers embedded in the matrix of the composite laminate, and the refractory bulletproof panel is when a projectile is projected onto the panel, Meets one or more of the protection levels of anti-projectiles as defined by NIJ standard protective clothing classes II-A, II, III-A, III and IV.

  As still another embodiment of the present invention, a fireproof bulletproof panel having a first surface and a second surface, each of which is a first polymer matrix material having a first flame retardant resin. A fire resistant bulletproof panel is provided that includes a striking face portion having a first plurality of layers comprising embedded fibers. The fireproof bulletproof panel is further disposed adjacent to the striking surface, and each of the second includes a fiber embedded in a second polymer matrix material having a second flame retardant resin and is secured to an adjacent layer. A pointing unit having a plurality of layers.

The perspective schematic diagram of the high performance composite material structure which has a core member concerning an embodiment. Schematic which shows the state which expand | deployed the high performance composite material structure of FIG. The perspective schematic diagram of the core member of Drawing 1 concerning an embodiment. Schematic of the several layer contained in an example of the laminated body of the composite material structure concerning embodiment. Schematic of the apparatus used for manufacture of the composite material laminated body of the composite material structure concerning embodiment. The rear view of the freezing trailer containing the composite material structure or laminated body concerning embodiment. The perspective view of the air cargo container containing the composite material structure or laminated body concerning embodiment. The perspective view of the rail freight container containing the composite material structure or laminated body concerning embodiment. The perspective view of the container for integrated transport containing the composite material structure or laminated body concerning embodiment. The figure which showed the battery case containing the composite material structure or composite material laminated body concerning embodiment. The figure which showed the battery box containing the composite material structure or laminated body concerning embodiment. The perspective schematic diagram which shows the partial cross section of the fireproof bulletproof panel concerning embodiment.

  Hereinafter, the high-performance thermoplastic composite laminate according to the embodiment, the high-performance composite structure manufactured using the laminate, and the method of manufacturing the laminate and the structure will be described. High strength laminates and structures provide a solution to many needs. Certain resins, for example, meet specific needs such as aerospace applications, but are expensive and difficult to process, generally in addition to post-treatment on the resin to make the final product Requires a special process. For example, olefinic resins used in necessities generally undergo significant changes in the mechanical properties in the resulting structure when in contact with flame retardant adhesives. Also, such materials do not meet the general flame retardant requirements in the aerospace and other transportation industries. As an embodiment, the inventors of the present invention, for example, how to combine high-strength fibers contained in a thermoplastic matrix with a highly flame-retardant resin, provide corrosiveness, ignition, smoke, toxicity Composite materials that meet industrial needs with no potential for material generation (ie, high resistance to ignition, smoke, and toxic material generation) and excellent performance in terms of mechanical properties Create or suggest.

  Although details will be described later, here, as an embodiment, it is easy to manufacture, has high strength against weight, has high impact resistance, is not easily fatigued, has high chemical resistance, is heat resistant, has high fire resistance, Disclosure of composite materials, including thermoplastics reinforced with long fibers, with low or no generation of toxic substances and with desirable properties in other commercial applications. Moreover, although mentioned later for details, in embodiment, the composite material using high strength fibers, such as E glass fiber and S glass fiber, and the polyvinylidene fluoride (PVDF) resin is proposed. This composite material is molded into the shape of a high-performance tape-like laminate, a twisted laminate, a sandwich panel, etc., and does not ignite, smoke, toxic substances that meet the requirements of the aerospace industry, for example. Used to provide composite products that do not emit. Desirable characteristics can be obtained when materials such as carbon, aramid, basalt, and boron are used in the composite material described below.

  When a unidirectional tape is used as the configuration of the laminate disclosed in the present specification, the mechanical performance of the composite material is improved as compared with, for example, a laminate using a classic woven fabric. In addition, when fibers such as glass fiber are used, relatively expensive resins (eg, PVDF) that meet the requirements for fumes, fires, and generation of toxic substances are low cost materials (eg, 50 to 85 weight percent). (Within range) and the desired mechanical properties are obtained. Further, as will be described later, the laminate disclosed in the present specification provides high strength and fire resistance even in the form of a tape in addition to the shape of the laminated body that has been twisted. Generally, the high-strength reinforced thermoplastic material and the structure according to the embodiment include a combination of a thermoplastic matrix material, high-strength reinforced fibers, and optionally other reinforced materials.

  Next, a composite material structure 10 according to an embodiment will be described with reference to the drawings. As shown in FIGS. 1 and 1A, the composite structure 10 is sandwiched between a first outer layer 12, a second outer layer 14, and the first outer layer 12 and the second outer layer 14. A core member 16 is provided. The core member 16 is not necessarily arranged so as to be in direct contact with the first outer layer 12 and the second outer layer 14. For example, as shown in FIGS. 1 and 1A, one or more intermediate layers 17 may be disposed between the first outer layer 12 and the second outer layer 14. Thus, the core member 16 may be sandwiched between, for example, two intermediate layers 17. The number of used intermediate layers 17 may be changed as necessary. Further, the intermediate layer 17 may not be used.

  The composite structure 10 shown in FIGS. 1 and 1A is a substantially rectangular composite material “sandwich panel”, but the configuration of the composite structure 10 is not limited to that shown, and the composite structure 10 may be configured in any shape, size, or thickness depending on the final product in which it is used. The composite material structure 10 includes a plurality of layers, for example, a first outer layer 12, a second outer layer 14, and an intermediate layer 17, and a core member 16. The core member 16 depends on the configuration of the article or product. Any shape, size, thickness, dimension, etc. may be used. Examples of these articles and their descriptions will be described later, following the description of the composition of the composite material according to the embodiment.

  As a suitable material for the core member 16 of FIGS. 1 and 1A, a foam is usually used. In one embodiment, the foam comprises a PVDF foam, such as, for example, a Zotec brand polyvinylidene fluoride (PVDF) foam. However, in embodiments, the core member 16 may comprise any suitable material, such as described herein with respect to the first outer layer 12, the second outer layer 14, and the intermediate layer 17, for example. Materials and combinations thereof.

  The first outer layer 12, the second outer layer 14, the one or more intermediate layers 17, and materials and manufacturing methods used for components and structures using the same will be described later, but are not limited thereto. Although a specific thermoplastic material will be described below, the composite structure 10 including the first outer layer 12, the second outer layer 14, and the intermediate layer 17 may be any suitable, fiber reinforced thermoplastic. May be made with. The thermoplastic resin may be further reinforced with a reinforcing material other than fibers, or may not be reinforced. It may also be accompanied by a suitable thermoplastic coating.

  In an embodiment, in the “sandwich panel” shown in FIGS. 1 and 1A, the layers of the laminate (eg, first outer layer 12, second outer layer 14, and intermediate layer 17) are foamed thermoplastic foam. The body (for example, the core member 16) is attached to the opposite surface of the sheet by, for example, fixing using an appropriate adhesive. In one embodiment, the layer of the laminate attached to the opposing faces of the thermoplastic foam sheet is a fiber reinforced thermoplastic tape, depending on the properties required for the final product. Thus, for example, those having characteristics such as unidirectionality and multiaxial fiber arrangement are used. In a particularly desirable embodiment, the high strength layers (first outer layer 12, second outer layer 14) comprise, for example, a PVDF resin matrix reinforced with high strength long fibers (eg, glass fibers). In addition, the core member 16 includes PVDF foam. By using PVDF material for the structure according to the embodiment, the structure can have desirable fire resistance and flame retardancy.

  In an embodiment, at least one of the first outer layer 12, the second outer layer 14, and the intermediate layer 17 includes a plurality of composite material layers. The plurality of composite material layers include at least a first composite material layer and a second composite material layer. The first composite material layer and the second composite material layer each include a plurality of fibers in a thermoplastic matrix. The plurality of composite material layers are fixed to each other to form a composite material laminate. In one embodiment, all of the first outer layer 12, the second outer layer 14, and the intermediate layer 17 have the configuration described above. In some embodiments, at least one of the first outer layer 12, the second outer layer 14, the intermediate layer 17, and the core member 16 includes PVDF.

  In embodiments, the at least one composite laminate of the first outer layer 12, the second outer layer 14, and the intermediate layer 17 each includes one or more composite layers and is often affixed to each other. Two or more composite material layers including a first composite material layer and a second composite material layer are included. Each of the plurality of composite material layers includes a plurality of fibers. A plurality of fibers contained in each of the first composite material layer and the second composite material layer is impregnated with a thermoplastic matrix material.

  In embodiments, the thermoplastic matrix material may be any material or combination of materials as long as it is a suitable thermoplastic material for the application. These materials include, for example, polyvinylidene fluoride (PVDF), polyamide (nylon), polyethylene, polypropylene, polyethylene terephthalate, polyphenylene sulfide, polyetheretherketone (PEEK), polyphenylene sulfide that provide desirable fire resistance to composite materials. (PSS), polyether amide (PEI), fluorinated polymers, other high performance resins exhibiting desirable properties, other thermoplastic polymers, and combinations thereof.

  In one embodiment, the plurality of fibers included in the first composite material layer are substantially parallel to each other, and the plurality of fibers included in the second composite material layer are substantially parallel to each other. In one embodiment, the fibers of each layer are arranged side by side in the longitudinal direction and are continuous over the entire width of the layer. In the following description, the composite material layer is referred to as a layer or a sheet. In the embodiment, the composite material layer has “unidirectionality” which is a characteristic in which the directions of fibers are aligned in the longitudinal direction.

  In another embodiment, the plurality of fibers included in the first composite material layer are arranged to cross (cross) the plurality of fibers included in the second composite material layer. For example, the fibers of the first composite layer may be at an angle in the range of about 0 degrees to about 90 degrees with respect to the fibers of the second composite layer, or in the range of about 15 degrees to about 75 degrees. They are arranged to intersect at an angle. In embodiments, an angle in the range of 0 degrees to about 90 degrees may be employed.

  In the embodiment, the plurality of fibers included in the first composite material layer may be the same as or different from the plurality of fibers included in the second composite material layer. Various types of fibers having different strengths are used for the composite material layer. For example, the fibers include E glass fiber and S glass fiber. E glass is a low alkali borosilicate glass, which has excellent electrical and mechanical properties and high chemical resistance. Since E glass exhibits a high electric resistance value, it is suitable for a composite material laminate for electrical use. Note that “E” means electrical.

  S glass is a material with higher strength and higher cost than E glass. S-glass is a magnesia-alumina-silicate glass and is generally used for aerospace applications where high tensile strength is required. Originally, “S” means high strength. Both E-glass and S-glass are particularly suitable fibers for use in the embodiments disclosed herein.

  When E glass fiber is included in a thermoplastic polymer matrix material, its weight ratio can be varied. In an embodiment, the weight ratio range of E-glass as a reinforcing material is, for example, from about 10 ounces to about 40 ounces per square yard (oz./sq. Yd.). Also, the range is desirably from about 19 ounces to 30 ounces, and more desirably from about 21.4 ounces to about 28.4 ounces. In one embodiment, the minimum weight of the cross layer is about 18 ounces per square yard of composite material. If the fibers in the cross layer are 70 weight percent, the weight of the reinforcing material in one square yard of the composite is 18 ounces of 70 percent.

  The amount of S or E glass fibers contained in the composite layer can be arbitrarily varied, for example, in the range of about 40 weight percent to 90 weight percent based on the total weight of the thermoplastic matrix and the fibers. Desirably within the range of about 50 weight percent to about 85 weight percent, and more desirably within the range of about 60 weight percent to about 80 weight percent.

  Other fibers may be used, in which case it is desirable that other fibers be used in combination with E-glass or S-glass, but other fibers may be used in place of E-glass or S-glass. . These other fibers include, for example, ECR, A-glass and C-glass, as well as quartz, magnesium aluminosilicate, non-alkali aluminoborosilicate, soda borosilicate, soda silicate, soda lime-aluminosilicate. Acid salt, lead silicate, non-alkali lead boro-alumina, non-alkali barium boro-alumina, non-alkali zinc boro-alumina, non-alkali iron aluminosilicate, cadmium borate, alumina fiber, asbestos, boron, silicon carbide, carbonized polyethylene Graphite and carbon derived from, polyvinyl alcohol, saran, aramid, polyamide, polybenzimidazole, polyoxadiazole, polyphenylene, PPR, petroleum and (isotropic) coal pitch, mesophase pitch, cellulose and polyacrylonitrile, La Mick fibers include, for example, steel, fiber metal such as aluminum alloy, and fibers made from those like them.

  If high performance is required and high costs are justified, high-strength organic polymer fibers made from aramid exemplified by Kevlar and various carbon fibers may be used. High performance unidirectional fiber bundles generally have a tensile strength greater than 7 grams per denier. Examples of such high-performance fiber bundles include aramid, extended chain ultrahigh molecular weight polyethylene (UHMWPE), poly [p-phenylene-2,6-benzobisoxazole] (PBO), and poly [diimidazopyridinoline. (Dihydroxy) phenylene] and combinations thereof.

  These extremely high tensile strength materials are particularly suitable for reinforcing composite panels.

  Any type of fiber known by those skilled in the art may be employed without departing from the scope of the present invention broader than the embodiments disclosed herein. For example, aramid fibers such as products sold under the name Twaron or Technora, basalt and carbon fibers such as products sold under the name Toray, Fortafil or Zoltek, products sold under the name Vectran, etc. Liquid Crystal Polymer (LCP) may be employed. In the embodiment, organic fibers, non-organic fibers, and metal fibers may be used alone or in combination.

  In embodiments, the composite layer may optionally include continuous fibers, finely cut fibers, randomly mixed fibers, woven fibers, and the like. In a preferred embodiment, the fibers are all composite material layers arranged in the longitudinal direction and do not include fibers arranged in the transverse direction.

  Additional materials may also be used. Such materials include foams, metals (eg, aluminum steel, other ferrous metals, non-ferrous metals, etc.), plastics, epoxides, composite materials, drugs, and other suitable materials. These materials may be used, for example, to impart specific mechanical, spatial or other properties uniformly or in specific areas throughout the thermoplastic composite structure or laminate according to the embodiment. , Used as a reinforcing material, additive, or insert. In the composite material, the laminate, and the structure according to the embodiment, the fiber, the material added as an option, the reinforcing material, and the like may be used in various combinations, and the amount in the combination may be arbitrarily changed. Moreover, the material added as an option mentioned above may be used combining arbitrarily.

  Also, continuous reinforcing fibers, i.e., fibers having a length equal to the length of the material or structure, can be used in the composite structure to increase the strength in the direction along the fiber direction. If the arrangement and tension of the fibers can be kept constant in the step of impregnating the reinforcing fibers with the matrix material, the physical properties of the composite materials and their structures or laminates to be manufactured can be improved.

  In the embodiment, since the fibers contained in the composite material layer are oriented in the longitudinal direction, one composite material layer contained in the composite material laminate is one or more other composite material layers contained in the composite material laminate. May be arranged in a specific positional relationship.

  In one desirable embodiment, the composite laminate comprises a plurality of tapes or layers comprising fibers arranged so as to be substantially parallel to one another, wherein one layer comprises the fibers of the layer in which the fibers are adjacent; For example, it arrange | positions so that it may cross at about 90 degrees or less. In an embodiment, the fibers are evenly distributed over the entire width of the layer. In other embodiments, a tape is provided having fibers disposed in a thermoplastic matrix. Also, in other embodiments, a tape or laminate having crossed layers, for example, comprising two layers each containing fibers in a thermoplastic matrix, the fibers contained in one layer being included in the other layer A material is provided that is arranged to be approximately 90 degrees to the fibers to be reinforced.

  In an embodiment, the thermoplastic matrix of one or more layers included in the composite laminate used as at least one material of the first outer layer 12 and the second outer layer 14 is, for example, a thermoplastic matrix comprising PVDF. It is. Examples of the thermoplastic matrix include polyamide (nylon), polyethylene, polypropylene, polyethylene terephthalate, polyphenylene sulfide, polyether ketone, and combinations thereof. As the thermoplastic matrix, polyvinylidene fluoride (PVDF) may be used alone or in combination with other matrix components. By using PVDF, fire resistance can be imparted to the manufactured structure.

  Moreover, the fracture resistance of a composite material laminated body can be improved by using polyethylene for a thermoplastic matrix material. When polyethylene is used, for example, equivalent fracture resistance is realized in a lighter weight as compared with a composite material laminate using polypropylene. In addition, since a complicated process is required to produce a monomer for polypropylene, the price of polypropylene tends to fluctuate greatly, but the price of polyethylene is stable. Polyethylene composite laminates are lighter compared to, for example, polypropylene composite laminates, so depending on the container made of polyethylene composite laminate or using polyethylene composite laminate as the backing For example, more cargo can be transported, and the fuel efficiency and cost-effectiveness of trucks, railways, ships, etc. using such containers are improved.

  In an embodiment, a copolymer of polyethylene and polypropylene may be used as the thermoplastic matrix. For example, depending on the application and the properties required for that application, it may be desirable to use a copolymer of greater than about 50 weight percent polyethylene and less than about 50 weight percent polypropylene.

  In other embodiments, the thermoplastic matrix of one or more layers is combined in an appropriate weight ratio and coextruded polyethylene and polyethylene terephthalate (sometimes also referred to as poly), broadly abbreviated as PET. You may prepare. For example, in the embodiment, the PET polymer used is a thermoplastic PET polymer used for a synthetic fiber, a beverage, food, a container containing other liquid, a thermoforming application, a high-performance resin in combination with glass fiber, or the like. Resin. PET homopolymers may be used with comonomers such as CHDM and isophthalic acid. These comonomers lower the PET melting temperature and the PET crystallinity. Accordingly, the resin has plasticity at a lower temperature and can be molded with a smaller force. In an embodiment, a PET homopolymer or copolymer may be used for a release film that is added by painting, for example, in a post-treatment. Such additional layers are also laminated to the main composite structure.

  Polyethylene thermoplastic polymers can be used as the polymeric matrix material used in the various embodiments disclosed herein. The amount of the thermoplastic resin in the weight ratio varies depending on the physical properties required depending on the intended use of the product. Polyethylene is classified into a plurality of different categories mainly depending on density and branching amount, and the mechanical properties of polyethylene vary depending on variables such as the degree and type of branching amount, crystallized structure, molecular weight and the like. In a preferred embodiment, the polyethylene used includes low density polyethylene (LDPE), ultra high molecular weight polyethylene (UHMWPE), ultra low molecular weight polyethylene (ULMWPE or PE-WAX), high molecular weight polyethylene (HMWPE), high density polyethylene (HDPE). ), High density crosslinked polyethylene (HDXLPE), crosslinked polyethylene (PEX or XLPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), and combinations thereof. Particularly effective types of polyethylene include HDPE, LLDPE, LDPE and combinations thereof, with LDPE being particularly effective. The individual properties of the various types of polyethylene used in the thermoplastic matrix according to the embodiment are described below.

LDPE has a density in the range of 0.910 to 0.940 g / cm ^{3 and} a high ratio of short chain branching to long chain branching. Therefore, in general, the chain portion does not firmly enter the crystal structure. Such materials exhibit strong intermolecular forces due to the small attractive or induced dipole attraction. As a result, the tensile strength is low and high flexibility is exhibited. LDPE is made by free radical polymerization. Due to the high branching rate of the long chains, the melted LDPE exhibits a unique desirable fluidity.

UHMWPE is a polyethylene having a molecular weight of 1 million units, and generally has a molecular weight of about 3 to 6 million. Due to this large molecular weight, UHMWPE is a very tough material, but the chain is not efficiently incorporated into the crystal structure and is less dense than high density polyethylene (e.g., 0.930 to 0.935 g / cm < ³ >). UHMWPE is made by a variety of catalyst technologies, but in general Ziegler catalysts are used for its production. Because UHMWPE exhibits outstanding toughness and resistance to cutting, abrasion and chemicals, this material is widely useful in a variety of applications.

HDPE has a density of 0.941 g / cm ³ or more. HDPE has a low branching rate and therefore exhibits strong intermolecular forces and tensile strength. HDPE is produced by a chromium or silica based catalyst, a Ziegler-Natta catalyst, or a metallocene catalyst. Selection of an appropriate catalyst (eg, a chromium-based catalyst or a Ziegler-Natta catalyst) and reaction conditions will ensure that there is a lack of branching.

  PEX (also referred to as XLPE) is a medium to high density polyethylene that contains crosslinks in the polymer structure that change the thermoplastic to an elastomer. Thereby, the characteristics at high temperature are improved, the fluidity is low, and the chemical resistance is high.

MDPE has a density in the range of 0.926 to 0.940 g / cm ³ . MDPE is made with a chromium or silica based catalyst, a Ziegler-Natta catalyst, or a metallocene catalyst. MDPE exhibits excellent impact resistance and drop weight resistance. This material is less prone to notch than HDPE and has better stress cracking resistance than HDPE.

LLDPE has a density in the range of 0.915 to 0.925 g / cm ³ . LLDPE is a linear polymer with a substantially significant number of short branches, generally copolymerizing ethylene with short chain alpha-olefins (eg, 1-butene, 1-hexene and 1-octene). It is made by. LLDPE has a higher tensile strength than LDPE and exhibits higher impact and fracture resistance than LDPE. LDPE also has toughness, flexibility and relatively high transparency.

VLDPE has a density in the range of 0.880 to 0.915 g / cm ³ . VLDPE is a linear polymer with a substantial number of short branches, generally copolymerizing ethylene with short chain alpha-olefins (eg, 1-butene, 1-hexene and 1-octene). Made with. VLDPE is generally produced using metallocene catalysts, which incorporate more comonomer. VLDPE is also used as an impact modifier mixed with other polymers.

  In addition to the specific polymers described above, copolymers and combinations using any of the materials described above may be employed in embodiments. Further, in addition to or instead of copolymerization with alpha-olefins, ethylene (or polyethylene) may be copolymerized with various other monomers and ionic compositions that produce ionized free radicals. For example, when vinyl acetate is used, an acrylate salt such as ethylene vinyl acetate copolymer (EVA) is produced. In addition, the thermoplastic matrix may include a polyvinylidene fluoride (PVDF) alone or in combination with other matrix components to impart fire resistance to the resulting structure.

  In embodiments, the thermoplastic matrix of one or more composite layers of the composite laminate may comprise polyethylene alone or in combination with other polymers, copolymers or components such as PVDF. For example, polyethylene and PVDF may be used as matrix materials with high molecular weight thermoplastic polymers such as polypropylene, nylon, PEI (polyetherimide), and copolymers thereof, or any of the components described above.

  In an embodiment, the composite layer comprises about 60 weight percent to about 10 weight percent polymeric matrix, desirably about 50 weight percent to about 10 weight percent polymeric matrix, and more desirably about 40 weight percent. Percent to about 15 weight percent of the polymeric matrix. The range may also be, for example, from about 40 weight percent to about 20 weight percent, or from about 30 weight percent to about 25 weight percent. The above-mentioned weight percent is the weight percent of the polymer matrix material with respect to the total weight of the polymer matrix material and the fibers.

  In one embodiment, the proportion of fibers contained in the one or more composite layers is greater than about 50 weight percent (based on the sum of the weight of the polymer matrix and the fibers in the layer), desirably greater than about 85 weight percent. . Various types of fibers can be used, but as described above, glass fibers are particularly suitable from the viewpoint of rigidity.

  In one embodiment, the composite laminate includes a first layer and a second layer secured to each other, the fibers contained in each of the layers are arranged to cross each other, and the first layer is the first layer. The two layers include fibers that are different from the fibers included, and one or both of the first layer and the second layer includes polyethylene. The composite laminate includes at least two different types of fibers. That is, the fibers included in the first composite material layer are arranged in a direction transverse to the different types of fibers included in the adjacent second composite material layer. The angle between these fibers is for example 90 degrees. The first composite material layer and the second composite material layer arranged in this way are hereinafter expressed as being in a transverse relationship with each other (for example, at 90 degrees with respect to each other) without referring to the fibers contained in each layer. .

  “Different types of fibers” is to be interpreted broadly and the composite laminate includes at least two composite layers, each of which is a different material or the same material. It means that it is made of different grade materials. Details will be described later in the description of the application of the composite laminate. For example, the front surface of the panel including the composite laminate is made using Kevlar 129 fiber, and the back side or the back side portion of the panel has higher performance. It may be made using a material.

  Optionally, the composite laminate may include a composite layer disposed parallel to the adjacent composite layer. In this case, desirably, adjacent composite layers comprise the same type of fibers. One or more layers of the matrix material, preferably all layers, comprise polyethylene. Further, the matrix material may vary from layer to layer and may be different thermoplastics, polymers, or combinations thereof. The part of the composite material laminate including the first type of fibers may be formed by stacking the composite material layers so that the fibers are parallel to each other.

  In a particularly effective embodiment, the composite laminate may be formed by stacking a plurality of composite layers, each containing either E glass fiber or S glass fiber, at an angle of about 90 degrees to each other.

  In an example of the structure of the layer including at least the first layer and the second layer included in the composite material laminate, the second layer is disposed at 90 degrees with respect to the first layer. Depending on the required properties, the second layer may be placed at other angles less than 90 degrees. In the embodiment, a three-layer configuration may be adopted. In this case, assuming that the first layer is the reference direction (that is, 0 degree), the second layer is arranged at a first angle (for example, a positive acute angle such as 45 degrees) with respect to the first layer, The third layer has a second angle different from the first angle with respect to the first layer (eg, a negative acute angle (or 315 degrees), such as -45 degrees), in which case the acute angle in the opposite direction to the second layer. ). The second layer and the third layer may be perpendicular to each other or may not be perpendicular. Products using a thermoplastic matrix can easily change the relative orientation of the fibers in adjacent layers during the final molding step in production.

  In other embodiments, at least two of the plurality of composite layers of approximately the same areal density are disposed within a range of 0 degrees to 90 degrees with respect to each other, or within a range of about 15 degrees to about 75 degrees Arranged in. “Area density” (usually expressed in pounds per square foot (lbs./sq. Ft.)) Is used in comparing the relative strengths of the different layers. When the surface density is high, the fracture strength of the layer is generally high. In the embodiment, the composite material laminate may include at least two composite material layers including a first layer and a second layer having a higher surface density than the first layer. In embodiments, a suitable areal density for the composite laminate is, for example, in the range of about 1 pound to 10 pounds per square foot.

  FIG. 3 is a schematic view of a composite material laminate 200 according to one embodiment. The composite laminate 200 can be used for at least one of the first outer layer 12, the second outer layer 14, and the intermediate layer 17 shown in FIGS. 1 and 1A. Moreover, the composite material laminated body 200 can be used as a configuration of any product using the composite material. In the embodiment, the composite material laminate 200 includes at least a first composite material layer 220 and a second composite material layer 240. The number of layers included in the composite material laminate may be any number such as two layers, three layers, and four layers. As described above, in embodiments, the at least one layer of thermoplastic matrix material comprises PVDF, and may further comprise polyethylene or the like. In the embodiment, each of the first composite material layer 220 and the second composite material layer 240 is a unidirectional layer, and includes fibers having directivity in the longitudinal direction. The first composite material layer 220 and the second composite material layer 240 are individually manufactured in a series of manufacturing processes and accumulated in individual rolls. A composite laminate such as the composite laminate 200 shown in FIG. 3 has two or more composite material layers as fats and oils, and these composite material layers are arranged, for example, in a direction in which fibers included in each cross each other. It is fixed in a state. Any suitable thermoplastic material may be used for one or more of these layers. FIG. 3 shows an example of the arrangement of various layers, and the order of stacking, materials, and the like are variously changed according to demands. Therefore, the combination and order of the first composite material layer 220 and the second composite material layer 240 are not limited.

  In the configuration shown in FIG. 3, one or more layers may be added. For example, a layer of high-strength fibers such as mixed thermoplastic fibers or glass fibers may be placed anywhere in the laminate (eg, between layers or outside the laminate) and function as a structural layer Good. An example of such a structural layer is a mixed laminate product. A commercially available product suitable for this layer is TWINTEX (TWINTEX is a registered trademark of Fiberglass Industry in the United States). According to the manufacturer of the product, TWINTEX is a thermoplastic glass reinforcement (roving) made of a mixture of E-glass and fine fibers of polypropylene and is well adapted to be woven into the fabric. Immobilization is performed by heating the roving at a temperature higher than the melting temperature of the polypropylene matrix (180 to 230 degrees Celsius), pressurizing, and cooling by pressurization. The glass content is, for example, 53 weight percent, 60 weight percent, or 70 weight percent. The weaving method is, for example, plain weave or twill weave. The size and shape of the structural layer is determined according to the intended application, as with the other layers shown in FIGS. 1 and 1A.

  In an embodiment, the thermoplastic matrix material of the first outer layer 12, the second outer layer 14, or the intermediate layer 17 may further include a thermosetting material. For example, depending on the intended application, the above-described fibers may be embedded in a material based on a combination of thermoplasticity and thermosetting in the amount described above. Examples of such a thermosetting matrix material include phenols, polyesters, epoxies, and combinations thereof.

  Various methods can be adopted as a method for manufacturing the composite material and its structure. For example, various methods such as a doctor blade method, lamination, pultrusion molding, and extrusion molding can be employed as a method of impregnating fibers embedded in a layer with a matrix material or wrapping fibers with a matrix material. The composite material layer, composite material, composite material laminate, panel, and the like of the composite material laminate according to the embodiment may be manufactured by any suitable method.

  In one embodiment, “sandwich panels” such as single layered sheets, laminates formed by lamination, and composite structures 10 may be made from unidirectional tape, for example. The unidirectional tape is manufactured using various methods such as a melting process and a force vapor deposition method. A multi-layer laminate is generally produced by a hydraulic press or a pneumatic press that can be heated and cooled in a single mold. As a particularly suitable method, there is a method of manufacturing a material by a continuous belt press using Teflon (registered trademark). Steel belts that can be heated, pressurized, and cooled may be used. According to these methods, it is possible to produce a continuous laminate that can be wound around a roll.

  Also, in embodiments, the composite material layer may be processed into a complex shape, such as an aircraft interior panel, by compression molding. The product so processed is a multi-layer sheet or a combination of a core member, such as Zortec PVDF foam, formed into a structural composite panel. Laminates having various configurations such as two layers, three layers, and four layers may be processed into a tubular shape by winding or the like, and may be used as pipes that are excellent in structural characteristics, erosion resistance, and fire resistance. In addition, the product including the structural panel and pipe according to the embodiment is required to have corrosion resistance and fire resistance, generation of smoke and toxic substances is prohibited, and light weight and high strength structure is required. Also suitable for applications in industry, gas industry and mining industry. Thus, the composite material according to the embodiment is suitable for use in various industries and has advantages in various applications. For example, as a product or a structure using the composite material according to the embodiment, for example, a floor and a wall of a cabin inside an aircraft in the aerospace industry or a covering member thereof, other aircraft structure, a floor in a railway or a bus, Bulletproof products such as walls, their coverings, oil drilling equipment, certain transport-related products such as fire-resistant cargo containers, fire-resistant or flame-resistant protective clothing, fire-resistant or flame-resistant bulletproof panels , Etc.

  In the embodiment, an intermediate material in which a thermoplastic matrix pre-impregnated with a unidirectional continuous reinforcing fiber (prepreg) is formed into a tape shape by drawing or extrusion may be used. For example, in a composite panel such as composite structure 10, a structure comprising a plurality of layers of thermoplastic tape reinforced with continuous fibers as described above may be made of the same, similar or different materials exhibiting the required properties. It may be combined with a foamed thermoplastic foam.

  In other embodiments, with respect to the method of manufacturing the composite material and its product, for example, a composite layer reinforced with fibers comprising a plurality of fibers in a thermoplastic matrix (e.g., first composite material layer 220, second composite material). Suitable processing devices for the production of the material layer 240) include coated belts, such as laminating devices, which can be purchased from Maschinen Fabric Herbert Meyer Ltd., located in Dörth, Hertz-Meyerstrasse 1, Roths, Germany. The standard belt laminating system used is available.

  Further, for example, in addition to or instead of the above-described method, other manufacturing methods such as a method of forming a composite material laminate by bonding a plurality of composite material layers together may be used. Such methods include, for example, a method in which a plurality of composite material layers are sequentially stacked and then heated and pressed, or a panel of a composite material laminate is formed using an adhesive. As the adhesive, any of liquid, hot melt, reactive hot melt or film, epoxy, methyl acrylate, urethane, etc. may be used. Also, sonic vibration welding or solvent bonding may be used. In general, a composite material laminate is formed by sequentially stacking a plurality of layers and then pressurizing them while heating them with a press machine, for example, and welding adjacent layers.

  U.S. Pat. No. 8,201,608 and its contents by the same applicant as the present application are incorporated herein as reference information disclosing suitable apparatus and methods for the production of composite layers. These devices and methods can be used to produce composite laminates, materials, and structures disclosed herein.

  Accordingly, the following description is a modification of these devices and methods, such as the addition of reference numbers, for the description of the fabrication of composite laminates and structures described herein.

  For example, a schematic block diagram of FIG. 4 shows as an apparatus 31 an example of a suitable apparatus used in the manufacture of a composite laminate and structure as shown in the composite laminate 200 of FIG. As shown in FIG. 4, the device 31 includes a rewind processing unit 32. In the embodiment, during operation, a material such as a composite material layer having a plurality of fibers in the thermoplastic matrix is unwound from the roll in the unwinding processing unit 32 and supplied to the next processing unit. The apparatus 31 includes an additional processing unit 34 at a position adjacent to the rewinding processing unit 32. In the addition processing unit 34, the subsequent composite material is added on the composite material rewound from the rewinding processing unit 32. These added layers are arranged such that the fibers of the added composite material layer are directed at different angles with respect to the fibers of the preceding composite material that has been rewound from the rewinding processing unit 32. However, the embodiment is not limited in this respect, and the fibers constituting a part of the layer added to the fibers constituting the part of the composite material unwound from the unwinding processing unit 32 are substantially parallel. You may arrange | position so that it may become. The device 31 optionally includes a second rewinding processing unit 36 at a position adjacent to the additional processing unit 34. In the second unwinding section 36, one or more additional layers of composite material are unwound from the roll. The layer rewound from the second rewinding processing unit 36 is disposed above, for example, any of the composite material rewound from the rewinding processing unit 32 and the additional layer added in the additional processing unit 34. The A heat processing unit 38 is provided downstream of the additional processing unit 34. In the heat treatment unit 38, the plurality of laminated composite material layers are heated and fixed to each other. Further, a processing unit 40 is provided downstream of the heat processing unit 38. The processing unit 40 includes one or more calendar roll assemblies 41. The calendar roll assembly 41 will be described later. In the processing of the processing unit 40, an intake processing unit 42 for winding the composite material laminate is disposed. The progress direction of the processing of the composite material from the unwinding processing unit 32 to the capture processing unit 42 indicated by an arrow in FIG. 4 is hereinafter referred to as “processing direction”. In this specification, “upstream” and “downstream” are used to indicate the direction of processing or a relative position with respect to the direction of processing.

  In the embodiment, the individual shape, size, and configuration of the composite material laminate according to requirements are realized by individual processing using the above-described processing apparatus. For example, when a composite laminate is made that is used as one or more layers of the composite structure 10, the composite structure 10 is assembled into the required shape and the components are secured.

  The composite structure 10 or composite laminate produced by the apparatus and method described above is used in a wide variety of end uses. Among such end uses, those that are particularly suitable include freight container related uses and freight vehicle related uses in addition to construction related uses. In embodiments, the composite structure 10 or composite laminate may be configured for wall, liner, panel, flooring, container, or other construction and transportation related applications. Transportation-related applications include applications related to cargo transportation vehicles including aircraft and trailers. For example, these materials are used for panels, liners, containers, flooring materials, floor base materials, doors, ceiling members, wall members, wall covering materials and the like having various sizes and strengths. In particularly desirable embodiments, the composite structure 10 or composite laminate is associated with panels, liners, marine containers, aircraft, railroads, trucks, buses, etc. that require structural resistance and corrosion resistance, for example. Constructed for structures, pipes, etc.

  Depending on the article, different types of materials may be used. In each article, a single material may be used, or a combination of a plurality of materials may be used. These articles are tough and give properties such as high durability. Specifically, the composite material structure 10 or the composite material laminate may be processed into a final product such as a wall, a door, a panel, a liner, a container, or a floor member. These articles exhibit excellent properties such as high strength, light weight, corrosion resistance, fire resistance, no smoke and no toxic substances.

  In the following, further examples of final products or applications using the composite material structure 10 or the composite material laminate will be described. As shown in FIG. 5, the composite material structure 10 or the composite material laminate can be used as a liner that protects an inner portion of, for example, a vehicle trailer, other transportation vehicles, ships, containers, and the like. FIG. 5 shows a liner 700 provided on the inner portion 702 of the vehicle trailer 704. In an embodiment, the liner 700 is a composite panel that exhibits superior properties compared to, for example, a standard finely cut glass thermoset product. For example, when the liner 700 includes polyethylene, it is lighter, easier to clean, less susceptible to fouling and less wear than a panel based on polypropylene. The liner 700 may be disposed as a liner that protects the inner wall, a liner that protects the outer wall, or the like in addition to the liner that protects the ceiling. The liner 700 is used for a liner that protects a wall of a refrigerated container (large-sized freezer) and other transportation-related applications. The liner 700 has a high durability and is configured as a semi-rigid structure or panel, and may be specifically designed, molded, or the like so as to improve the cooling effect in a cooled container such as a large freezer.

  In another embodiment of the final product, as shown in FIG. 5, the composite structure 10 or composite laminate is a panel 710 for flooring or underfloor material such as trailers and other vehicles, ships, containers, etc. It may be configured as. In embodiments, the panel 710 may be coated with a durable flooring made of composite material, or a composite material layer, for example.

  In addition, the composition and configuration of the embodiments described in the present specification may be variously combined.

  Furthermore, the composite laminates described herein are typically used in various types of cargo transportation devices such as trailers, vans, delivery vehicles, rail vehicles, aircraft, ships, and shipping containers used in them. Is available. The “trailer” includes any cargo transportation device, and the “transport container” includes any container used in the cargo transportation device.

  The composite structure 10 including the composite material laminate is configured as a panel used for a vehicle trailer (truck), and as another embodiment, a liner or panel for protecting the inside of a railway vehicle, and protecting an inside of an aircraft. It may be configured as a liner or panel, a liner or panel that protects the inside of a container, such as an intermodal container, a construction structure, a pipe, and the like.

Further, for example, the container itself may be manufactured or retrofitted using a composite material, a structure using the composite material, or a composite laminate. FIG. 6 is a perspective view of an air freight container 970 which is another example of the final product. The air freight container 970 uses the composite material structure 10 or the composite material laminate in the inner part. The air freight container 970 may be made of a composite material, as described above, or may have been refurbished using the composite material.
FIG. 7 shows a perspective view of a railway vehicle 980 as another embodiment of the final product. The rail vehicle 980 includes the composite material structure 10 or the composite material laminate as the liner 982. However, the liner may be placed at various locations on the container body, such as the inner portion of the railcar wall.

  FIG. 8 is a perspective schematic view of an intermodal container 990 that includes the composite structure 10 as a liner 992 according to an embodiment. The integrated transport container 990 includes a ceiling member 994, an inner wall member 996, a flooring 998, and a door member 999. The liner according to embodiments may be placed at various locations on containers and other components. As shown in FIG. 8, the liner 992 may be placed as a dressing on the flooring 998 or may be integrated with the flooring 998. The liner 992 may also be disposed on at least a portion of the inner wall member 996 or may be disposed on the inner portion of the ceiling member 994. FIG. 8 shows a scuff panel 997 made of liner 992 or covered with liner 992. The integrated transport container 990 can be loaded and unloaded again from one type of transportation to another, for example, from railroad to ship, then truck, and so on. It can be moved. In an embodiment, the size of the intermodal container 990 meets the requirements of the ISO standard. For example, the total length is in the range of 8 feet to 50 feet and the height is in the range of 8 feet to 9 feet 6 inches.

  FIG. 9 is a diagram showing another application of the composite material structure 10 or the composite material laminate. Specifically, FIG. 9 shows a battery case including the composite material structure 10 or the composite material laminate. FIG. 10 is a view showing still another application including the composite material structure 10 or the composite material laminate, specifically, a battery box.

  The composite material structure 10 or composite material stack may be attached to structures such as inner floor members, sidewall members, ceiling members, scuff plates, and other container parts. Further, for example, the entirety of containers, pipes and the like for air freight, railroad and intermodal transportation may be made of the composite material structure 10 or the composite material laminate. Further, the panels, liners, and structures described herein may be used on a part or all of the outer surface of a trailer, container, or the like. In that case, ultraviolet resistance and abrasion resistance may be imparted to these structures. Also included in the embodiments are retrofits of composite structures 10 or laminates, or existing structures using panels, liners, etc. using them.

  Further, as described above, the material according to the embodiment described in the present specification may be used for a protective device or a bulletproof material for a vehicle or an individual, for example. For example, the materials according to the embodiments described herein can be used as fire resistant bulletproof composites or bulletproof panels. For example, the structure shown in FIGS. 1, 3 or 11 can be used as a fireproof composite bulletproof panel. Bulletproof materials and bulletproof panels are used, for example, to make fireproof portable bulletproof shields such as bulletproof clipboards used by police officers, providing fireproof armor for non-moving places such as control rooms and security station In addition, a fireproof bulletproof device is also provided for vehicle occupants and the like. In the embodiment shown in FIG. 11, the panel 20 includes a striking surface portion 22 having a plurality of first layers 22a, 22b and the like and constituting the striking surface 23 of the panel. Each of the plurality of layers of the striking face portion 22 includes a plurality of first type fibers 24 disposed in a first matrix material 26. In each of the layers indicated by layers 22a and 22b, the plurality of fibers 24 are substantially parallel, and the plurality of layers form an angle with respect to the fibers contained in one adjacent layer. Are arranged as follows. In the example shown in the figure, the angle between the fibers is 90 degrees, but the layers may be arranged at other suitable angles, for example, an angle smaller than 90 degrees. The panel 20 further includes a support portion 28 having a back layer 30 and an inner laminated portion 33 as an option. The inner laminated portion 33 includes a plurality of composite material layers each including a second type of fiber 35 in a second matrix material 37. The back layer 30 includes, for example, a layer of matrix material that is substantially free of fibers and not a composite material. In other embodiments, the number of layers and their composition may be varied depending on the application. For example, the panel 20 is applied to a laminate of a tape crossing layer including a plurality of first type fibers, a tape crossing layer including a plurality of second type fibers, and a layer that is not a composite material. Manufactured by pressing. For example, the panel is manufactured by sequentially stacking a plurality of layers, and heating and pressurizing the stacked layers with, for example, a press machine and welding adjacent layers to each other. In one embodiment, the panel 20 includes a striking surface portion mainly including E glass fibers as low performance fibers and a support portion including S glass fibers as high performance fibers. Depending on the performance criteria required for the individual panels, the panel thickness and the relative thickness of the part of the panel containing the E glass and the part of the S glass may be varied. Desirably, E glass and S glass are approximately equal in weight ratio to the panel.

  In certain specific embodiments, the E-glass fiber meets ASTM D578-98, paragraph 4.2.2 criteria, and the yield of roving is about 250 to 675 yards per pound, or the weight of roving ( Tex) is about 735 grams to 1985 grams per kilometer. S glass fiber meets ASTM C162-90 or ASM 3832B standards, contains fine fibers with a diameter of about 9 micrometers, and has a roving weight (tex) of about 675 grams to 1600 grams per kilometer, or The yield is about 310 to 735 yards per pound.

  However, as the fiber 24 and the fiber 35, any of the fibers according to the embodiments described in the present specification may be used, or a combination thereof may be used. In addition, any of the composite materials according to the embodiments described in the present specification may be used for the layer of the panel 20, or a combination thereof may be used.

  The content of the composite material layer is expressed by the yield of the fibers used and the weight ratio of the fibers in the layer composed of the matrix and the fibers. For example, in one embodiment, the composite layer comprises E-glass in a polypropylene matrix material. The fiber yield is in the range of about 56 to 1800 yards per pound of fiber, and in one embodiment is, for example, about 675 yards. Also, the ratio of fibers to the total weight of fibers and matrix material is, for example, in the range of about 40 weight percent to 92 weight percent, and in one embodiment, for example, in the range of 60 weight percent to 80 weight percent. is there. The diameter of the fine fibers is, for example, in the range of about 0.005 micrometers to 0.025 micrometers. As the matrix material, any of the matrix materials according to the embodiments described in the present specification may be used, or a combination thereof may be used. Desirably, the matrix material includes a refractory polymer matrix material such as PVDF. Any of the matrix materials according to the embodiments described herein are used for the first matrix material 26 and the second matrix material 37 alone or in combination with other matrix materials.

  Bulletproof materials, including bulletproof panels, are tested according to standards that evaluate their ability to withstand the impact of bullets. Such a standard is briefly described below. As a standard for evaluating the performance of a bulletproof material, for example, there is a standard named “NIJ Standard for Bulletproof Protective Material” (NIJ Standard) established by the National Institute of Justice of the Ministry of Justice. Because ballistic threats from bullets or other projectiles vary depending on, for example, the projectile's composition, shape, diameter, mass, impact velocity, etc., the NIJ standard changes bulletproof materials to different protective grades such as: Classification. Type II-A (low speed 357 magnum, 9 mm), Type II (high speed 357 magnum, 9 mm), Type III-A (44 magnum, submachine gun, 9 mm), Type III (high output rifle), Type IV (Tetsuko Rifle) ).

  In the following, the above protection grade will be described more specifically. Type II-A (low speed 357 magnum, 9 mm): Protective materials classified as type II-A are 357 Magnum bullets with a soft point with an apparent mass of 10.2 g and a measurement speed of 381 plus or minus 15 meters / second Provides protection against standard test fire. The type II-A protective material has a protective performance against a 9 mm bullet with a full metal jacket having an apparent mass of 8 g and a measurement speed of 332 plus or minus 12 meters / second.

  Type II (High Speed 357 Magnum, 9 mm): This grade of protective material is capable of shooting with a projectile equivalent to a 357 Magnum bullet with a soft point with an apparent mass of 10.2 g and a measurement speed of 425 plus or minus 15 meters / second. It has protective performance against it. The type II protective material has a protective performance against a 9 mm bullet with a full metal jacket having an apparent mass of 8 g and a measurement speed of 358 plus or minus 12 meters / second.

  Type III-A (44 Magnum, submachine gun, 9 mm): This grade of protective material provides protection against most handgun threats, with an apparent mass of 15.55 g, measuring speed of 426 plus or minus 15 meters It has a protective performance against projectiles with characteristics equivalent to 44 Magnum bullets of lead semi-wad cutter gas-checked per second. Further, the type III-A protective material has a protective performance against 9 mm submachine gun bullet fire. This bullet is a 9mm full metal jacket bullet with an apparent mass of 8g and a measurement speed of 426 plus or minus 15 meters / second.

  Type III (High Power Rifle): This grade of protective material has protection against 7.62 mm (308 Winchester (Winchester is a registered US trademark)) ammunition and most handgun threats.

  Type IV (peeling rifle): This grade of protective material has a protective performance against 30 caliber armored shooting with an apparent mass of 10.8 g and a measuring speed of 868 plus or minus 15 meters / second.

  For the promotion of the above standards, another test for protective material is the V50 test defined in MIL-STD-622, ie ballistic test for V50 protective material. U.S. Pat. No. 7,598,185 contains a description of this test, the contents of which are hereby incorporated by reference into the present application.

  The protective material according to the embodiment including the fireproof bulletproof panel described above is the NIJ standard of protection grade II-A, II, III-A, III and IV described above when the projectile is fired against the protective material. Meets the level of protection for at least one projectile and passes the V50 test described above.

  Although the composite material or the laminated body exemplified in the composite material structure 10 includes one or two layers in some of the above-described embodiments, the embodiment is not limited in this respect, and the composite material is used. Any appropriate number of layers (for example, two layers, three layers, four layers, etc.) may be employed in the laminate exemplified by the structure 10, and their configurations may be changed according to the intended end use. It's okay. For example, a panel, liner or container comprising a layer containing a low-priced and low-performance E glass fiber in a thermoplastic matrix containing polyethylene and a layer containing a high-priced and high-performance S glass fiber in a thermoplastic matrix containing polyethylene Such a structure may be manufactured.

  In embodiments, in forming a panel from a layer of thermoplastic matrix material, by substantially eliminating the thermosetting matrix, the time is shorter than the time required to cure the thermosetting matrix material and at low pressure. The formation of the panel is realized. In addition, a panel composed of a layer containing a thermoplastic matrix material containing polyethylene does not require deaeration and emits little or no VOC. Optionally, metals, ceramics, and other materials may be added to the composite material panel described herein. In addition, after the panels and other structures described in the present specification are manufactured, for example, composite materials, elastomers, metals, and the like may be used to protect the structures from ultraviolet rays, moisture, and other environmental effects. It may be covered with a housing or the like. In addition, an additive may be added to the matrix material for the purpose of improving fire resistance, preventing the generation of smoke and toxic substances, and improving the appearance.

  Also, the final strength, stiffness, and other desirable properties of the final product will vary depending on, for example, the thermoplastic material used, the type of reinforcing material used and other materials, size, orientation, etc. Furthermore, the strength and rigidity of the final product also vary depending on the overall shape, such as the overall length, width, thickness, and cross-sectional area of the final product.

  In the present application, “first”, “second”, and similar expressions do not mean any order, quantity, importance, or the like, and are used to distinguish one element from another. Further, in the present application, the expression “a” is not intended to limit the quantity to one, and means that there is at least one object to be referred to. In the present application, “about” added to an expression indicating a quantity includes the exact quantity indicated by the phrase, but is used in the sense that it is not limited to the exact quantity. The features according to the plurality of embodiments described in the present specification may be arbitrarily combined as appropriate.

  The present invention has been described with reference to specific embodiments, but various modifications or alternatives to those embodiments are also within the scope of the technical idea of the present invention and the claims of the present application. It will be understood by those skilled in the art who have read and understood the above disclosure.

  Further, the present invention is not limited to the specific configuration described in the present specification or illustrated in the drawings of the present application, and may be modified from the disclosure scope or equivalent to the disclosure scope. This constitutes the present invention.

DESCRIPTION OF SYMBOLS 10 ... Composite material structure, 12 ... 1st outer layer, 14 ... 2nd outer layer, 16 ... Core member, 17 ... Intermediate | middle layer, 20 ... Panel, 22 ... Layer, 22 ... Hitting surface part, 23 ... Hitting surface , 24 ... fiber, 26 ... matrix material, 28 ... support part, 30 ... back layer, 31 ... device, 32 ... rewinding processing part, 33 ... inner lamination part, 34 ... additional processing part, 35 ... fiber, 36th 2 rewinding processing unit, 37 ... matrix material, 38 ... heating processing unit, 40 ... processing unit, 41 ... calendar roll assembly, 42 ... uptake processing unit, 200 ... composite material laminate, 220 ... first composite material Layer, 240 ... second composite layer, 700 ... liner, 702 ... inner part, 704 ... vehicle trailer, 710 ... panel, 970 ... air freight container, 980 ... railway vehicle, 982 ... liner, 990 ... container for integrated transport Na, 992 ... liner, 994 ... ceiling member, 996 ... the inner wall member, 997 ... scuff panel, 998 ... flooring, 999 ... door member.

Claims (18)

A first outer layer comprising polyvinylidene fluoride (PVDF) ;
A second outer layer;
A core member sandwiched between the first outer layer and the second outer layer,
The core member includes a polyvinylidene fluoride (PVDF) foam,
The first both the outer layer and the second outer layer, the composite material structure comprising a thermoplastic matrix reinforced by embedded fibers. At least one of the first outer layer and the second outer layer comprises a plurality of composite material layers including at least a first composite material layer and a second composite material layer;
Each of the first composite material layer and the second composite material layer has the fibers embedded in the thermoplastic matrix;
The composite material structure according to claim 1 , wherein the plurality of composite material layers are fixed to each other to form the composite material structure. At least one of the first outer layer and the second outer layer is coated ;
The composite material structure according to claim 1 , wherein at least one of the first outer layer and the second outer layer includes a twisted structure or a tape structure . The composite material structure according to claim 1 , wherein the fibers are parallel to each other. The first composite material layer and the second composite material layer include fibers of different lengths;
The first composite layer comprises E-glass fibers;
Composite structure of claim 2 wherein the second composite layer comprising S-glass fibers. A panel comprising the composite material structure according to claim 1 . Composite structure of claim 1 comprising one or more intermediate layers between the second outer layer and the first outer layer. The core member, the composite material structure as claimed in claim 1 comprising the foam of the first outer layer or the second outer layer by Ri thick foamed polyvinylidene fluoride (PVDF). A pipe comprising the composite material structure according to claim 1 . A battery box comprising the composite material structure according to claim 1 . A battery case comprising the composite material structure according to claim 1 . A method of manufacturing a composite structure according to claim 1, comprising:
How comprising the step of forming the unidirectional tape product layer body by melt processing. The method of claim 12 , comprising securing the laminate to a core member comprising a polyvinylidene fluoride (PVDF) foam. A bulletproof panel comprising the composite material structure according to claim 1. At least one of the one or more intermediate layers comprises polyvinylidene fluoride (PVDF).
The composite material structure according to claim 7. The fibers included in the first composite material layer are arranged so as to intersect the fibers included in the second composite material layer.
The composite material structure according to claim 2. The fibers included in the first composite material layer are arranged so as to intersect with the fibers included in the second composite material layer at an angle within a range of 0 to 90 degrees.
The composite structure according to claim 16. The fibers included in the first composite material layer are arranged so as to intersect with the fibers included in the second composite material layer at an angle in a range of 15 degrees to 75 degrees.
The composite structure according to claim 16.

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