• 专利附录
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    • 专利摘要:
    "DRY SELF-SUPPORTING FIBROUS MATERIAL, RIBBED TAPE OR TAG, METHOD FOR MAKING A RIBBED TAPE OR TAG, PREFORM TO RECEIVE LIQUID MATRIX RESIN BY RESIN INFUSION, AND, BINDING COMPOSITION". Disclosed in this document is a dry, self-supporting fibrous material, the fibers of which have been treated with a binder composition. The fibrous material can be grooved in tapes or tow that are suitable for use in an Automated Tape Deposition (ATL) or Automated Fiber Laying (AFP) process. This fibrous material is suitable for forming preforms which are configured to receive a matrix resin by infusion of resin in the manufacture of structural composite parts.
    公开号:BR112014015254B1
    申请号:R112014015254-3
    申请日:2012-12-19
    公开日:2021-02-23
    发明作者:Dominique Ponsolle；Carmelo Luca Restuccia；William Jacobs；Robert Blackburn；Carmelo Lofaro；Richard Price；Marc Doyle；Mitchell Smith；Mark Roman；Abdel Abusafieh
    申请人:Cytec Industries Inc；
    IPC主号:
    专利说明:

    [0001] The present disclosure refers to the field of pre-formation and manufacturing in resin infusion of structural composite components.
    [0002] In recent years, the aerospace and automotive industries have shown increasing levels of interest in the application of resin infusion processes to manufacture structural components.
    [0003] Dry flexible and preformable fibrous products can indeed have significant advantages over standard pre-impregnated materials due to their longer service life and applicability to more complex geometries and around narrow radii.
    [0004] The aspects of interdependence and criticality in the selection of materials and processing stages are of particular significance in the automated deposition / infusion process, in which the stages of fiber placement, pre-formation and resin injection are different in phase, but coupled in aspects related to material selection and processing.
    [0005] Gummies and binders, in fact, can simultaneously affect the processing and thermomechanical performance of composite structures.
    [0006] The curing kinetics of composites and thermomechanical properties can in fact be influenced by the formation of an interface region between the fibrous component and the host matrix. In addition, fiber / gum / resin interactions occurring during the infusion stage can affect the wetting and local flow behavior by the development of unbalanced stoichiometric and compositional regions.
    [0007] Most fibers and fibrous products used in composites are coated with gums, binders and / or finishes that serve multiple purposes, including facilitating handling, protecting the compaction fibers and process-induced damage, aiding in compatibility and wetting of fibers by the resin, and global intensification of the performance of composites.
    [0008] Several dry unidirectional tape products use a carbon web of unidirectional carbon fibers that has been thermally or adhesively glued to a carrier fabric or curtain to support the unidirectional carbon fibers. Several commercial versions are available from V2 Composites, Sigmatex and other textile producers. The limitations of these current products lie in the inability to groove and apply these products via an automated deposition process without deforming and fraying the edges.
    [0009] In other conventional materials, such as the NCF textile (non-corrugated fabric), the unidirectional fiber (UD) tow is held together by sewing the threads crossing over several carbon tow. On some occasions, very fine fibers are placed through the transverse direction of the weft to provide more lateral stability for UD fiber tow. In this case, the tow is not spread and there are gaps between tow as wide as 2 mm. Saertex and Sigmatex provide this type of products.
    [00010] Another conventional method of forming a dry unidirectional tape is the technique comprising spreading a fiber web and keeping the fibers strewn with thin linked yarns usually made of epoxy coated glass yarns or polyester or polyamide yarns with an activation point of low heat passing through the width of the ribbon and keeping the fibers spread together. The retention threads are not woven with the weft fibers, but are deposited on the upper and / or lower faces of the weft. In this type of product, the weft fibers are generally well spread, leaving very little definition of tow and gaps between tow, similar to the standard spread tape produced in pre-impregnated tape machines.
    [00011] It is believed that none of the binder compositions or material solutions of the state of the art meets the physical, thermomechanical and process requirements for the production of dry fibrous materials that are suitable for use in Automated Tape Laying (ATL) and Automated Fiber Placement (AFP) to form preforms for subsequent resin infusion in the manufacture of composite parts. SUMMARY
    [00012] A dry self-supporting fibrous material of structural fibers to be used for subsequent resin infusion is disclosed in this document. The fibrous material contains structural fibers that are joined together by a binder component present in an amount of 15% by weight or less of the material. The binder component does not form a continuous film on the surface of the fibrous material. The fibrous material is characterized in that it is permeable to fluid, more specifically it is permeable to liquid resins, it crimps less through groove and has a lower dimensional variation than the fibrous material without binder.
    [00013] A binder composition to be applied to structural fibers is also disclosed in this document. The binder composition is a dispersion carried in water containing (i) one or more polymers selected from: polyurethane; polyhydroxyether; a copolymer thereof; a product of their reaction; and a combination of them; (ii) a crosslinker; and optionally, (iii) a catalyst of sufficient acid intensity to catalyze the crosslinking reaction. BRIEF DESCRIPTION OF THE DRAWINGS
    [00014] FIG. 1 illustrates a unidirectional non-wavy fabric (UD NCF).
    [00015] FIG. 2 illustrates a carbon fiber web spread with binding threads.
    [00016] FIG. 3 is a SEM image showing the veil side of a fibrous material treated with a binder according to an example.
    [00017] FIG. 4 is an SEM image showing the fiber weft side of the fibrous material shown in FIG. 3.
    [00018] FIG. 5 is a graph showing the relative volume of resin infused through the thickness of a preform as a function of time, according to an example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
    [00019] The technological challenges associated with the manufacture of narrow width fibrous products suitable for automated deposition processes, more specifically, ATL and AFP, determined the need for binder compositions capable of providing cohesion and integrity to the fibers during grooving, handling and deposition and prevent the creation of confusing edges which can dramatically affect the speed and yield of the process.
    [00020] One aspect of the present disclosure is a dry self-supporting fibrous material of structural fibers that has been treated with a unique liquid binder composition, in which the resulting fibrous material treated with a binder is permeable to liquid resin and the binder composition does not form a continuous film on the surface of the fibrous material. The binder composition is present in an amount of 15% or less by weight, for example, 0.1 and 15% by weight based on the total weight of the fibrous material and the structural fibers are the largest component of the fibrous material (for example , greater than 50% by weight based on the total weight of the fibrous material). The fibrous starting material to be treated with the binder composition can be in the form of fibers (including unidirectional or multidirectional fibers), yarns, tow, woven and non-woven fabrics.
    [00021] In one embodiment a dry unidirectional fiber web composed of unidirectional structural fibers (eg, carbon fibers) in sand weights in line with pre-impregnated state-of-the-art tape is glued to a non-woven veil of thermoplastic fibers using a continuous process on a hot melt production line. The glued unidirectional tape / veil structure is then coated with the liquid binder composition disclosed in this document. In one embodiment, the non-woven veil contains randomly arranged thermoplastic fibers that are soluble in epoxy resins. The detailed description of the resin-soluble veil can be found, for example, in published patent application US 2006/0252334. Unidirectional tape can be made by a conventional pre-impregnation method of spreading a weave of structural fibers and using a tape machine to do so. A thermoplastic resin-soluble veil is then laminated to the structural fibers scattered to maintain the shape of the tape.
    [00022] In another embodiment, a non-woven veil composed of structural fibers (for example, carbon fibers) is laminated on a fiber web (ie, a scattered fiber web) and a thermoplastic modified epoxy-based binder is coated or deposited on the web, then the web is laminated to the fiber web using a pre-impregnated tape machine to form the dry tape. Subsequently, the dry tape is coated by dip coating with the water-borne binder composition disclosed in this document. The water-borne binder composition disclosed in this document does not completely coat the modified epoxy-based binder. The resulting binder-coated tape is grooved into narrow tapes or tow of desired widths that are suitable for ATL / AFP, for example, 0.6096m or less, or 0.0381m or less. In one embodiment, the modified epoxy-based binder contains one or more multifunctional epoxy resins and a thermoplastic polymer, and can be in the form of particles or film. The incorporation of the modified epoxy-based binder on the surfaces of the weft and fiber web can also facilitate the connection of the grooved tape / tow to the tool surface or to a previously deposited tape / tow.
    [00023] The unique liquid binder composition disclosed in this document is used to coat or infiltrate the fibrous material. The fibrous material treated with a binder is suitable for the manufacture of preforms which are subsequently infused with liquid resin. As such, the binder-treated fibrous material is a fluid-permeable product that is very low in resin content (i.e., the content of binder resin not the matrix resin to be injected later) prior to resin infusion. The resin-infused preforms are then cured to form composite parts.
    [00024] The liquid binder composition as discussed above is based on a dispersion carried in water containing: (i) one or more polymers selected from polyhydroxyethers, polyurethanes, copolymers thereof, reaction products thereof, or combinations thereof; (ii) a crosslinker; and optionally (iii) a catalyst.
    [00025] In one embodiment, the binder composition is applied as a polymer emulsion to coat or infiltrate fiber or textile yarns / tow at room temperature. The water is then removed / evaporated according to a controlled time / temperature profile to achieve the desired balance of physical properties. The resulting coated yarns / tow or fibrous textiles are suitable for use in automatic tape and fiber deposition technologies, such as automated tape deposition (ATL) and automated fiber placement (AFP) to manufacture preforms which are configured to receiving liquid matrix resin in a subsequent resin infusion process. The binder composition can be applied to yarns / tow or textiles in a concentration between 0.1 and 15% by weight in relation to the total weight of the final product.
    [00026] When the binder composition is applied to fibrous materials in large sizes, the resulting binder-treated materials can be grooved in elongated strips or narrow width tow so that they are suitable for use in the production of fiber preforms dried via ATL and AFP processes. The binder composition of the present invention consistently improves the handling and grooving of fibrous threads / tow or textiles coated or infiltrated into narrower products and their formation in the preform before they are infused with resin. The binder composition also provides improvements in the bond strength between the coated fibrous component and the composite matrix after infusion and curing without unduly sacrificing important physical properties of laminates, such as the glass transition temperature (Tg) in dry and hot conditions / (H / W) and mechanical performance.
    [00027] Performance in the production of preforms and composite parts is increased by using binders that help stabilize unidirectional structural fiber textiles to groove in narrow tapes, contribute to the process of depositing tape and making preform and not interfere with the resin infusion process or with the mechanical performance of the final composite part. In addition, in some embodiments, a very light non-woven veil is bonded to the unidirectional structural fiber textile prior to bonding and grooving. The veil intensifies the diffusion of resin in the plane during the resin injection cycle. In some respects, perforations of the unidirectional structural fibrous textile can be useful to improve the diffusion of resin through the thickness of the textile material during the resin infusion process.
    [00028] Benefits resulting from using a dry unidirectional tape in an ATL / AFP process include the effective creation of a necessary preform through reduced touch labor, high deposition rates and the ability to create the pre -forms in an in situ manner, eliminating the need for any dedicated heat and pressure pre-forming cycle. In comparison to more traditional textile routes dry ATL / AFP is expected to return a very low level of scrap material due to the elimination of any need to bundle large layers of a textile roll.
    [00029] The resulting benefits for composites made from a dry unidirectional tape over traditional textiles include improved mechanical properties, very good fiber volume fraction and excellent cured layer thickness (CPT) which is not deteriorated by the addition of the very light veil. The volume fraction of composite fiber is calculated using the following equation:
    where: Vf = Fiber volume fraction Wf = Fiber weight Wm = Weight of matrix resin Pf = Fiber density pm = Density of matrix resin.
    [00030] CPT is the theoretical thickness of an individual layer which is a function of the weight of the fiber area, resin content, fiber density and resin density.
    [00031] As an added benefit, the web, which is located in the interlaminar region between layers of structural fibers and highly loaded with resin, can act as a carrier for materials such as hardening particles or hardening fibers for further hardening of the resulting composite. .
    [00032] High quality grooved tapes and grooved tow can be obtained by sufficiently high cohesion between the filaments. Good cohesion can prevent individual filaments from separating from the grooved ribbon / bur during the grooving process and other subsequent manipulations, such as when the ribbon / bur is processed using automated machines.
    [00033] In some respects, the liquid binder composition disclosed in this document penetrates the structure of the unidirectional tape, before grooving, and holds the filaments together. This penetration is also useful for controlling the width of the resulting grooved tape.
    [00034] In some embodiments, the type and amount of binder and / or bonding agents does not impede the automated deposition process or the manufacture of the composite, in particular the injection of resin, and does not alter the mechanical performance of the composite or its Tg.
    [00035] In some modalities, good deposition performance and high yield are achieved due to grooved ribbon / tow attributes, such as good cohesion and stability, good robustness to the process, in particular agitation and friction, and the ability to pick up on the tool or first layer and subsequent layers.
    [00036] The attachment of a layer of fibrous material to the tool or an anterior layer can be achieved using a binder that is activated by heat during the deposition process. It is preferable that the binder does not impede the deposition process, the manufacture of the composite, the mechanical performance of the composite or its Tg.
    [00037] Diffusion of resin through a preform during the resin injection cycle can be a function of the permeability of the preform and the direction of displacement of the resin compared to the permeability distribution. For example, in some cases, infusion parallel to the layers of the unidirectional structural carbon fiber textile can be achieved easily, although diffusion of the resin through the thickness can be more challenging, due to very small gaps or gaps between the fibers, for example. example, unidirectional tapes, hence limiting the flow of resin through the thickness. Providing perforations of the wefts, such as about 10 per cm2, allows the resin to flow sufficiently in the Z direction. The way the one-sided tape layer is fabricated can affect the convenience of having perforations to facilitate the flow of resin. For example, air permeability through a thickness greater than 25 cm3 / min may be required for the preform, and greater than 50 cm3 / min may be preferred, depending on the process window of the resin system used and the thickness of the preform to be infused. Binding compositions
    [00038] Binders have several purposes, such as for cohesion of structural fibers, for structural bonding fibers and to provide grip, so that the material remains in a stationary position during the deposition process. A binder can be selected to help maintain the cohesion of the fibers that form the unidirectional or textile layer during the grooving process. It is useful if the binder does not impede the deposition process or the manufacture of composite and, in particular, the resin injection process. Binders for bonding fibers can be reactive or non-reactive with the resin matrix when forming a composite material and examples include thermoplastic binders. The binder should generally not significantly affect the mechanical performance of the resulting composite or lower its Tg. In addition, it is preferable that the binder is easy to process and has a low cost.
    [00039] A binder composition for treating fibers / structural textile material for the purpose disclosed in this document is a waterborne binder composition containing one or more polymers selected from the group consisting of polyurethanes, aromatic polyhydroxy ethers, copolymers, mixtures, reaction products or mixtures thereof, in combination with at least one aminoplastic crosslinker and, optionally, a catalyst of sufficient acid intensity to catalyze the crosslinking reaction. Acid catalysts can include, but are not limited to, proton donor acids, such as carboxylic acids, phosphoric acids, alkyl acid phosphates, sulfonic, disulfonic acids and / or Lewis acids, such as chloride, bromide or aluminum halide, halide ferric, boron trihalides and many others in both categories, as is known to one skilled in the art. In a preferred embodiment, the crosslinker is a melamine-based crosslinker, for example, class tri to hexamethoxyalkyl melamine of aminoplastic crosslinkers.
    [00040] The polyurethane can be synthesized by reacting a polyisocyanate with one or more polyols having an average numerical molar mass (Mn) of at least 400 g / mol selected from a group consisting of aliphatic or aromatic polyether polyols and optionally polyester polyols : a compound capable of forming anions and with at least two groups that are reactive towards isocyanate groups; a low molar mass polyol with Mn of 60 to 400 g / mol; a combination of them.
    [00041] Suitable polyisocyanates (meaning compounds having a plurality of isocyanate groups) to prepare the polyurethane include any organic polyisocyanate, preferably monomeric diisocyanates. Especially preferred are polyisocyanates, especially diisocyanates having aliphatically and / or cycloaliphatically linked isocyanate groups, although polyisocyanates having aromatically linked isocyanate groups are not excluded and can also be used.
    [00042] Examples of suitable polyisocyanates which can be used include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-l, 6- hexamethylene diisocyanate, 1,12-dodecanediisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and / or -1,4-diisocyanate, l-isocyanate-2-isocyanatomethyl cyclopentane, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), 2,4- and / or 2,6-hexahydrotoluylene diisocyanate, 2,4'- and / or 4 , 4'-dicyclohexylmethane diisocyanate, a, a, a ', a-tetramethyl-1,3- and / or -1,4-xylene diisocyanate, 1,3- and 1,4-xylylene diisocyanate , 1-isocyanato-1-methyl-4 (3) - isocyanatomethylcyclohexane, 1,3- and 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluylene diisocyanate, diphenyl methane-2 , 4'- and / or -4,4'-diisocyanate, naphthalene-1,5-diisocyanate, triphenylmethane-4,4 ', 4' '- triisocyanate, polyphenyl polymethylene polyisocyanates of the type obtained condensation of aniline with formaldehyde according to used by phosgenation and mixtures of the aforementioned polyisocyanates.
    [00043] Suitable polyols preferably have a numerical average molar mass (Mn) of 400 g / mol to 5000 g / mol. Examples of suitable polyols include polyether aliphatic polyols, such as polyoxyethylene glycol, polyoxypropylene glycol, or mixed polymers of such units, polyester polyols obtained by polycondensation of diols or polyols with dicarboxylic or polycarboxylic acids, such as polyester polyols including adipate polyethylene, mixed polyesters derived ethylene glycol, hexane diol, trimetill propane, adipic and terephthalic acid, etc. Other building blocks that can constitute, or be included in, such polyester polyols are hydroxycarboxylic acids, such as hydroxybutyric acid or hydroxy capranoic or its lactones.
    [00044] Suitable polyether aromatic polyols are epoxy resins and or phenoxy resins or mixtures thereof.
    [00045] The terms "poly (hydroxyether)" and "phenoxy" in this document refer to substantially linear polymers having the general formula:

    [00046] where D is the radical residue of a dihydric phenol, E is a radical residue containing hydroxyl of an epoxide and n represents the degree of polymerization and is at least 30 and preferably 80 or more. The term "poly (hydroxyether) thermoplastic" is intended to include mixtures of at least two poly (hydroxyether) thermoplastics.
    [00047] The dihydric phenol contributing to the residue of the phenol radical, D, can be either a mononuclear dihydric phenol or a dihydric polynuclear, such as those having the general formula:

    [00048] where Ar is a divalent aromatic hydrocarbon, such as naphthylene and, preferably, phenylene, X and Y which may be the same or different are alkyl radicals, preferably having 1 to 4 carbon atoms, halogen atoms , that is, fluorine, chlorine, bromine and iodine or alkoxy radicals, preferably having 1 to 4 carbon atoms, a and b are integers having a value d 0 to a maximum value corresponding to the number of hydrogen atoms in the aromatic radical ( Ar) which can be substituted by substituents and R is a bond between adjacent carbon atoms, as in dihydroxydiphenyl or is a divalent radical including, for example,

    [00049] and divalent hydrocarbon radicals, such as alkylene, alkylidylene, cycloaliphatic, for example, cycloalkylidene, halogenated alkoxy or alkylene substituted by aryloxy, alkylidene and cycloaliphatic radicals, as well as alkylene and aromatic radicals including halogenated, aromatic radicals substituted by alkyl, alkoxy or aryloxy and a ring fused to an Ar group; or R1 can be polyalkoxy or polysiloxy or two or more alkylidene radicals separated by an aromatic ring, a tertiary amino group, an ether bond, a carbonyl group or a sulfur-containing group, such as sulfoxide and the like.
    [00050] Examples of dihydric polynuclear phenols include, but are not limited to: Bis (hydroxyphenyl) alkanes, such as 2,2-bis- (4-hydroxyphenol) propane, 2,4'-dihydroxydiphenylmethane, bis (2- hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane, 1,1-bis (4-hydroxyphenyl ethane, 1,2-bis (4-hydroxyphenyl) ) - ethane, 1,1, -bis (4-hydroxy-2-chlorophenyl) ethane, 1,1-bis- (3-methyl-4-hydroxyphenyl) ethane, 1,3-bis (3-methyl-4- hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) -propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (2-isopropyl-4-hydroxyphenyl ) propane, 2,2-bis- (4-hydroxylnaphthyl) propane, 2,2-bis (4-hydroxyphenyl) -pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) ) heptane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) cyclohexylmethane, 1,2-bis (4-hydroxy-phenyl-1,2, -bis (phenyl) propane, 2,2, -bis (4 -hydroxyphenyl) -1-phenyl-propane and the like; Di (hydroxyphenyl) sulfones, such as bis (4-hydroxy-phenyl) sulfone, 2,4'-dihydroxydiphenyl sulfone, 5 '-chloro-2,4'-dihydroxydiphenyl sulfone, 5'-chloro-4,4'-dihydroxydiphenyl sulfone and the like; Di (hydroxyphenyl) ethers, such as bis (4-hydroxy-phenyl) ether, 4,3'-, 4,2'-, 2,2 ', -2,3'-, dihydroxydiphenyl ethers, 4, 4'-dihydroxy-2,6-dimethyldiphenyl ether, bis (4hydroxy-3-isobutylphenyl) ether, bis (4-hydroxy-3-isopropylphenyl) ether, bis (4-hydroxy-3-isopropyl) ether, bis ( 4-hydroxy-3-chlorophenyl) ether, bis (4-hydroxy-3fluorfenyl) ether, bis (4-hydroxy-3-bromophenyl) ether, bis (4-hydroxynaphthyl) ether, bis (4-hydroxy-3-chloronaftyether , bis (2-hydroxydiphenyl) -ether, 4,4'-dihydroxy-2,6-dimethoxydiphenyl ether, 4,4-dihydroxy-2,5-diethoxydiphenyl and the like. Also suitable are the bisphenol reaction products of 4-vinylcyclohexene and phenols, for example, 1,3-bis (p-hydroxyphenyl) -1-ethylcyclohexane and the dipentene bis-phenol reaction products or their isomers and phenols, such as 1,2-bis (p- hydroxyphenyl) -1-methyl-4-isopropylcyclohexane, as well as bisphenols such as 1,3,3 'trimethyl-1- (4-hydroxyphenyl) -6-hydroxyindane, 2,4-bis (4-hydroxyphenyl) -4-methylpentane and the like.

    [00051] where X and Y are previously defined, a and b have values from 0 to 4 inclusive, and R is a divalent saturated aliphatic hydrocarbon radical, particularly alkylene and alkylidene radicals, having from 1 to 3 carbon atoms and radicals cycloalkylene having up to and including 10 carbon atoms.
    [00052] Mixtures of dihydric phenols can also be used and whenever the term "dihydric phenol" or "dihydric polynuclear phenol" is used in this document, mixtures of these compounds are intended to be included.
    [00053] The epoxide contributing to the radical residue containing hydroxyl, E, can be mono-epoxide or diepoxide. A monopoxide contains an oxirane group and provides a radical E residue containing a single hydroxyl group, a diepoxide contains two such oxirane groups and provides a radical E residue containing two hydroxyl groups. Saturated epoxides, by which the term ethylene-free diepoxides, that is,> C-C <and acetylenic installation, that is, -C = C-, are preferred. Particularly preferred are saturated halo-substituted mono-epoxides, i.e., saturated epichlorohydrates and diepoxides that contain only carbon, hydrogen and oxygen, especially those in which adjacent or adjacent carbon atoms form a part of an aliphatic hydrocarbon chain. Oxygen in such diepoxides can be, in addition to oxygen oxirane, oxygen ether -0-, oxacarbonyl oxygen carbonyl oxygen and the like.
    [00054] Specific examples of monoepoxides include epichlorohydrins, such as epichlorohydrin, epibromohydrin, 1,2-epoxy-1-methyl-3-chloropropane, 1,2-epoxy-1-butyl-3-chloropropane, 1,2- epoxy-2-methyl-3-fluorpropane and the like.
    [00055] Illustrative diepoxides include diethylene glycol bis (3,4-epoxycyclohexane-carboxylate), bis (3,4-epoxycyclohexyl-methyl) adipate, bis- (3,4-epoxycyclohexyl-methyl) phthalate, 6-methyl-3, 4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate, 2-chloro-3,4-epoxycyclohexylmethyl-2-chloro-3,4-epoxycyclohexane-carboxylate, diglicidyl ether, bis (2,3-epoxycyclopentyl) - ether , 1,5-pentanediol bis (4-methyl-3,4-epoxycyclohexyl-methyl) ether, bis (2,3-epoxy-2-ethylhexyl) adipate, diglycidyl maleate, diglycidyl phthalate, 3-oxate-tetracyclo [ 4.4.0.17,10.02,4] -undec-8-yl 2,3-epoxy-propyl ether, bis (2,3-epoxycyclopentyl) sulfone, bis (3,4-epoxyhexoxypropyl) sulfone, 2,2'-sulfonildietyl, bis (2,3-epoxycyclopentanecarboxylate), 3-oxathetracyclo- [4.4.0.1 7,10.0 2.4] -undec-8-yl 2,3-epoxybutyrate, 4-pentenal-di- (6-methyl-3,4 - epoxycyclohexylmethyl) acetal, ethylene glycol bis (9,10-epoxystearate), diglycidyl carbonate, bis (2,3-epoxybutylphenyl) -2-ethylhexyl phosphate, diepoxidioxane, butadiene dioxide and dioxide 2,3-dimethyl butadiene.
    [00056] Examples of compounds capable of forming anions include polyols, particularly diols and polyamines, particularly diamines, or hydroxyamines, which take from 1 to 3 carboxyl or sulfonic acid groups per molecule.
    [00057] Examples of carboxylate-containing compounds of this composition include the reaction of isocyanate-terminated polyol prepolymers (obtained by reacting excess diisocyanate with hydroxyl-containing prepolymers) with hydroxyl-containing carboxylic acids. Examples of cationic terminated compounds of this invention include quaternary ammonium or phosphonium prepolymers. Such cationic compositions can be prepared by reacting alcohols containing tert-amine with the isocyanate-terminated prepolymers mentioned above followed by reacting with a quarternizing agent such as dimethyl sulfate or an alkyl halide as is known to one skilled in the art.
    [00058] Examples of low molecular weight polyols with a molar mass of preferably 60 to 400 include ethylene glycol, diethylene glycol, 1,4-butane diol, cyclohexane diol and any other diol known to those skilled in the art.
    [00059] Examples of preferred water-borne phenoxy resin are condensation polymers derived from bisphenol-A (2,2-bis (p-hydroxyphenyl) propane and epichlorohydrin having the structural formula:

    [00060] Examples of polyhydroxyether water dispersions are Phenoxy PKHB, PKHH and PKHC marketed under the trade name PKHW 34, 35 and 38 by InChem.
    [00061] Suitable crosslinkers include aminoplastics, or amino resin crosslinkers which are the reaction products of urea or melamine with formaldehyde and an alcohol. In addition to urea and melamine, other compounds with similar functionality, such as benzoguanamines, glycolurils, cyclic ureas, hydantoins, primary and secondary amides, carbamates, etc., can also be used where certain property advantages are required.
    [00062] The crosslinking reaction ("cure") is mainly one of transeterification between hydroxyl groups in the main polymeric portion and alkoxymethyl or alkoxybutyl groups on the amino resin. In addition to the transeterification reaction, the amino resin almost always undergoes self-condensation reactions to some extent, more or less dependent on the type of amino resin.
    [00063] Another attribute of amino crosslinkers is that their hydrophilic or hydrophobic characteristics can be adapted so that it is possible for a person skilled in the art to select whether the amino resin crosslinker predominantly resides in the organic phase or in the aqueous phase of the aqueous dispersions. There may be certain advantages for the amino resin crosslinker to reside in one phase or the other, particularly if it is desired to apply the composition by different methods, such as dipping, roller coating or spraying, where one or both phases may or may not be desired to remain on the substrate before curing.
    [00064] The main by-products of the curing reaction include methanol and / or butanol and water. Curing temperatures are typically in the range of 180 to 465 ° F (82 to 232 ° C) for times ranging from 15 to 30 min at the lower end of the temperature range to perhaps just a few seconds at the upper end. There are highly catalyzed amino resin formulations that cure at room temperature, such as those found in the wood and plastic coating industry, but most commercially available formulations are typically cured at elevated temperatures and are described in the present invention.
    [00065] In a preferred embodiment of this invention a monomeric alkyloxymethyl melamine (Chemical Structure 1) with lower levels of dimeric and trimeric analogues (Chemical Structures 2 and 3, respectively) which is linked via bridges or methylene, -N- CH2N - or methylenoxy -NCH2OCH2-N can be used. Structure 1. Alkylated aminoplastic melamine monomer
    where R is an alkyloxymethyl and preferably a reactive methoxymethyl group. Structure 2. Alkylated aminoplastic melamine dimer
    where R is an alkyloxymethyl and preferably a reactive methoxymethyl group. Structure 3. Trimer of an alkylated aminoplastic melamine
    where R is an alkyloxymethyl and preferably a reactive methoxymethyl group.
    [00066] Various catalysts can optionally be used to accelerate the crosslinking reaction of the composition, depending on the curing temperature and the particular amino resin used. Suitable catalysts include strong acids that are able to catalyze the reaction between the aminoplastic and the resin, including superacids and blocked versions of them. In a preferred embodiment, a blocked acid can be used to achieve high reaction rates, while providing improved formulation stability and keeping the pH value unchanged. Blocked sulfonic acid catalysts, for example, blocked amine sulfonic acid catalyst, are particularly suitable.
    [00067] In a preferred embodiment, the liquid binder composition is an aqueous dispersion containing a polyhydroxyether-polyurethane copolymer; methoxyalkyl melamine (for example, tri-hexa methoxyalkyl melamine) as an aminoplastic crosslinker; and a blocked acid catalyst (such as blocked sulfonic acid catalyst), wherein: a. the copolymer can have a numerical molecular weight (Mn) in the range of 10,000 to 100,000 Da and a polydispersity (Mw / Mn) in the range between 1.1 and 5, and b. the copolymer can have an average particle size (d50) in the range of 0.1 to 50 microns.
    [00068] The amount of binder applied to the fibers can be less than about 15% by weight and, preferably, less than 10% and, more preferably, less than 5%, such as, 4%, 3%, 2 % or 1%.
    [00069] In some embodiments, the copolymer's polyhydroxyether portion contains a Bisphenol-A, and the copolymer's polyurethane portion is based on polyisocyanate and a polyol selected from a group consisting of aliphatic or aromatic polyether polyester and polyester polyols.
    [00070] The disclosed binder composition can be used for the impregnation, at room temperature, of self-supporting dry fibrous products suitable for automated deposition processes (eg ATL / AFP) with no limitation on the width of the product. The binder can be applied to fibrous products by coating by liquid immersion, roller coating or spraying on the fiber web. In addition, the binder composition can be applied to all or specific areas of the fibrous product using standard manufacturing processes.
    [00071] When the unidirectional material or dry self-supporting textile is used in a resin injection process, it is useful if the binder does not form a continuous film on the surface of the unidirectional material or textile, which can prevent the resin from satisfactorily penetrating through the preform thickness comprising the unidirectional or textile material during the resin injection cycle. Fibrous materials
    [00072] The initial fibrous materials to be treated with the liquid binder disclosed in this document may be in the form of a self-supporting unidirectional tape, for example, having a width ranging from about several inches wide to narrow widths as low as XA inches , or a non-corrugated fabric. The self-supporting unidirectional tape can be wound on spools and can be used in the ATL / AFP process. Non-corrugated fabric (NCF) containing unidirectional tow that is sewn together. The towings may or may not touch each other, so gaps are present between towings, thus providing permeations in the material. In contrast, unidirectional tape does not contain stitching because it contains a type of binder chemistry that holds the fibers together. Unifiber is a trade name for a product that contains fine threads that tie the fibers together in such a way that there are no gaps or permeations.
    [00073] In certain embodiments, a non-woven veil composed of fibers randomly arranged is laminated to a fiber weave of structural fibers to form a dry ribbon which is later coated with the liquid binder composition disclosed in this document. The veil can provide permeability to the binder-coated fibrous material. In some respects, the veils are made of structural material similar to that used as structural fibers, such as carbon, glass and aramid. Other purposes of veils include a means to hold the fibers together; however, this is not the fundamental importance of the veils in this application. The web itself may contain additional bonding or stiffening agents / particles.
    [00074] The term "fibrous material" as used in this document can include structural fibers or fibrous materials adapted for the structural reinforcement of composites. Structural fibers can be made of high-strength materials, such as carbon, glass and aramid. The fibers can take the form of any one of short fibers, continuous fibers, fiber sheets, fabrics and combinations thereof. The fibers can still adopt any of the unidirectional, multidirectional configurations (for example, bi or three-directional), non-woven, woven, knitted, stitched, dotted, rolled and braided, as well as structures of spiral, felt and chopped carpet. Woven fiber structures can comprise a plurality of woven tow having less than about 1000 filaments, less than about 3000 filaments, less than about 6000 filaments, less than about 12000 filaments, less than about 24000 filaments, less than about of 48000 filaments, less than about 56000 filaments, less than about 125000 filaments and more than about 125000 filaments. In other embodiments, the tow can be held in position by cross tow seams, weft insertion point seams or a small amount of resin, such as a gomanting agent.
    [00075] The fibrous product that has been treated with the binder composition according to the present disclosure is a dry, self-supporting fibrous material. The term "dry" as used in this document refers to a material that can be considered to have a dry feel which is not sticky to the touch and substantially without any matrix resin. The term "self-supporting" refers to a cohesive form of fibers or filaments that do not separate from each other, for example, during the grooving process and other subsequent manipulations, such as when the fibrous product is processed using automated machines. For example, self-supporting refers to the ability of the dry self-supporting fibrous product to maintain the integrity of the fibrous material such as a favorable edge quality, that is, a clean edge, without bridge fibers, down, or other observed defects which would otherwise could occur during the grooving process if binder treatment was not used. In some aspect, the self-supporting fibrous product has edges after grooving that are substantially free of protruding dry filaments.
    [00076] The fibrous material treated with a binder can generally maintain its position without the need for an additional carrier fabric or curtain to prevent the fibers from separating. In addition, the dry self-supporting fibrous material can be stored at room temperature and does not need to be refrigerated, due to the fact that it does not contain a substantial amount of a matrix resin, in contrast to pre-impregnated materials. Veil
    [00077] In some embodiments, a non-woven veil can be used in addition to the binder composition to improve the permeability in the plane of the material and favor the flow of resin in the plane. In some respects, the veil can be a very light weight veil of about 1 g to 8 g per square meter of dry, self-supporting fibrous material which is laminated to it.
    [00078] In addition, the veil can provide stability in the direction of the weft across the unidirectional or textile material, such as a unidirectional tape.
    [00079] In an even more beneficial aspect, the veil can be used as a carrier for particles or composite stiffening fibers in the interlaminar region.
    [00080] The veil can be of the same material nature as the fibers of the unidirectional or textile material, or alternatively, it can be made of one or more organic materials, such as some thermoplastic stiffening materials. In addition, the veil may comprise a hybrid blend of both the same type of fibers and at least one organic material.
    [00081] The veil and the binder composition are used to help deposit the fibrous material in the machine by applying heat (hot air, laser or IR) and pressure via the compaction roller. When polymer webs are used, the preferred softening point of polymer webs and binders is 150 ° C or less in order to allow the material to bond and form a consolidated preform at acceptable machine speeds.
    [00082] In some respects, the flat resin injection cycle is 3 times faster than a similar composite without a lightweight veil, consequently the achievable layer flow length is significantly improved by a factor of 7. Perforations
    [00083] In some embodiments, the fibrous material treated with a ligand contains perforations in it. “Perforation” as used in this document may include perforations through the entire thickness of the fibrous material. Perforated materials can provide air permeability above 50 cm3 / min and allow infusion of preforms with thicknesses greater than 30 mm in reasonable infusion times, for example, <4 hours.
    [00084] Perforations can be performed by needle piercing, laser beams or any other available methods to pierce the material through its thickness. Drilling hole dimensions, usually the diameter, are combined with the drilling density to achieve the expected air permeability. More air permeability is needed to form thicker preforms, that is, with more layers, than with thinner preforms.
    [00085] Generally, a minimum of 20 cm3 / min is desirable for an effective flow of the resin. However, for preforms with a thickness greater than 25 mm (1 ”), a minimum of 50 cm3 / min is desirable. Of course, the desired air permeability can also be a function of the viscosity of the resin and the processing conditions at a given temperature and the complexity of the part.
    [00086] For perforated materials, the fibers forming the unidirectional fiber web (UD) preferably do not move and cover the perforated holes after the drilling step has been carried out, otherwise the gain in air permeability would be reduced or zero. The binder composition disclosed in this document previously holds the fibers together and prevents them from covering the drilled holes.
    [00087] Perforation of the fibrous material also includes the creation of some small cracks or gaps between the fibers during the process of forming the UD fiber web. Preform
    [00088] The term "preform" or "fiber preform", as used in this document, includes a set of fibers, layers of fibers or layers of fabric, such as unidirectional fibers and woven fabrics that are ready to receive a liquid resin in a resin infusion process.
    [00089] It has been found that using the fibrous material treated with a self-supporting binder, in some cases, results in high-performance composites made via a resin infusion process. EXAMPLES
    [00090] The following examples refer to unidirectional fiber materials (UD) for ATL / AFP application. Example 1
    [00091] The following fabrics were used in this Example. (1) A unidirectional non-corrugated fabric (UD NCF), supplied by Saertex, is shown in Fig. 1. This fabric is produced at 1.27 meters in width. Definition of carbon tow is very present and inter-tow clearances are up to 2 mm wide. Polyester sewing thread keeps the carbon tow together. Thin polyester yarns are deposited through the fabric to provide lateral integrity and stability to the fabric. (2) A weft spread with binder threads (Sigmatex Unifiber fabric) is shown in Fig. 2. Carbon spars are spread and held together by epoxy-coated glass threads on both sides of the tapes. There is no inter-clear or marginal clearance.
    [00092] Both fabrics were coated with a binder with a thermoplastic modified binder, based on epoxy (Cycom® 7720 from Cytec Engineered Materials). A powder spreading method was used to deposit about 5 g / m2 of the binder composition on both sides of each tissue. The fabrics with the scattered powder were passed through a double belt press to further direct the binder through the fiber web and ensure a good cohesion of the UD fiber web. This is called a stabilization step. In addition, a very light carbon veil with a fabric weight of 4g / m2 was laminated on one side of each fabric at the same time as the fabric was passed through the double press to fix the binder. Dual belt processing conditions were a speed of 2 m / min and a temperature of 210 ° C. The laminated, stabilized fabrics were very stable, although malleable, allowing manipulation to the desired shape without loss of fiber or fraying of the edge.
    [00093] Then, the stabilized fabrics were grooved to 50mm wide ribbons having a width variation less than + / -1.0 mm. The edge quality of the grooved tapes was sufficiently clean with limited bridge fibers, down and other defects observed. However, product quality could still be improved for the manufacture of large aircraft components, using automated high-speed production processes. Example 2
    [00094] A series of different catalyzed and non-catalyzed bonding agents based on families of polyhydroxyether or polyurethane, copolymers or combinations thereof have been mixed according to the compositions disclosed in Table 1. EP1 is a solid epoxy novolac emulsion 53% marketed by COIM (Italy). PU1 is a 52% solid water dispersion of a 2,2-bis (4-hydroxyphenyl) propane modified polyurethane with a numerical average molecular weight of ~ 30,000 Daltons. The polyurethane portion was obtained by the reaction of isocyanate diisocyanate and polypropylene glycol. PU2 is a 40% solid self-crosslinking thermoplastic polyurethane dispersion in water marketed by BASF, while PU3 and PU4 are 43% and 34% solid self-crosslinking polyester urethane dispersions in water marketed by Bayer Material Science. PHE1 is a 34% solid polyhydroxyether emulsion in water available from Inchem (US). TABLE 1 - Binding compositions
    • Alkylated MethylMelamine (AMM) t Modified Aliphatic Polyisocyanate (MAPI) Blocked p-Toluenesulfonic acid (bp-TSA) tt Deionized water
    [00095] Binding agents were used to dip the same unidirectional, non-corrugated fabric (Saertex, Germany) described in Example 1.
    [00096] Binder-coated fabrics were evaluated for curtain capacity, anti-stripping behavior, shrinkage and self-bonding ability. Curtain was determined by hot winding at 145 ° C (temperature ramp rate of 3 ° C / min from room temperature) for 1 minute of 350x350mm coated fabric in a tapered tool (height = 86mm, inner diameter = 120mm , external diameter = 310 mm) under vacuum (60 mmHg vacuum during the entire test) and determining the number of folds. Materials giving less than 6 folds were considered excellent (A), materials resulting in 6 to 12 folds were considered acceptable (B) while materials producing more than 12 folds were considered unacceptable (C).
    [00097] Anti-stripping behavior was determined on a developmentally controlled down feather meter having four sections (outlet, friction rollers, gripping plate and winder) operating at a speed of 20 m / min. The amount of fluff accumulated on the gripping plate over a period of 5 minutes was weighed and the materials were classified accordingly. Feather is the debris loosened by tow that rubs against the friction rollers and is collected by the gripping plate. Materials resulting in more than 500 mg of down were considered unacceptable (C), materials shedding between 200 mg and 500 mg were considered acceptable (B), while materials creating less than 200 mg of down were considered excellent (A). Shrinkage was determined by measuring the width of the pure and binder-coated tissue after heat treatment (3 minutes at 100 ° C + 4 minutes at 130 ° C). Materials resulting in less than 1% shrinkage were considered excellent (A), materials giving 1 to 2% were considered acceptable (B) while materials giving more than 2% were considered unacceptable (C). Self-bonding capacity was determined by applying a pressure of 10N using a compaction roller at a temperature of 100 ° C for 5 seconds. The results are shown in Table 2. TABLE 2 - Physical properties of fabrics coated with ligand
    A = excellent. B = acceptable. C = unacceptable.
    [00098] Depending on the binder composition and the content in the fibrous product, a specific pattern of physical properties can be achieved using the binder compositions described in Table 1. Example 3
    [00099] Some of the binder compositions disclosed in Table 1 were used to coat by immersion at room temperature the same unidirectional, non-wavy fabric (Saertex-Germany) described in Example 1. All coated fabrics were then dried for 3 minutes at 100 ° C. ° C and then for 4 minutes at 130 ° C in an oven.
    [000100] The non-corrugated fabrics coated with ligand were then cut into smaller layers and the layers were deposited in a stacking sequence. The deposition was then preformed in an oven at 130 ° C for 30 minutes and infused with Prism® EP2400 (stiffened epoxy system available from Cytec Engineered Materials). Panels having a Vf (fraction of fiber volume) in the range of 55 to 57% were produced after curing the preformed infused at 180 ° C for 2 h.
    [000101] For comparison purposes, the same pure unidirectional uncoated (uncoated) fabric was used to prepare otherwise identical test panels (Control 1). A variety of mechanical tests were performed on the panels and the results are shown below in Table 3. Table 3. Thermomechanical performance of infused panels Prism® EP2400
    Example 4
    [000102] Intermediate module carbon fibers (Tenax IMS 65) were formed on a 12 ”wide 196 g / m2 unidirectional web using a pre-impregnated tape machine while a 4 g / m2 carbon web and 5 g / m2 of epoxy-based binder modified by thermoplastic was laminated to the unidirectional web in the same pre-impregnated tape machine. The resulting unidirectional tape was subsequently coated with liquid with the binder described in Example 2d to achieve a binder coating of 3 g / m2. SEM Pictures, Figs. 3 and 4, show on both the veil side and the fiber weft side, the presence of binders that do not form a film, each having distinctive morphology with the binder described in Example 2d forming droplets smaller than the diameter of the fiber carbon, while the other binder forms much larger binder particle sizes that overlap multiple fibers, but do not form a film.
    [000103] This unidirectional tape was then slotted into multiple tow of different widths. Each tow width was measured using an electronic automated measuring device equipped with a very fine resolution digital camera. Approximately 2900 measurements were collected for each burlap width. Table 4 below summarizes the measurement analysis. Table 4. Target and experimental grooved tape widths
    In Table 4, VOC is the coefficient of variation and it is calculated by dividing the standard deviation (Std dev) by the mean (Avg). Example 5 Comparative example - permeability assessment in the Z direction
    [000104] The permeability of resin in the z direction of the material described in Example 4 (6.35 mm - l / 4 ”wide) was compared to that of a carbon tow coated / formed of commercial binder (IMS60 24K) of equal width and similar area weight.
    [000105] Preforms were manufactured using an AFP machine with a laser head to compact dry tissues applying approximately 100N of pressure and a local surface temperature in the range of 120 ° C to 180 ° C. Quasi-isotropic preforms of 150 x 150 mm of approximately 10 mm were deposited with a target clearance setting of 0 mm between adjacent tow.
    [000106] Preforms were then infused with Prism® EP2400 (stiffened epoxy system available from Cytec Engineering Materials) at 100 ° C using a bagging arrangement to promote resin flow through the thickness and a vacuum <500 Pa. volume of infused resin was monitored over time.
    [000107] Fig. 5 shows the relative volume of resin infused through the thickness of the preform as a function of time.
    [000108] The preform manufactured using the material described in Example 4 resulted in the best permeability values, allowing the entire resin to flow through the thickness of the preform in less than 1 hour, while only 20% of the volume of resin penetrated the burlap preform formed in more than 1 hour due to the lower width tolerance of the product, its propensity to nest during the deposition process and the resulting high variation in the local CPT.
    权利要求:
    Claims (14)
    [0001]
    1. Grooved tape formed from groove of a dry self-supporting fibrous material, the fibrous material characterized by the fact that it comprises: a layer of dry structural fibers laminated in a non-woven web of randomly arranged fibers; and a water-borne binder composition distributed to structural fibers and the non-woven web, said water-borne binder composition comprising (i) a copolymer or polyhydroxyether and polyurethane reaction product and (ii) an aminoplastic crosslinker, wherein the structural fiber layer is in the form of unidirectional fibers or a fabric the water-borne binder composition is present in an amount of 15% or less by weight based on the total weight of the fibrous material and does not form a continuous film on the material surface fibrous, and the fibrous material is permeable to liquid resin.
    [0002]
    Grooved tape according to claim 1, characterized in that the layer of structural fibers is not bonded to a layer other than the non-woven web.
    [0003]
    Grooved tape according to claim 1, characterized in that the binder composition still comprises a catalyst of sufficient acid intensity to catalyze the crosslinking reaction.
    [0004]
    Grooved tape according to claim 1, characterized in that the fibrous material still comprises particles of an epoxy-based binder.
    [0005]
    5. Slotted tape according to claim 1, characterized by the fact that the non-woven web has a real weight of 1 to 8 grams per square meter of dry self-supporting fibrous material.
    [0006]
    Grooved tape according to claim 1, characterized in that the non-woven web comprises thermoplastic fibers that are soluble in epoxy resins.
    [0007]
    7. Slotted ribbon according to claim 1, characterized in that the veil comprises fibers made of carbon or polymeric material.
    [0008]
    8. Slotted ribbon according to claim 1, characterized in that the veil comprises glass fibers or aramid.
    [0009]
    Grooved tape according to claim 4, characterized in that the layer of structural fibers is in the form of unidirectional fibers and the non-woven web is composed of carbon fibers.
    [0010]
    10. Slotted ribbon according to claim 1, characterized in that the non-woven web comprises carbon fibers.
    [0011]
    11. Grooved tape according to claim 1, characterized in that the grooved tape has a width of 0.6096 meters or less.
    [0012]
    Grooved tape according to claim 1, characterized in that the grooved tape has a width of 0.0381 meters or less.
    [0013]
    13. Method for making a grooved ribbon as defined in claim 1, characterized in that it comprises: laminating a layer of structural fibers in a non-woven web of fibers arranged at random to form a laminated structure; coating the laminated structure with a water-borne binder composition comprising the copolymer or product of the polyhydroxyether and polyurethane reaction, the aminoplastic crosslinker and, optionally, a catalyst; drying the coated laminated structure; and grooving the tape-coated structure.
    [0014]
    14. Method according to claim 13, characterized in that it further comprises depositing particles of an epoxy-based binder on the structural fiber layer or on the web prior to lamination.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014015254B1|2021-02-23|grooved ribbon, and method for making a grooved ribbon
    US10583615B2|2020-03-10|Dry fibrous tape for manufacturing preform
    BR102016024828A2|2017-05-02|polyurethane prepregs with adjustable adhesive
    同族专利:
    公开号 | 公开日
    US10369773B2|2019-08-06|
    CA3046599C|2020-04-14|
    CN103906610B|2016-03-30|
    MX2014007082A|2014-10-24|
    JP6494126B2|2019-04-03|
    CA2859806A1|2013-06-27|
    BR112014015254A2|2017-07-04|
    AU2017200495B2|2018-08-09|
    AU2012359036B2|2017-02-02|
    US20140370237A1|2014-12-18|
    US10112375B2|2018-10-30|
    US20180072037A1|2018-03-15|
    US9393758B2|2016-07-19|
    EP2794221A2|2014-10-29|
    KR101993358B1|2019-06-26|
    TWI618834B|2018-03-21|
    AU2012359036A1|2014-02-20|
    EP3266917B1|2019-04-17|
    IN2014CN04426A|2015-09-04|
    JP2015504118A|2015-02-05|
    WO2013096377A2|2013-06-27|
    US20160303842A1|2016-10-20|
    RU2014115681A|2016-02-10|
    ES2734398T3|2019-12-05|
    MY169084A|2019-02-14|
    JP6126623B2|2017-05-10|
    MX340903B|2016-07-29|
    CA3046599A1|2013-06-27|
    ES2822980T3|2021-05-05|
    AU2017200495A1|2017-02-16|
    TW201335462A|2013-09-01|
    EP2794221B1|2018-04-04|
    RU2628374C2|2017-08-16|
    CA2859806C|2019-08-13|
    EP3266578B1|2020-07-15|
    EP3266917A1|2018-01-10|
    WO2013096377A3|2014-02-27|
    BR112014015254A8|2019-02-12|
    KR20140109360A|2014-09-15|
    ES2674933T3|2018-07-05|
    CN103906610A|2014-07-02|
    EP3266578A1|2018-01-10|
    JP2017149964A|2017-08-31|
    MX361377B|2018-12-05|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-08| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-02-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-23| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161577990P| true| 2011-12-20|2011-12-20|
    US61/577990|2011-12-20|
    PCT/US2012/070480|WO2013096377A2|2011-12-20|2012-12-19|Dry fibrous material for subsequent resin infusion|
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