# US 11,028,244 B2 · Prepreg, laminate body, fiber reinforced composite material, and manufacturing method for fiber reinforced composite material > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,028,244 B2 - Document ID: US11028244B2 - Status: Granted - Kind: B2 - Application number: 15/778,563 - Filed: 2016-12-14 - Published: 2018-12-13 - Granted: 2021-06-08 - Earliest claimed: 2015-12-16 - Assignees: Toray Industries, Inc. - Applicants: Toray Industries, Inc. - Inventors: Alfred P. Haro; Nobuyuki Arai - Web page: https://patentgrep.com/patent/US11028244B2 ## CPC - B32B 5/024: {Woven fabric} - B29B 11/16: comprising fillers or reinforcement {(non-woven fabrics per se D04H1/00, D04H3/00)} - B32B 5/12: characterised by the relative arrangement of fibres or filaments of {different layers, e.g. the fibres or filaments being parallel or perpendicular to each other} - C08J 5/04: Reinforcing macromolecular compounds with loose or coherent fibrous material - C08J 5/042: {with carbon fibres} - C08J 5/243: {using carbon fibres} - B29K 2063/00: Use of {EP, i.e.} epoxy resins {or derivatives thereof}, as moulding material - B29K 2307/04: Carbon - B32B 2260/023: Two or more layers - B32B 2260/046: Synthetic resin - C08J 2363/00: Characterised by the use of epoxy resins; Derivatives of epoxy resins - C08J 2481/06: Polysulfones; Polyethersulfones - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - B29B: PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS ## Abstract A permeable laminate body containing at least one partially impregnated prepreg which includes at least component (A) containing a matrix of reinforcing fiber, component (B) containing a thermosetting resin, and, optionally, component (C) containing a particle or a fiber of a thermoplastic resin exhibits long out time processability with good storage stability, achieving when molded and cured a fiber reinforced composite having a low void ratio and providing excellent mechanical performance. ## Claims ### Claim 1 A partially impregnated prepreg configured to be laid up in multiple plies in a laminate body, the partially impregnated prepreg comprised of a component (A) comprising a matrix of reinforcing fiber and a component (B) comprising a thermosetting resin, wherein i) the matrix of reinforcing fiber is partially impregnated by component (B) and ii) the laminate body has a permeability of at least 4.0E-14 m2 after an out time of 20 days at 23° C. and a void ratio after cure of <1%. ### Claim 2 (depends on 1) The partially impregnated prepreg according to claim 1, wherein the laminate body has a permeability of not greater than 1.0E-13 m2. ### Claim 3 (depends on 1) The partially impregnated prepreg according to claim 1, wherein the laminate body satisfies the following condition: P0day−P20day at 24 hr vacuum is 1.0E-14 m2 wherein P0day is the permeability parameter of 0 day out time prepreg at 24 hr vacuum, and wherein P20day is the permeability parameter of 20 day out time prepreg at 24 hr vacuum, wherein the permeability difference of P0day−P20day is 1.0E-14 m2. ### Claim 4 (depends on 1) The partially impregnated prepreg according to claim 1, wherein component (B) has a viscosity at 30° C. of between about 20,000 and 140,000 Pa·s and a minimum viscosity of between about 0.1 and about 15 Pa·s. ### Claim 5 (depends on 1) The partially impregnated prepreg according to claim 1, wherein component (B) is additionally comprised of at least one thermoplastic resin dissolved in the thermosetting resin selected from the group consisting of polyvinyl formals, polyamides, polycarbonates, polyacetals, polyvinylacetals, polyphenyleneoxides, polyphenylenesulfides, polyarylates, polyesters, polyamideimides, polyimides, polyetherimides, polysulfones, polyethersulfones, polyetherketones, polyetheretherketones, polyaramids, polyethernitriles, polybenzimidazoles, derivatives thereof, and combinations thereof. ### Claim 6 (depends on 5) The partially impregnated prepreg according to claim 5, wherein the at least one thermoplastic resin has a number average molecular weight in the range of from about 10,000 to about 70,000. ### Claim 7 (depends on 5) The partially impregnated prepreg according to claim 5, wherein the thermoplastic resin of component (B) is present in component (B) in an amount which is 5-30 weight parts per 100 weight parts of the thermosetting resin. ### Claim 8 (depends on 1) The partially impregnated prepreg according to claim 1, wherein the thermosetting resin includes at least one epoxy resin selected from the group consisting of solid bisphenol A epoxy resins, a solid bisphenol F epoxy resins, and novolac epoxy resins, and combinations thereof. ### Claim 9 (depends on 8) The partially impregnated prepreg according to claim 8, wherein the epoxy resin or combination of epoxy resins has an EEW in the range of about 100 to about 800. ### Claim 10 (depends on 8) The partially impregnated prepreg according to claim 8, wherein the epoxy resin or combination of epoxy resins has a softening point in the range of about 50° C. to about 125° C. ### Claim 11 (depends on 8) The partially impregnated prepreg according to claim 8, wherein the epoxy resin or combination of epoxy resins is present in an amount which is 5-40 weight parts per 100 weight parts of the thermosetting resin. ### Claim 12 (depends on 1) The partially impregnated prepreg according to claim 1, wherein the prepreg is additionally comprised of a component (C) comprising a particle and/or fiber of thermoplastic resin. ### Claim 13 (depends on 12) The partially impregnated prepreg according to claim 12, wherein the particle and/or fiber of thermoplastic resin of component (C) is present in an amount of about 6 wt % to about 20 wt % based on the weight of the thermosetting resin. ### Claim 14 (depends on 12) The partially impregnated prepreg according to claim 12, wherein components (B) and (C) together represent from about 32% to about 45% of the total weight of the partially impregnated prepreg. ### Claim 15 (depends on 12) The partially impregnated prepreg according to claim 12, wherein the component (C) is substantially locally distributed on or near a surface of the prepreg. ### Claim 16 (depends on 1) The partially impregnated prepreg according to claim 1, wherein the prepreg comprises a first layer comprised of a portion of the thermosetting resin and a second layer comprised of the matrix of reinforcing fiber. ### Claim 17 (depends on 16) The partially impregnated prepreg according to claim 16, wherein the first layer is at or near a surface of the prepreg up to a depth of 20% from the surface. ### Claim 18 (depends on 1) The partially impregnated prepreg according to claim 1, wherein only one side of the prepreg is covered substantially by component (B). ### Claim 19 (depends on 1) The partially impregnated prepreg according to claim 1, wherein both sides of the prepreg are covered substantially by component (B). ### Claim 20 (depends on 1) The laminate body comprised of a plurality of partially impregnated prepregs in accordance with claim 1. ### Claim 21 (depends on 20) A fiber reinforced composite material comprising at least one laminate body in accordance with claim 20, wherein the laminate body has been thermally cured. ### Claim 22 (depends on 21) The fiber reinforced composite material of claim 21, wherein after the cure cycle, the void ratio is <1%. ### Claim 23 (depends on 20) A fiber reinforced composite material comprising at least one laminate body in accordance with claim 20, wherein the matrix of reinforcing fiber is unidirectional or has a fabric weave structure. ### Claim 24 (depends on 20) A method for manufacturing a fiber reinforced composite material, comprising molding the laminate body of claim 20 using a vacuum pump and oven. ### Claim 25 A process for making a partially impregnated prepreg, comprising partially impregnating a component (A) comprising a matrix of reinforcing fiber with a component (B) comprising a thermosetting resin to form the partially impregnated prepreg, wherein component (B) is selected to have viscosity characteristics such that when the prepreg is laid up in multiple plies after an out time of 20 days at 23° C. to form a laminate body, the laminate body has a permeability of at least 4.0E-14 m2 and the void ratio of the laminate body after cure is <1%. ### Claim 26 A partially impregnated prepreg, comprising a component (A) comprising a matrix of reinforcing fiber and a component (B) comprising a thermosetting resin, wherein component (A) is partially impregnated by component (B) and wherein component (B) comprises an amount of one or more epoxy resins which are solid at 30° C. and/or an amount of at least one thermoplastic resin dissolved in the thermosetting resin which is or are effective to impart to component (B) a viscosity at 30° C. of between about 20,000 and 140,000 Pa•s and a minimum viscosity of between about 0.1 and about 15 Pa•s. ### Claim 27 A process for making a fiber reinforced composite material, comprising the steps of a) laying up a plurality of plies of prepreg to obtain a laminate body and b) curing the laminate body to obtain the fiber reinforced composite material, wherein the prepreg comprises a partially impregnated prepreg comprised of a component (A) comprising a matrix of reinforcing fiber and a component (B) comprising a thermosetting resin, wherein i) the matrix of reinforcing fiber is partially impregnated by component (B) and ii) the partially impregnated prepreg, when laid up in multiple plies after an out time of 20 days at 23° C., provides a test laminate body having a permeability of at least 4.0E-14 m2 and a void ratio after cure of <1%. ### Claim 28 A process for making a fiber reinforced composite material, the process comprising: i) forming a laminate body having a permeability of at least 4.0E-14 m2 after an out time of 20 days at 23° C. by laying up a plurality of plies of prepreg, each ply comprising a partially impregnated prepreg comprised of a component (A) including a matrix of reinforcing fiber and a component (B) including a thermosetting resin, wherein the matrix of reinforcing fiber is partially impregnated by component (B); and ii) curing the laminate body to obtain a fiber reinforced composite material having a void ratio after cure of <1%.