# US 2014/0155540 A1 · Molding material, molding method using same, method for producing molding material, and method for producing 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 2014/0155540 A1 - Document ID: US20140155540A1 - Status: Published application - Kind: A1 - Application number: 14/128,868 - Filed: 2012-06-20 - Published: 2014-06-05 - Earliest claimed: 2011-06-24 - Assignees: Toray Industries, Inc. - Inventors: Naokichi Imai; Atsuki Tsuchiya; Masato Honma; Kohei Yamashita; Shunsuke Horiuchi; Koji Yamauchi - Web page: https://patentgrep.com/patent/US20140155540A1 ## CPC - B29B 15/12: of reinforcements of indefinite length - B29B 15/127: {by spraying} - B29C 70/003: {characterised by the matrix material, e.g. material composition or physical properties} - B29C 70/30: Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core - B29C 70/40: Shaping or impregnating by compression (B29C70/34 takes precedence){not applied} - B29C 70/48: and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM] {, e.g. by vacuum} - B29C 70/521: {and impregnating the reinforcement before the die} - C08J 5/04: Reinforcing macromolecular compounds with loose or coherent fibrous material - C08J 5/042: {with carbon fibres} - C08L 71/08: Polyethers derived from hydroxy compounds or from their metallic derivatives (C08L71/02 takes precedence) - C08J 2371/12: Polyphenylene oxides - C08J 2377/00: Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers - C08J 2379/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors - C08J 2381/04: Polysulfides - C08J 2471/12: Polyphenylene oxides - 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 - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - 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) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract Provided is a molding material comprising a composite of 1 to 50 wt % of a continuous reinforcing fiber bundle (A) and 0.1 to 20 wt % of a poly(phenylene ether ether ketone) oligomer (B); and 30 to 98.9 wt % of a thermoplastic resin (C) adhering to the composite, wherein the component (B) has a melting point of not higher than 270° C. Also provided are a method for molding the molding material, a method for producing the molding material, and a method for producing a fiber-reinforced composite material. A molded article having high heat resistance and dynamic properties can be easily produced without impairing the economic efficiency and productivity during the process for producing a molding material. In addition, a fiber-reinforced composite material can be produced with more ease and high productivity. ## Claims ### Claim 1 A molding material comprising: a composite of 1 to 50 wt % of a continuous reinforcing fiber bundle (A) and 0.1 to 20 wt % of a poly(phenylene ether ether ketone) oligomer (B); and 30 to 98.9 wt % of a thermoplastic resin (C) adhering to the composite, wherein the component (B) has a melting point of not higher than 270° C. ### Claim 2 (depends on 1) The molding material according to claim 1, wherein the component (B) comprises a cyclic poly(phenylene ether ether ketone) in an amount of 60 wt % or more. ### Claim 3 (depends on 1) The molding material according to claim 1, wherein the component (B) is a mixture of cyclic poly(phenylene ether ether ketone)s having different numbers of repeating units (m). ### Claim 4 (depends on 1) The molding material according to claim 1, wherein the composite further comprises 0.001 to 20 mol % of a polymerization catalyst (D) per 1 mol of ether ether ketone structural unit in the component (B). ### Claim 5 A molding material comprising: a composite of 1 to 50 wt % of a continuous reinforcing fiber bundle (A) and 0.1 to 30 wt % of a poly(phenylene ether ether ketone) (B′); and 20 to 98.9 wt % of a thermoplastic resin (C) adhering to the composite, wherein the component (B′) is a poly(phenylene ether ether ketone) obtained by polymerizing a poly(phenylene ether ether ketone) oligomer (B) having a melting point of not higher than 270° C. using a polymerization catalyst (D). ### Claim 6 (depends on 5) The molding material according to claim 5, wherein the component (B′) has a crystal melting enthalpy ΔH determined by DSC of not less than 40 J/g. ### Claim 7 (depends on 1) The molding material according to claim 1, wherein the component (A) contains at least 10,000 carbon fiber monofilaments. ### Claim 8 (depends on 1) The molding material according to claim 1, wherein the component (C) is at least one selected from polyamide resin, polyetherimide resin, polyamide-imide resin, polyether ether ketone resin, and polyphenylene sulfide resin. ### Claim 9 (depends on 4) The molding material according to claim 4, wherein the component (D) is an alkali metal salt. ### Claim 10 (depends on 1) The molding material according to claim 1, wherein the component (A) is arranged substantially parallel to the direction of the shaft center, and the length of the component (A) is substantially the same as the length of the molding material. ### Claim 11 (depends on 10) The molding material according to claim 10, wherein the composite forms a core structure, and the component (C) surrounds the composite to form a core-sheath structure. ### Claim 12 (depends on 11) The molding material according to claim 11, wherein the form of the molding material is a long-fiber pellet. ### Claim 13 A molding material comprising a reinforcing fiber substrate (A′), a poly (phenylene ether ether ketone) oligomer (B), and a polymerization catalyst (D), wherein the component (B) has a melting point of not higher than 270° C. ### Claim 14 (depends on 13) The molding material according to claim 13, wherein the component (B) comprises a cyclic poly(phenylene ether ether ketone) in an amount of 60 wt % or more. ### Claim 15 (depends on 13) The molding material according to claim 13, wherein the component (B) is a mixture of cyclic poly(phenylene ether ether ketone)s having different numbers of repeating units (m). ### Claim 16 (depends on 13) The molding material according to claim 13, wherein the component (A′) is a carbon fiber. ### Claim 17 (depends on 13) The molding material according to claim 13, wherein the content of the component (A′) is 30 wt % or more. ### Claim 18 (depends on 13) The molding material according to claim 13, wherein the content of the component (D) is 0.001 to 20 mol % per 1 mol of ether ether ketone structural unit in the component (B). ### Claim 19 (depends on 13) A molding method, comprising press-molding the molding material according to claim 13 using a mold. ### Claim 20 (depends on 19) The molding method according to claim 19, wherein the component (B) is polymerized into a poly(phenylene ether ether ketone) (B′) in the mold. ### Claim 21 (depends on 20) The molding method according to claim 20, wherein the surface temperature of the mold during polymerization of the component (B) into the component (B′) is not higher than the melting point of the component (B′). ### Claim 22 (depends on 20) The molding method according to claim 20, wherein after the component (B) is polymerized into the component (B′) in the mold, the mold is opened without cooling to take out a molded article. ### Claim 23 A method for producing a molding material, comprising the steps of: (I) drawing and continuously feeding a reinforcing fiber substrate (A′); (II) combining the component (A′) with a poly(phenylene ether ether ketone) oligomer (B) to form a composite; (III) polymerizing the component (B) into a poly(phenylene ether ether ketone) (B′); and (IV) cooling and taking up the composite of the component (A′) and the component (B′), wherein the component (B) has a melting point of not higher than 270° C. ### Claim 24 (depends on 23) The method for producing a molding material according to claim 23, wherein the component (B) comprises a cyclic poly(phenylene ether ether ketone) in an amount of 60 wt % or more. ### Claim 25 (depends on 23) The method for producing a molding material according to claim 23, wherein the component (B) is a mixture of cyclic poly(phenylene ether ether ketone)s having different numbers of repeating units (m). ### Claim 26 (depends on 23) The method for producing a molding material according to claim 23, wherein a polymerization catalyst (D) is further combined with the other components in the step (II). ### Claim 27 (depends on 23) The method for producing a molding material according to claim 23, wherein the steps (I) to (IV) are performed on-line. ### Claim 28 (depends on 23) The method for producing a molding material according to claim 23, wherein the take-up speed in the step (IV) is 1 to 100 m/min. ### Claim 29 (depends on 23) The method for producing a molding material according to claim 23, wherein in the step (II), the heat-melted component (B) is applied to the component (A′) to form a composite. ### Claim 30 (depends on 23) The method for producing a molding material according to claim 23, wherein in the step (II), the component (B) in at least one form selected from the group consisting of particles, fibers, and flakes is applied to the component (A′) to form a composite. ### Claim 31 (depends on 23) The method for producing a molding material according to claim 23, wherein in the step (II), the component (B) in at least one form selected from the group consisting of a film, a sheet, and a nonwoven fabric is applied to the component (A′) to form a composite. ### Claim 32 A method for producing a fiber-reinforced composite material, comprising the steps of: (I-1) placing a reinforcing fiber substrate (A′) in a mold; (II-1) heat-melting a poly(phenylene ether ether ketone) oligomer (B) to form a melt solution; (III-1) injecting the melt solution obtained in the step (II-1) into the mold of the step (I-1) to impregnate the component (B) into the component (A′); and (IV-1) thermally polymerizing the component (B) into a poly(phenylene ether ether ketone) (B′), wherein the component (B) used in the step (II-1) has a melting point of not higher than 270° C. ### Claim 33 A method for producing a fiber-reinforced composite material, comprising the steps of: (I-2) drawing and continuously feeding a reinforcing fiber substrate (A′); (II-2) heat-melting a poly(phenylene ether ether ketone) oligomer (B) in an impregnation bath to form a melt solution; (III-2) passing the component (A′) continuously through the impregnation bath of the step (II-2) to impregnate the component (B) into the component (A′) and winding the resulting composite around a mandrel; and (IV-2) thermally polymerizing the component (B) into a poly(phenylene ether ether ketone) (B′), wherein the component (B) used in the step (II-2) has a melting point of not higher than 270° C. ### Claim 34 A method for producing a fiber-reinforced composite material, comprising the steps of: (I-3) drawing and continuously feeding a reinforcing fiber substrate (A′); (II-3) heat-melting a poly(phenylene ether ether ketone) oligomer (B) in an impregnation bath to form a melt solution; (III-3) passing the component (A′) continuously through the impregnation bath of the step (II-3) to form a composite of the component (B) and the component (A′) impregnated therewith; and (IV-3) pultruding the composite obtained continuously through a mold to thermally polymerize the component (B) into a poly(phenylene ether ether ketone) (B′), wherein the component (B) used in the step (II-3) has a melting point of not higher than 270° C. ### Claim 35 (depends on 32) The method for producing a fiber-reinforced composite material according to claim 32, wherein the component (B) comprises a cyclic poly(phenylene ether ether ketone) in an amount of 60 wt % or more. ### Claim 36 (depends on 32) The method for producing a fiber-reinforced composite material according to claim 32, wherein the component (B) is a mixture of cyclic poly(phenylene ether ether ketone)s having different numbers of repeating units (m). ### Claim 37 (depends on 32) The method for producing a fiber-reinforced composite material according to claim 32, further comprising adding a polymerization catalyst (D) to a melt solution of the component (B). ### Claim 38 (depends on 32) The method for producing a fiber-reinforced composite material according to claim 32, wherein in the step (II-1), (II-2), or (II-3), the melt viscosity of the melt solution of the component (B) is adjusted to 10 Pa·s or lower. ### Claim 39 (depends on 32) The method for producing a fiber-reinforced composite material according to claim 32, wherein in the step (IV-1), (IV-2), or (IV-3), the thermal polymerization is performed at a temperature of 160° C. to 330° C.