# US 5,705,120 A · Method of producing graphite fiber-reinforced fluororesin composites > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,705,120 A - Document ID: US5705120A - Status: Granted - Kind: A - Application number: 08/580,488 - Filed: 1995-12-29 - Granted: 1998-01-06 - Earliest claimed: 1994-02-08 - Assignees: Osaka Gas Co., Ltd. - Inventors: Takuya Ueno; Masayuki Inamori - Web page: https://patentgrep.com/patent/US5705120A ## CPC - C08K 7/06: Elements - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) ## Abstract The graphite fiber-reinforced fluororesin composite including 99 to 40 parts by weight of a fluororesin, e.g. polytetrafluoroethylene, and 1 to 60 parts by weight of a graphite fiber. The graphite fiber has a specific surface area of 0.6 to 25 m.sup.2 /g and, as determined by X-ray photoelectron spectroscopic analysis, (1) a surface atomic oxygen/atomic carbon ratio of 0.10 to 0.20, (2) a surface atomic halogen/atomic carbon ratio of 0.05 to 1.8 or (3) a surface atomic oxygen/atomic carbon ratio of 0.10 to 0.20 and a surface atomic halogen/atomic carbon ratio of 0.05 to 1.8. Such fiber may, for example, be obtained by subjecting a graphite fiber to oxidizing treatment, halogenating treatment, or oxidizing and halogenating treatments. The graphite fiber imparts high mechanical strength characteristics and wear resistance to the composite. ## Claims ### Claim 1 A method of producing a graphite fiber-reinforced fluororesin composite which comprises molding a composition comprising a fluororesin and a graphite fiber with a specific surface area of 0.6 to 25 m.sup.2 /g and a surface atomic oxygen/atomic carbon ratio of 0.10 to 0.20 as determined by X-ray photoelectron spectroscopic analysis, wherein said graphite fiber is a fiber obtainable (1) by oxidizing a graphite fiber at a temperature of 60.degree. C. to 120.degree. C. in a liquid phase containing an oxygen-containing compound, or at a temperature of 500.degree. to 1,000.degree. C. in a gas phase containing an oxygen-containing compound, (2) by comminuting a graphite fiber to 10 to 700 .mu.m in length in an oxygen-containing gas atmosphere, (3) by applying an inorganic oxidizing agent to the surface of a graphite fiber and heating the same at a temperature of 300.degree. to 1,000.degree. C., (4) by subjecting a graphite fiber to electrolytic oxidation in an electrolyte solution capable of electrolytic oxidation using said fiber as the positive electrode, where an electric current of not less than 100 coulombs/g is passed through the electrolyte solution and the bath temperature is in the range of 20.degree. C. to 100.degree. C., or (5) by subjecting a graphite fiber to a plasma discharge treatment in the presence of an inert gas at a pressure of 0.001 to 10 Torr by applying an electric power of 10 W to 100 KW at a frequency of 10 kHz to 100 MHz and contacting the fiber with an oxygen-containing gas. ### Claim 2 (depends on 1) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 1 which comprises compression-molding the composition comprising the fluororesin and the graphite fiber and annealing the resultant molding or subjecting said composition to injection or extrusion molding. ### Claim 3 (depends on 1) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 1 wherein the composition comprises 92 to 75 parts by weight of the fluororesin and 8 to 25 parts by weight of the graphite fiber. ### Claim 4 (depends on 1) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 1 wherein said graphite fiber has a specific surface area of 0.8 to 10 m.sup.2 /g and and a surface atomic oxygen/atomic carbon ratio of 0.12 to 0.20 as determined by X-ray photoelectron spectroscopic analysis. ### Claim 5 (depends on 1) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 1 wherein said fluororesin is polytetrafluoroethylene. ### Claim 6 (depends on 1) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 1 wherein said graphite fiber is a graphite fiber obtainable by subjecting a carbon-fiber or an infusibilized precursor fiber to heat treatment at a temperature not lower than 2,200.degree. C. ### Claim 7 (depends on 1) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 1 wherein said graphite fiber is a graphite fiber obtainable by subjecting a graphite fiber having an X-ray photoelectron spectroscopic surface atomic oxygen/atomic carbon ratio of 0.10 to 0.20 to at least one of the following treatments (6) to (10) to further have an X-ray photoelectron spectroscopic surface atomic halogen/atomic carbon ratio of 0.05 to 1.8 (6) chemical reaction with a halogen or a halogen-containing inorganic compound, (7) a plasma discharge treatment in a halogen-containing gas, (8) polymerizing a halogen-containing monomer, (9) sizing with a halogen-containing compound, or (10) grafting with a halogen-containing compound. ### Claim 8 (depends on 7) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 7 wherein the halogen-containing component in methods (7) to (10) is a fluorine-containing component. ### Claim 9 (depends on 1) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 1 wherein said graphite fiber is a graphite fiber obtainable by grafting a halogen-containing compound to a graphite fiber with an X-ray photoelectron spectroscopic surface atomic oxygen/atomic carbon ratio of 0.10 to 0.20 to further have an X-ray photoelectron spectroscopic surface atomic halogen/atomic carbon ratio of 0.05 to 1.8. ### Claim 10 (depends on 9) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 9 wherein the halogen-containing compound is a fluorine-containing compound having terminal reactive group capable of reaction with a group produced by the oxidation of said graphite fiber. ### Claim 11 (depends on 9) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 9 wherein the halogen-containing compound is a fluorine-containing compound having an epoxy group, an acyl halide group or a carboxylic group. ### Claim 12 (depends on 1) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 1 wherein said graphite fiber is a graphite fiber obtainable by sizing a graphite fiber having an X-ray photoelectron spectroscopic surface atomic oxygen/atomic carbon ratio of 0.10 to 0.20 with a halogen-containing compound to further have an X-ray photoelectron spectroscopic surface atomic halogen/atomic carbon ratio of 0.05 to 1.8. ### Claim 13 (depends on 12) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 12 wherein said halogen-containing compound is a fluorine-containing component. ### Claim 14 (depends on 12) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 12 wherein the halogen-containing compound is a fluorinated pitch. ### Claim 15 (depends on 1) A method of producing a graphite fiber-reinforced fluororesin composite according to claim 1 wherein said graphite fiber has a specific surface area of 1 to 6 m.sup.2 /g and a surface atomic oxygen/atomic carbon ratio of 0.15 to 0.20 as determined by X-ray photoelectron spectroscopic analysis, and said fluororesin is polytetrafluoroethylene.