JP2012149368A5 - - Google Patents

Description

Examples of the group containing a hydrocarbon having 1 to 22 carbon atoms and an ester structure in the general formulas (I) to (IV), (VI), and (VII) include an acetoxymethyl group, an acetoxyethyl group, and an acetoxypropyl group. group, acetoxy butyl group, meta Krilo yl oxy ethyl group and a benzoyloxy ethyl group, and the like.

Specific examples of the aliphatic polycarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, slip phosphate, azelaic acid, sebacic acid, undecalactone down diacid, dodecanoic diacid, tridecane Diacid, tetradecanedioic acid, pentadecanedioic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, pentylmalonic acid, hexylmalonic acid, dimethylmalonic acid, diethylmalonic acid, methylpropylmalonic acid, methylbutyl Malonic acid, ethylpropylmalonic acid, dipropylmalonic acid, methylsuccinic acid, ethylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-methyl -3-Ethylglutaric acid, 3,3-diethylglutaric acid, 3,3-dimethylglutaric acid , 3-methyladipic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid.

Specific examples of the aliphatic monocarboxylic acids, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, octyl acid, pelargonic acid, lauric acid, myristic acid, stearic acid , Behenic acid, undecanoic acid, acrylic acid, methacrylic acid, crotonic acid and oleic acid.

In the present invention, from the viewpoint of adhesion of the carbon fiber and the matrix resin is further improved, after the oxidation treatment, it is preferred to wash the carbon fiber in an alkaline aqueous solution. Among these, it is preferable to perform a liquid phase electrolysis treatment with an acidic electrolyte followed by washing with an alkaline aqueous solution.

After laminating the obtained prepreg, a composite material is produced by a method of heating and curing the matrix resin while applying pressure to the laminate. As a method for applying heat and pressure, a press molding method, an autoclave molding method, a packing molding method, a wrapping tape method, an internal pressure molding method, and the like are employed. The composite material is formed by directly impregnating the matrix resin with carbon fiber without using a prepreg, followed by heat curing, for example, a hand lay-up method, a resin injection molding method, a resin transfer molding method, etc. It can also be produced by the method. In these methods, it preferred you to mix to the resin prepared immediately before use 2 liquid base and curing agent of the matrix resin.

Examples of uses of the molded body comprising the carbon fiber and the thermosetting resin and / or the thermoplastic resin of the present invention include, for example, a personal computer, a display, an OA device, a mobile phone, a portable information terminal, a facsimile, a compact disc, a portable MD, and a mobile phone. Cases for electrical and electronic equipment such as radio cassettes, PDAs (mobile information terminals such as electronic notebooks), video cameras, digital still cameras, optical equipment, audio equipment, air conditioners, lighting equipment, entertainment equipment, toy goods, and other home appliances And internal materials such as trays and chassis, and their cases, mechanical parts, panels and other building materials applications, motor parts, alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, suspension parts, exhaust valves, etc. fuel Coupling, exhaust system or various intake system pipes, air intake nozzle snorkel, intake manifold, various arms, various frames, various hinges, various bearings, fuel pump, gasoline tank, CNG tank, engine coolant joint, carburetor main body, carburetor spacer , Exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, radiator motor Brush holders, water pump impellers, turbine vanes, wiper motor parts, distributors, starters Switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, coil for fuel-related electromagnetic valve, connector for fuse, battery tray, AT bracket, headlamp support, pedal housing, handle, door beam, protector, chassis , Frame, armrest, horn terminal, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, noise shield, radiator support, spare tire cover, seat shell, solenoid bobbin, engine oil filter, ignition device case, under cover , Scuff plate, pillar trim, propeller shaft, wheel, fender, fascia, bumper -, Bumper beams, bonnets, aero parts, platforms, cowl louvers, roofs, instrument panels, spoilers and various module-related parts, parts and skins, landing gear pods, winglets, spoilers, edges, ladders Elevator, off Eari ring, aircraft-related parts, such as ribs, members and outer plate, such as windmill blades and the like. In particular, it is preferably used for aircraft members, windmill blades, automobile outer plates, casings of electronic devices, trays, chassis, and the like.

<Measurement of interfacial shear strength (IFSS)>
Interfacial shear strength (IFSS) is measured by the following procedures (a) to (d).
(A) Preparation of resin 100 parts by mass of bisphenol A type epoxy resin compound “jER” (registered trademark) 828 (manufactured by Mitsubishi Chemical Corporation) and 14.5 parts by mass of metaphenylenediamine (manufactured by Sigma-Aldrich Japan) , Put each in a container. Thereafter, heating is performed at a temperature of 75 ° C. for 15 minutes in order to reduce the viscosity of the jER828 and dissolve the metaphenylenediamine. Then, both are mixed well and vacuum defoaming is performed at a temperature of 80 ° C. for about 15 minutes.
(B) Fixing the carbon fiber single yarn to the special mold Pull out the single fiber from the carbon fiber bundle, and fix both ends with an adhesive in a state where a constant tension is applied to the single fiber in the longitudinal direction of the dumbbell mold. Then, in order to remove the water | moisture content adhering to carbon fiber and a mold, it vacuum-drys for 30 minutes or more at the temperature of 80 degreeC. The dumbbell mold is made of silicone rubber, and the shape of the casting part is a central part width of 5 mm, a length of 25 mm, a both end part width of 10 mm, and an overall length of 150 mm.
(C) From resin casting to curing The resin prepared in the above procedure (b) is poured into the mold after the vacuum drying in the above step (b), and the heating rate is 1.5 ° C. using an oven. The temperature rises to 75 ° C./min and is held for 2 hours, then the temperature rises to 125 ° C. at a heating rate of 1.5 minutes and held for 2 hours, then the temperature drops to 30 ° C. at a cooling rate of 2.5 ° C./min To do. Then, it demolds and a test piece is obtained.
(D) Measurement of interfacial shear strength (IFSS) A tensile force was applied to the test piece obtained in the above procedure (c) in the fiber axis direction (longitudinal direction) to cause a strain of 12%, and then the test piece was tested with a polarizing microscope. The number of fiber breaks N (pieces) in the range of 22 mm at the center of each piece is measured. Next, the average broken fiber length la is calculated by the formula of la (μm) = 22 × 1000 (μm) / N (pieces). Next, the critical fiber length lc is calculated from the average broken fiber length la by the following formula: lc (μm) = (4/3) × la (μm). The strand tensile strength σ and the diameter d of the carbon fiber single yarn are measured, and the interface shear strength IFSS, which is an index of the bond strength between the carbon fiber and the resin interface, is calculated by the following equation. In the examples, the average of the number of measurements n = 5 was used as the test result.
Interfacial shear strength IFSS (MPa) = σ (MPa) × d (μm) / (2 × lc) (μm).

-Step I: Step of producing the carbon fiber used in the present invention
Spinning acrylonitrile 99 mole% and consisting of 1 mole% of itaconic acid copolymer and baking, the total number of filaments 24,000, the total fineness 800 tex, a specific gravity of 1.8, a strand tensile strength 6.2 GPa, the strand tensile A carbon fiber having an elastic modulus of 300 GPa was obtained. Subsequently, the carbon fiber was subjected to an electrolytic surface treatment using an aqueous solution of ammonium hydrogen carbonate having a concentration of 0.1 mol / l as an electrolytic solution at an electric charge of 120 coulomb per 1 g of carbon fiber. The carbon fiber subjected to the electrolytic surface treatment was subsequently washed with water and dried in heated air at a temperature of 150 ° C. to obtain a carbon fiber as a raw material. At this time, the surface oxygen concentration O / C was 0.22. This was designated as carbon fiber A used in the present invention.

Step II: A step of attaching the component (A) to the carbon fiber obtained in the step I The above (A-1) and acetone are mixed, and an approximately 1% by mass acetone solution that is uniformly dissolved is mixed. Obtained. Using this acetone solution, the component (A) was applied to the surface-treated carbon fiber A by an immersion method, and then heat treated at a temperature of 150 ° C. for 90 seconds to obtain a carbon fiber to which the component (A) was adhered. . (A) The adhesion amount of component was prepared so that it might become 0.1 mass part with respect to 100 mass parts of surface-treated carbon fibers. Then, as a result of measuring interfacial shear strength (IFSS) using the obtained carbon fiber, it was confirmed that IFSS was 27 MPa and adhesiveness was sufficiently high. The results are shown in Table 1.

-Step II: Step of attaching component (A) to carbon fiber used in the present invention The above-mentioned (A-3) and acetone were mixed to obtain an about 1% by mass acetone solution that was uniformly dissolved. Using this acetone solution, the component (A) was applied to the surface-treated carbon fiber B by the dipping method, followed by heat treatment at a temperature of 150 ° C. for 90 seconds to obtain a carbon fiber having the component (A) attached thereto. . (A) The adhesion amount of component was prepared so that it might become 0.1 mass part with respect to 100 mass parts of surface-treated carbon fibers. Then, as a result of measuring interfacial shear strength (IFSS) using the obtained carbon fiber, IFSS was 24 MPa, and it was confirmed that the adhesiveness was sufficiently high. The results are shown in Table 1.

Step II: A step of attaching the component (A) to the carbon fiber obtained in the step I. The above-mentioned (A-3) and acetone are mixed, and an approximately 1% by mass acetone solution that is uniformly dissolved is mixed. Obtained. Using this acetone solution, the component (A) was applied to the surface-treated carbon fiber C by a dipping method, followed by heat treatment at a temperature of 150 ° C. for 90 seconds to obtain a carbon fiber having the component (A) attached thereto. . (A) The adhesion amount of component was prepared so that it might become 0.1 mass part with respect to 100 mass parts of surface-treated carbon fibers. Then, as a result of measuring interfacial shear strength (IFSS) using the obtained carbon fiber, IFSS was 26 MPa, and it was confirmed that the adhesiveness was sufficiently high. The results are shown in Table 1.

-Step II: (A), (B) The step of attaching the components to the carbon fiber obtained in Step I (A-1) and the above (B-1) are mixed at a mass ratio of 3:97 Further, acetone was further mixed to obtain an acetone solution of about 1% by mass in which the components (A-1) and (B-1) were uniformly dissolved. Using this acetone solution, (A-1) and (B-1) were applied to the surface-treated carbon fiber A by a dipping method, followed by heat treatment at a temperature of 210 ° C. for 150 seconds, (A), (B) The carbon fiber to which the component was attached was obtained. The adhesion amount was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber. Subsequently, as a result of measuring the interfacial shear strength (IFSS) using the obtained carbon fiber, it was confirmed that IFSS was 40 MPa and the adhesiveness was sufficiently high. The results are shown in Table 2.

-Step II: (A), (B) The step of adhering the components to the carbon fiber obtained in Step I (A-3) and the above (B-2) are mixed at a mass ratio of 3:97 Further, acetone was mixed to obtain an acetone solution of about 1% by mass in which (A-3) and (B-2) were uniformly dissolved. Using this acetone solution, after applying (A-3) and (B-2) to the surface-treated carbon fiber A by an immersion method, heat treatment was performed at a temperature of 210 ° C. for 150 seconds, and (A), (B) The carbon fiber to which the component was attached was obtained. The adhesion amount was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber. Subsequently, as a result of measuring the interfacial shear strength (IFSS) using the obtained carbon fiber, it was confirmed that the IFSS was 42 MPa and the adhesiveness was sufficiently high. The results are shown in Table 3.

Step II: Steps (A) and (B) for adhering the components to the carbon fiber obtained in Step I (A-1) and (B-8) are mixed at a mass ratio of 3:97, Further, acetone was mixed to obtain an acetone solution of about 1% by mass in which (A-1) and (B-8) were uniformly dissolved. Using this acetone solution, after applying (A-1) and (B-8) to the surface-treated carbon fiber A by an immersion method, heat treatment was performed at a temperature of 210 ° C. for 150 seconds, and (A), (B) The carbon fiber to which the component was attached was obtained. The adhesion amount was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber. Subsequently, as a result of measuring the interfacial shear strength (IFSS) using the obtained carbon fiber, it was confirmed that IFSS was 35 MPa and the adhesiveness was sufficiently high. The results are shown in Table 4.

Step II: Mixing the components (A) and (B) to the carbon fiber obtained in Step I (A-7) and the above (B-8) at a mass ratio of 3:97 Further, acetone was mixed to obtain an acetone solution of about 1% by mass in which (A-7) and (B-8) were uniformly dissolved. Using this acetone solution, (A-7) and (B-8) were applied to the surface-treated carbon fiber A by a dipping method, followed by heat treatment at a temperature of 210 ° C. for 150 seconds, (A), (B) The carbon fiber to which the component was attached was obtained. The adhesion amount was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber. Subsequently, as a result of measuring the interfacial shear strength (IFSS) using the obtained carbon fiber, it was confirmed that IFSS was 37 MPa and the adhesiveness was sufficiently high. The results are shown in Table 4.

Step II: Mixing the components (A-8) and (B-8) with a mass ratio of 3:97 (A) and (B) attached to the carbon fiber obtained in the step I Further, acetone was mixed to obtain an acetone solution of about 1% by mass in which (A-8) and (B-8) were uniformly dissolved. Using this acetone solution, the components (A-8) and (B-8) were applied to the surface-treated carbon fiber A by a dipping method, followed by heat treatment at a temperature of 210 ° C. for 150 seconds, (A) The carbon fiber to which the component (B) was adhered was obtained. The adhesion amount was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber. Subsequently, as a result of measuring the interfacial shear strength (IFSS) using the obtained carbon fiber, it was confirmed that the IFSS was 36 MPa and the adhesiveness was sufficiently high. The results are shown in Table 4.