WO2020066969A1 - Composition de résine et produit moulé - Google Patents

Composition de résine et produit moulé Download PDF

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Publication number
WO2020066969A1
WO2020066969A1 PCT/JP2019/037180 JP2019037180W WO2020066969A1 WO 2020066969 A1 WO2020066969 A1 WO 2020066969A1 JP 2019037180 W JP2019037180 W JP 2019037180W WO 2020066969 A1 WO2020066969 A1 WO 2020066969A1
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Prior art keywords
component
mass
resin composition
parts
number average
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PCT/JP2019/037180
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Japanese (ja)
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大雅 坂井
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住友化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols

Definitions

  • the present invention relates to a resin composition and a molded product.
  • This application claims priority based on Japanese Patent Application No. 2018-180570 for which it applied to Japan on September 26, 2018, and uses the content here.
  • a sliding member that operates while being in contact with a mating member such as a gear or a piston is exemplified. These components are required to have a smooth surface and low friction between the components.
  • a property relating to low friction or slipperiness of a sliding member acting on a counterpart member is referred to as “slidability”.
  • the sliding member acts means that the sliding member comes into contact with the mating member and performs a frictional movement.
  • Patent Document 1 describes an invention aimed at providing a resin material having excellent slidability.
  • Patent Document 1 discloses a polysulfone (A) having a hydroxyl group and / or a salt thereof, a fluororesin (B), and a thermoplastic resin other than the polysulfone (A) and the fluororesin (B). (C) is described.
  • the present invention has been made in view of the above circumstances, and a resin composition capable of producing a molded article having high slidability and further producing a molded article exhibiting high dimensional stability even when used in a high temperature range. It is an object of the present invention to provide an article and a molded article having high slidability and exhibiting high dimensional stability even when used in a high temperature range.
  • the resin composition according to the present embodiment is a resin composition containing the following components (A), (B), and (C), and contains (B) component per 100 parts by mass of (A) component.
  • the resin composition has an amount of 35 parts by mass or more and 80 parts by mass or less, and the content of the component (C) with respect to 100 parts by mass of the component (A) is 25 parts by mass or more and 35 parts by mass or less.
  • Component (A) a crystalline thermoplastic resin having a melting point or a flow start temperature of 300 ° C. or higher.
  • Component (B) a carbon fiber having a number average fiber length of 120 ⁇ m or more and 300 ⁇ m or less and a number average fiber diameter of 2 ⁇ m or more and 10 ⁇ m or less.
  • Component (C) at least one or more inorganic fillers selected from plate-like fillers, scaly fillers, and granular fillers.
  • the component (A) preferably contains polyetheretherketone.
  • the polyether ether ketone is preferably represented by the following formula (A1) -1.
  • the component (A) preferably further contains a liquid crystal polyester.
  • the molded article according to the present embodiment is a molded article using the above resin composition as a forming material. That is, the present invention includes the following aspects.
  • Component (A) a crystalline thermoplastic resin having a melting point or a flow start temperature of 300 ° C. or higher.
  • Component (B) a carbon fiber having a number average fiber length of 120 ⁇ m or more and 300 ⁇ m or less and a number average fiber diameter of 2 ⁇ m or more and 10 ⁇ m or less.
  • Component (C) at least one type of inorganic filler selected from plate-like fillers, scaly fillers, and granular fillers.
  • a molded product having high slidability when a molded product is produced, a molded product having high slidability can be produced, and further, a resin composition capable of producing a molded product exhibiting high dimensional stability even when used in a high temperature range.
  • a molded product having high slidability and exhibiting high dimensional stability even when used in a high temperature range can be provided.
  • the resin composition of the present embodiment contains the following components (A), (B), and (C).
  • Component (A) a crystalline thermoplastic resin having a melting point or a flow start temperature of 300 ° C. or higher.
  • Component (B) a carbon fiber having a number average fiber length of 120 ⁇ m or more and 300 ⁇ m or less and a number average fiber diameter of 2 ⁇ m or more and 10 ⁇ m or less.
  • the resin composition of the present embodiment a molded article having high slidability can be produced, and a molded article exhibiting high dimensional stability even when used in a high temperature range can be produced.
  • the resin composition of the present embodiment can be suitably used as a material for sliding members such as gears and pistons, which require high slidability.
  • high slidability means both a state in which the sliding member itself is hardly deteriorated when the sliding member and the mating member act, and a state in which the mating member is hardly deteriorated. Include meaning.
  • “having high dimensional stability even in a high temperature range” means that a linear expansion coefficient (CTE) is 30 ppm or less in a temperature range from 200 ° C. to 250 ° C.
  • the resin composition of the present embodiment may be a mixture of the component (A), the component (B), the component (C), and other components used as necessary, and may be obtained by melt-kneading. Further, a melt-kneaded product of these components may be used. Examples of the melt-kneaded product include, for example, a pellet-shaped resin composition.
  • the content of the component (B) is 35 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the component (A). Further, the content of the component (C) is 25 parts by mass or more and 35 parts by mass or less based on 100 parts by mass of the component (A).
  • each component will be described.
  • the component (A) is a crystalline thermoplastic resin.
  • the component (A) has a melting point or a flow start temperature of 300 ° C. or higher.
  • the resin composition of the present embodiment containing the component (A) By using the resin composition of the present embodiment containing the component (A), a molded article having high heat resistance can be produced.
  • the crystalline thermoplastic resin one kind selected from aromatic polyether ether ketone (PEEK), aromatic polyether ketone (PEK), liquid crystal polyester (LCP), polyphenylene sulfide (PPS), polyimide (PI) or Two or more types are mentioned.
  • aromatic polyetheretherketone (PEEK), aromatic polyetherketone (PEK), and liquid crystal polyester (LCP) are preferable.
  • examples of the upper limit of the melting point or the flow start temperature of the component (A) include 400 ° C or lower, 390 ° C or lower, and 380 ° C or lower.
  • the melting point can be measured using a differential scanning calorimeter (DSC-50, manufactured by Shimadzu Corporation). The position of the endothermic peak on the hottest side that appears when the temperature of the component (A) is raised at a rate of 10 ° C./min is defined as the melting point of the component (A).
  • liquid crystal polyester is charged into a cylinder equipped with a die having a nozzle having an inner diameter of 1 mm and a length of 10 mm using a flow tester (CFT-500 type) manufactured by Shimadzu Corporation. While heating at a rate of 4 ° C./min under a load of 9.8 MPa (100 kg / cm 2 ), the liquid crystal polyester is melted and extruded from a nozzle to a temperature showing a viscosity of 4800 Pa ⁇ s (48,000 poise). .
  • Aromatic polyetheretherketone As the component (A), an aromatic polyetheretherketone is preferable.
  • the aromatic polyetheretherketone is referred to as “PEEK”.
  • the melting point of PEEK is 300 ° C. or more and 350 ° C. or less. A more specific example is 334 ° C.
  • PEEK is a resin having a phenyl ketone structure and two continuous phenyl ether structures as main structures.
  • PEEK is preferably a resin composed of a repeating structural unit represented by the following formula (A10) or (A11).
  • Ar n1 to Ar n4 each represent a phenylene group which may have a substituent or a naphthalenediyl group which may have a substituent.
  • the substituent which the naphthalenediyl group may have is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
  • the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the alkoxy group having 1 to 6 carbon atoms include a methoxy group and an ethoxy group.
  • repeating structural unit represented by the formula (A10) a repeating structural unit represented by the following (A10) -1 is preferable.
  • repeating structural unit represented by the formula (A11) a repeating structural unit represented by the following (A11) -1 is preferable.
  • Vitrex PEEK As a commercial product having a repeating structural unit represented by the above formula (A10) -1, there is a product name of Vitrex PEEK (manufactured by VICTREX).
  • the grades of Vitrex PEEK include 150P, 380P, and 450P.
  • the melt viscosities defined below for these grades are 1500 poise, 3800 poise and 4500 poise, respectively.
  • the melt viscosity of PEEK is preferably 500 to 3000 poise, more preferably 700 to 2500 poise, and particularly preferably 900 to 2000 poise.
  • melt viscosity This is the apparent melt viscosity when the resin heated to 400 ° C. is extruded at a shear rate of 1000 sec ⁇ 1 according to ISO11443.
  • the nozzle for extruding the resin has an inner diameter of 1 mm and a length of 10 mm.
  • Aromatic polyetherketone As the component (A), an aromatic polyether ketone is preferable.
  • the aromatic polyether ketone is referred to as “PEK”.
  • the melting point of PEK is from 330 ° C. to 350 ° C., more specifically, 343 ° C.
  • PEK is a resin having both a phenyl ketone structure and a phenyl ether structure as main structures.
  • PEK is preferably a resin composed of a repeating structural unit represented by the following formula (A2) or (A3). -(-O-Ar n4 -CO-Ar n5 -) -...
  • Ar n4 to Ar n6 are each a phenylene group which may have a substituent or a naphthalenediyl group which may have a substituent.
  • the substituent which the naphthalenediyl group may have is an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms.
  • the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the alkoxy group having 1 to 6 carbon atoms include a methoxy group and an ethoxy group.
  • the melt viscosity of PEK is preferably from 500 to 3000 poise, more preferably from 700 to 2500 poise, and particularly preferably from 900 to 2000 poise.
  • a repeating structural unit represented by the formula (A2) a repeating structural unit represented by the following (A2) -1 is preferable.
  • a repeating structural unit represented by the formula (A3) a repeating structural unit represented by the following (A3) -1 is preferable.
  • the liquid crystal polyester is a liquid crystal polyester exhibiting liquid crystallinity in a molten state, and has a flow start temperature of 300 ° C. or higher.
  • the flow start temperature is preferably 450 ° C. or lower.
  • the liquid crystal polyester may be described as “LCP”.
  • the liquid crystal polyester may be a liquid crystal polyester amide, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a liquid crystal polyester imide.
  • the liquid crystal polyester is preferably a wholly aromatic liquid crystal polyester using only an aromatic compound as a raw material monomer.
  • liquid crystal polyester examples include the following. 1) (i) an aromatic hydroxycarboxylic acid, (ii) an aromatic dicarboxylic acid, and (iii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine and an aromatic diamine.
  • the component (A) may be used alone or in combination of two or more.
  • examples include PEEK alone, PEK alone, LCP alone, PPS alone, PI alone, a combination of PEEK and LCP, and a combination of PEK and LCP.
  • PEEK alone from the viewpoint of improving the fluidity of the resin composition, it is preferable to use substantially only PEEK as the component (A), and it is preferable to use PEEK and LCP in combination.
  • “Substantially using only PEEK” means that the mass of PEEK contained in the total amount of component (A) is 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more. This means that it may be 100% by mass. It is preferable to use PEEK alone as the component (A) or to use PEEK and LCP in combination.
  • the LCP is preferably from 10 to 40 parts by mass, and more preferably from 15 to 30 parts by mass, per 100 parts by mass of PEEK. It is more preferable that the amount be not more than part by mass.
  • the content of the component (A) with respect to the total amount of the resin composition is preferably from 10% by mass to 62% by mass, more preferably from 30% by mass to 62% by mass, and more preferably from 50% by mass to 60% by mass. The following are particularly preferred.
  • the component (B) is a carbon fiber having a number average fiber length of 120 ⁇ m to 300 ⁇ m and a number average fiber diameter of 2 ⁇ m to 10 ⁇ m.
  • the number average fiber length of the component (B) is preferably 130 ⁇ m or more, more preferably 140 ⁇ m or more, and particularly preferably 150 ⁇ m or more.
  • the number average fiber length of the component (B) is preferably 250 ⁇ m or less, more preferably 200 ⁇ m or less, and particularly preferably 195 ⁇ m or less.
  • the upper limit and the lower limit of the number average fiber length of the component (B) can be arbitrarily combined.
  • the combination examples include 130 ⁇ m to 250 ⁇ m, 140 ⁇ m to 200 ⁇ m, and 150 ⁇ m to 195 ⁇ m.
  • the number average fiber diameter of the component (B) is preferably 4 ⁇ m or more, and more preferably 9 ⁇ m or less.
  • the carbon fiber used in the present embodiment is preferably a fibrous substance in which 90% or more of the chemical composition is carbon. It is preferable to use polyacrylonitrile, pitch, regenerated cellulose, or the like as a raw material for carbon fibers. Fiber precursors spun using these raw materials and processed at 1000 ° C. or more and 2000 ° C. or less can be used. Those graphitized at 2000 to 3000 ° C. can be preferably used because they exhibit high strength and high elasticity. In order to obtain a fiber having higher strength and higher elasticity, it is preferable to use polyacrylonitrile as a raw material.
  • the component (B) contained in the resin composition according to this embodiment has a number average fiber length of 3 mm to 10 mm and a number average fiber diameter of 2 ⁇ m to 10 ⁇ m. It can be obtained by melt-kneading the components (A) and (C).
  • the strength of the molded article of the resin composition can be increased.
  • the number average fiber length is equal to or more than the above lower limit, the dimensional stability of the molded article becomes good even in a high temperature region.
  • the number average fiber length is equal to or less than the above upper limit, it is possible to suppress the carbon fibers from floating on the surface of the molded article of the resin composition. For this reason, the surface condition of the molded article can be improved.
  • the fiber diameter and the fiber length of the carbon fiber are each indicated by a number average value. These can be determined, for example, by the following measurement method.
  • the resin composition according to the present embodiment is heated at 500 ° C. for 4 hours to remove the resin component.
  • About 1 g of the residue is collected in a conical beaker, and 150 ml of acetone is added and sufficiently dispersed. Thereafter, about 5 ml is taken, dropped on a slide glass and dried naturally.
  • the operation is performed so that about 1000 or more carbon fibers are collected on the slide glass.
  • the slide glass is set on a projector, enlarged and displayed 100 times, and the length of the enlarged and projected fiber is measured and recorded on a straight scale.
  • the component (C) and the component (B) (carbon fiber) are distinguished based on the shape of the enlarged and projected image.
  • Number average fiber diameter and fiber length are calculated by the following formula.
  • Number average fiber diameter (or number average fiber length) [(x1 + x2 +... + Xn) / n] ⁇ 1/100 (In the formula, x is the measured value of the fiber diameter (or fiber length) of each individual, and n is the number of each individual, for example, 400.)
  • carbon fibers made of polyacrylonitrile include Pyrofil M-FE and M-ME (trade names, manufactured by Mitsubishi Rayon Co., Ltd.), and Vesfight HTA-CMF-0070N / S, HTA-CMF-0160N (trade names). / S (manufactured by Toho Rayon Co., Ltd.).
  • Examples of commercially available carbon fibers using pitch as a raw material include M2007S (trade name, manufactured by Kureha Chemical Co., Ltd.).
  • the content of the component (B) is 35 to 80 parts by mass, preferably 40 to 75 parts by mass, based on 100 parts by mass of the component (A).
  • the content of the component (B) is equal to or more than the lower limit, the strength of a molded article using the resin composition can be increased.
  • the content of the component (B) is equal to or less than the above upper limit, it is possible to suppress an increase in surface resistance due to floating of carbon fibers on the surface of a molded article molded using the resin composition.
  • the content of the component (B) with respect to the total amount of the resin composition is preferably from 10% by mass to 35% by mass, and more preferably from 20% by mass to 35% by mass.
  • the component (C) is at least one type of inorganic filler selected from a plate-like filler, a flaky filler, and a granular filler.
  • Plate-like filler examples include talc, mica, graphite, wollastonite, barium sulfate and calcium carbonate. Mica may be muscovite, phlogopite, fluorophlogopite, or tetrasilicic mica.
  • Scale-like graphite is exemplified as the scale-like filler.
  • granular filler examples include alumina, titanium oxide, boron nitride, silicon carbide, and calcium carbonate. When a granular filler is used, it is preferable to use alumina.
  • the component (C) is preferably one or both of flaky graphite and mica.
  • the content of the component (C) is 25 parts by mass or more and 35 parts by mass or less based on 100 parts by mass of the component (A).
  • the content is the total amount of the inorganic fillers used.
  • the content of the component (C) is at least the lower limit, the strength of a molded article using the resin composition can be increased.
  • the content of the component (C) is equal to or less than the upper limit, it is possible to prevent the component (C) from floating on the surface of a molded article formed using the resin composition. Thereby, the surface friction of the molded product can be reduced.
  • the content of the component (C) with respect to the total amount of the resin composition is preferably from 1% by mass to 20% by mass, more preferably from 10% by mass to 20% by mass, and from 12% by mass to 17% by mass. The following are more preferred.
  • the resin composition of the present embodiment may contain a metering stabilizer, a release agent, an antioxidant, a heat stabilizer, an ultraviolet absorber, an antistatic agent, a surfactant, a flame retardant, and a colorant as optional components. Good.
  • the resin composition of the present embodiment can be produced by mixing the component (A), the component (B), the component (C), and other components used as required, all at once or in an appropriate order.
  • the resin composition of the present embodiment uses a carbon fiber raw material having a number average fiber length of 3 mm or more and 10 mm or less and a number average fiber diameter of 2 ⁇ m or more and 10 ⁇ m or less as a raw material of the component (B), and using another (A). It is preferable that the component (A), the component (C), and other components used as necessary are melt-kneaded using an extruder and pelletized.
  • a molded article molded using the resin composition of the present embodiment has high slidability and exhibits high dimensional stability even in a high temperature range.
  • the resin composition of the present embodiment has, as essential components, a component (A) having excellent heat resistance as a resin component, and components (B) and (C) capable of imparting dimensional stability and slidability to a molded product.
  • the present embodiment is a molded article using the above resin composition as a forming material.
  • the molded product of the present embodiment is preferably an injection molded product, and can be suitably used as a sliding member.
  • the molded product of the present embodiment is, for example, in the automotive field, as an injection molded product for an automobile interior material, an injection molded product for a ceiling material, an injection molded product for a wheel house cover, an injection molded product for a trunk room lining, an instrument panel skin material.
  • Injection molding products for handlebar covers injection molding products for armrests, injection molding products for headrests, injection molding products for seat belt covers, injection molding products for shift lever boots, injection molding products for console boxes, horn pads Injection molded products, injection molded products for knobs, injection molded products for airbag covers, injection molded products for various trims, injection molded products for various pillars, injection molded products for door lock bezels, injection molded products for grab boxes, defroster nozzles Injection molded products, injection molded products for scuff plates, injection molded products for steering wheels, steering columns Injection molded articles for bars and the like.
  • Injection molded products for automobile exterior materials include injection molded products for bumpers, injection molded products for spoilers, injection molded products for mudguards, and injection molded products for side moldings.
  • injection molded products for automobile parts include hoses for automobile headlamp injection molding, glass run channel injection molding, weather strip injection molding, drain hose injection molding, window washer tube injection molding, etc.
  • EGI tube EGI tube, armrest insert, armrest guide, armrest base, outer door handle, ash tray panel, ash tray lamp housing, upper garnish, antenna inner tube, ignition coil case, ignition coil bobbin, inside door lock knob, instrument Ment panel core, intercooler tank, inner lock knob, window glass slider, window pivot, window molding, window regulator handle, window regulator handle knob, water pump impeller, washer nozzle, washer motor housing, air spoiler, air duct, air duct intake, Air ventilation Air conditioner actuator, air control valve, air conditioner magnet clutch bobbin, air conditioner control knob, air flow meter housing, air regulator, extract grill, emblem, oil cleaner case, oil level gauge, oil braking valve, gasoline chamber, gasoline float, gasoline Injection nozzle, canister, carburetor, carburetor valve, cooler sirocco fan, cooler vacuum pump, cooling fan, clutch oil reservoir, glove door outer, glove box, glove box knob, glove box lid, condenser case, compressor valve, commutator, Circuit board, surge tank, thermostat housing, Id brake wire protector,
  • sensors LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, Headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystal displays, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, microwave oven parts, audio and audio equipment parts, lighting parts, air conditioner parts, Office computer-related parts, telephone-related parts, fax-related parts, copier-related parts, and the like.
  • the obtained resin composition was used to obtain a molded product having a length of 127 mm, a width of 12.7 mm, and a thickness of 6.4 mm using an injection molding machine (“PS40E5ASE” of Nissei Plastics Industries, Ltd.).
  • the deflection temperature under load of the obtained molded article was measured at a load of 1.82 MPa in accordance with ASTM D648.
  • Test piece First, the resin composition was molded using an injection molding machine (“PS40E5ASE” of Nissei Plastics Industries, Ltd.), and a molded product having dimensions of 64 mm (MD) ⁇ 64 (TD) mm ⁇ 3 mmt. I got The molded article was produced by injecting the resin composition from a one-point gate. Next, the dimensions of the molded product were measured precisely (2 decimal places in mm units) using a cutout of the central part of about 5 mm square as a test piece.
  • PS40E5ASE of Nissei Plastics Industries, Ltd.
  • Measurement condition of linear expansion coefficient 1) Apparatus: Thermomechanical analyzer (“TMA8310” manufactured by Rigaku Corporation) 2) Temperature condition: The temperature was raised from 50 ° C to 270 ° C at a rate of 10 ° C / min. 3) Atmosphere: Nitrogen gas atmosphere 4) Compressive load: 19.6mN 5) Measurement direction: MD, TD In this specification, “MD” means a direction parallel to the flow direction of the resin, and “TD” means a direction perpendicular to the MD.
  • ⁇ Method for measuring number average fiber length of component (B)> First, a pellet made of a resin composition manufactured by a method described later was heated at 500 ° C. for 4 hours to remove a resin component. Thus, a mixture of the component (B) and the component (C) was obtained. About 1 g of the obtained mixture was collected in a conical beaker, and 150 ml of acetone was added to sufficiently disperse the mixture. Thereafter, about 5 ml was collected and dropped on the entire surface of a slide glass, followed by natural drying. At this time, the operation was performed so that about 1000 or more carbon fibers were collected on a slide glass.
  • FIG. 1 is a schematic diagram illustrating a test method of a slidability test.
  • FIG. 1 shows a ring R and a test piece S.
  • a test piece S was cut out from the center of the molded product having the dimensions of 64 mm (MD) ⁇ 64 (TD) mm ⁇ 3 mmt described in the above (sample conditions) and 1).
  • the ring R is a stainless steel (SUS304) ring.
  • the width L 4 25.6 mm
  • the height L 5 300 mm
  • the inner diameter L 6 20 mm (contact area 2 cm 2 ).
  • the critical PV was determined by placing a cylinder on a test piece while applying pressure, rotating the cylinder, and measuring the degree of wear.
  • the limit PV was calculated by multiplying the rotational speed by the load pressure at which rapid wear occurs, while keeping the rotational speed of the cylinder constant.
  • "abrupt wear occurs” means that the surface of the test piece is melted or deformed by frictional heat or physical load on the sliding surface. An example of the deformation is a case where the surface of the test piece is shaved. Melting and deformation are visually observed.
  • a ring R is pressed as a mating member against a test piece S as a sliding member, and a load of 0.5 N / mm 2 (0.5 MPa) is applied from the direction indicated by the symbol P in FIG.
  • the ring R was rotated at 100 m / min in the direction of the curved arrow.
  • the load is increased by 0.1 N / mm 2 (0.1 MPa) every minute, and the product of the load pressure (MPa) when rapid wear occurs and the rotation speed (m / min) of the ring R is calculated. I asked.
  • the value of this product was defined as “limit PV” (unit: MPa ⁇ m / min) and is shown in Table 1.
  • ⁇ Method for measuring flow start temperature of liquid crystal polyester About 2 g of liquid crystal polyester was charged into a cylinder equipped with a die having a nozzle having an inner diameter of 1 mm and a length of 10 mm using a flow tester Shimadzu Corporation "CFT-500 type", and was filled with 9.8 MPa (100 kg / cm 2). While raising the temperature at a rate of 4 ° C./min under the load of (1), the liquid crystal polyester was melted and extruded from the nozzle, and a temperature showing a viscosity of 4800 Pa ⁇ s (48000 poise) was measured.
  • CCF carbon fiber raw material having a number average fiber diameter of 7 ⁇ m and a number average fiber length of 6 mm (TR06UL, Mitsubishi Rayon Co., Ltd.).
  • MCF carbon fiber raw material having a number average fiber diameter of 5 ⁇ m and a number average fiber length of 160 ⁇ m (HT M100 160 mu, manufactured by Teijin Limited) -CF fiber length
  • Number average fiber length ( ⁇ m) The number average fiber length ( ⁇ m) of carbon fibers measured using a pellet made of a resin composition and measuring according to the above ⁇ Method for measuring number average fiber length of component (B)>. is there.
  • -PTFE polytetrafluoroethylene (Fluon L169J, manufactured by Asahi Glass Co., Ltd.).
  • -Graphite CSP (manufactured by Nippon Graphite Industry Co., Ltd.).
  • Mica J-31M (manufactured by Yamaguchi Mica).
  • ⁇ Alumina AA-03 (Sumitomo Chemical Co., Ltd.)
  • Examples 1 to 9 to which the present invention was applied exhibited high dimensional stability with a linear expansion coefficient of 30 ppm or less in a high temperature range up to 250 ° C. This is dimensional stability equivalent to that of a metal material such as aluminum or stainless steel. Further, Examples 1 to 9 had high limit PV values and exhibited high slidability. In Comparative Examples 1 to 8 in which the present invention was not applied to the component (B) and the component (C), both the dimensional stability and the slidability in a high temperature range were not good. Furthermore, in the reference example using PES as the resin component, the molded product was deformed at 250 ° C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine caractérisée en ce qu'elle contient un constituant (A), un constituant (B) et un constituant (C) ci-dessous, la teneur en constituant (B) par rapport à 100 parties en masse du constituant (A) allant de 35 à 80 parties en masse, et la teneur en constituant (C) par rapport à 100 parties en masse du constituant (A) allant de 25 à 35 parties en masse. Constituant (A) : une résine thermoplastique cristalline présentant un point de fusion ou une température de début d'écoulement supérieure ou égale à 300 °C ; constituant (B) : une fibre de carbone présentant une longueur de fibre moyenne en nombre de 120 à 300 µm et un diamètre de fibre moyen en nombre de 2 à 10 µm ; et constituant (C) : au moins une charge inorganique choisie parmi une charge lamellaire, une charge en écailles et une charge granulaire.
PCT/JP2019/037180 2018-09-26 2019-09-24 Composition de résine et produit moulé WO2020066969A1 (fr)

Applications Claiming Priority (2)

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JP2018-180570 2018-09-26
JP2018180570A JP2020050748A (ja) 2018-09-26 2018-09-26 樹脂組成物及び成形品

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WO2020066969A1 true WO2020066969A1 (fr) 2020-04-02

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WO (1) WO2020066969A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022149330A1 (fr) * 2021-01-06 2022-07-14 株式会社荏原製作所 Palier lisse, dispositif de palier lisse et pompe

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7175011B2 (ja) * 2019-12-19 2022-11-18 株式会社大一商会 遊技機

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01242662A (ja) * 1988-03-23 1989-09-27 Yobea Rulon Kogyo Kk 摺動性樹脂組成物
JPH02218753A (ja) * 1988-09-09 1990-08-31 Kureha Chem Ind Co Ltd 摺動部材用樹脂組成物
JPH06172619A (ja) * 1992-12-02 1994-06-21 Toray Ind Inc 液晶性樹脂組成物
JPH0848887A (ja) * 1994-08-04 1996-02-20 Mitsui Toatsu Chem Inc 樹脂組成物
JPH0881629A (ja) * 1994-09-13 1996-03-26 Mitsui Toatsu Chem Inc オイルシールリング
JP2006511644A (ja) * 2002-12-18 2006-04-06 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フィラーを含有する低摩擦係数の熱可塑性組成物
JP2006515638A (ja) * 2002-12-18 2006-06-01 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 耐摩耗性が改善された高温ｌｃｐ
JP2007192242A (ja) * 2006-01-17 2007-08-02 Mitsui Chemicals Inc 溶融成形可能な熱可塑性ポリイミド樹脂からなるピストンリング

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01242662A (ja) * 1988-03-23 1989-09-27 Yobea Rulon Kogyo Kk 摺動性樹脂組成物
JPH02218753A (ja) * 1988-09-09 1990-08-31 Kureha Chem Ind Co Ltd 摺動部材用樹脂組成物
JPH06172619A (ja) * 1992-12-02 1994-06-21 Toray Ind Inc 液晶性樹脂組成物
JPH0848887A (ja) * 1994-08-04 1996-02-20 Mitsui Toatsu Chem Inc 樹脂組成物
JPH0881629A (ja) * 1994-09-13 1996-03-26 Mitsui Toatsu Chem Inc オイルシールリング
JP2006511644A (ja) * 2002-12-18 2006-04-06 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フィラーを含有する低摩擦係数の熱可塑性組成物
JP2006515638A (ja) * 2002-12-18 2006-06-01 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 耐摩耗性が改善された高温ｌｃｐ
JP2007192242A (ja) * 2006-01-17 2007-08-02 Mitsui Chemicals Inc 溶融成形可能な熱可塑性ポリイミド樹脂からなるピストンリング

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022149330A1 (fr) * 2021-01-06 2022-07-14 株式会社荏原製作所 Palier lisse, dispositif de palier lisse et pompe

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TW202024178A (zh) 2020-07-01

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