WO2018096908A1 - Composition de résine - Google Patents

Composition de résine Download PDF

Info

Publication number
WO2018096908A1
WO2018096908A1 PCT/JP2017/039768 JP2017039768W WO2018096908A1 WO 2018096908 A1 WO2018096908 A1 WO 2018096908A1 JP 2017039768 W JP2017039768 W JP 2017039768W WO 2018096908 A1 WO2018096908 A1 WO 2018096908A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
graphite yarn
resin composition
graphite
crystallite size
Prior art date
Application number
PCT/JP2017/039768
Other languages
English (en)
Japanese (ja)
Inventor
吉田　健
圭祐 羽儀
宏和 湯川
Original Assignee
ダイキン工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ダイキン工業株式会社 filed Critical ダイキン工業株式会社
Publication of WO2018096908A1 publication Critical patent/WO2018096908A1/fr

Links

Classifications

    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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

Definitions

  • the present invention relates to a resin composition.
  • Patent Document 1 discloses a pressure-resistant slidability formed by blending carbon fiber and a granular inorganic compound with a modified tetrafluoroethylene resin composed of a copolymer of tetrafluoroethylene and partially modified tetrafluoroethylene.
  • a fluorinated ethylene resin composition is described.
  • Patent Document 2 describes a resin composition for sliding parts comprising a specific proportion of (a) carbon fiber, (b) metal powder, and (c) a melt-processable fluorine-containing resin.
  • modified polytetrafluoroethylene is 60 to 90% by weight, the average fiber diameter is 5 to 30 ⁇ m, the first carbon fiber having an average fiber length of 20 to 60 ⁇ m is 10 to 30% by weight, and the average fiber diameter is 1 to 10% by weight of second carbon fibers having an average fiber length of 90 to 200 ⁇ m, and the first carbon fibers and the second carbon fibers are pitch-based carbon fibers having a random structure
  • a shaft seal material for a car air conditioner using a tetrafluoroethylene composition is described.
  • Patent Document 4 describes a resin molding material containing a resin, a carbon substance, and an inorganic substance, and containing an adhesive carbon substance as the carbon substance.
  • Patent Document 5 is a composite of a specific thermoplastic resin and a carbon fiber having a specific aspect ratio, satisfies the following requirements (A) to (E), and has a thermal conductivity of 0.7 W / m.
  • a heat-resistant heat conducting composite material characterized by being K or higher is described.
  • thermoplastic resin At least 50% by weight or more of the thermoplastic resin is made of a fluororesin
  • the carbon fiber is a graphitized carbon fiber using mesophase pitch as a starting material
  • the true density of the carbon fiber is 1.7 to 2.5 g / cc
  • D The crystallite size in the c-axis direction and ab-axis direction of the graphite crystal contained in the carbon fiber is both 20 nm or more
  • E Carbon fiber is mixed in the composite material at a ratio of 5 to 50% by weight.
  • the present invention has been made in view of the above-described present situation, and an object thereof is to provide a resin composition having a small wear coefficient and hardly damaging the surface of the aluminum article when contacted with the aluminum article.
  • the present inventors pay attention to the filler to be blended in the resin composition, and by using two specific types of graphite yarn as the filler, the wear coefficient is reduced.
  • the inventors have found that a composition that is small and hardly scratches the surface even when it comes into contact with an aluminum article can be obtained, and the present invention has been completed.
  • the present invention includes a heat-resistant resin, a graphite yarn (A) having a crystallite size in the c-axis direction of 100 ⁇ or less, and a graphite yarn (B) having a crystallite size in the c-axis direction of more than 100 ⁇ . It is a resin composition.
  • the total content of the graphite yarn (A) and the graphite yarn (B) is preferably 3 to 40% by mass with respect to the resin composition.
  • the mass ratio (A / B) of the content of the graphite yarn (A) and the graphite yarn (B) is 1.0 / 9.0 to 9.9 / 0.1. Is preferred.
  • the graphite yarn (A) is preferably other than pitch-based anisotropic graphite yarn.
  • the graphite yarn (B) is preferably a pitch-based anisotropic graphite yarn.
  • the heat resistant resin is preferably at least one selected from the group consisting of a fluororesin, a polyether ketone resin, a polyarylene sulfide resin, and a phenol resin.
  • the resin composition of the present invention has a small wear coefficient and is less likely to damage the surface of the aluminum article when it comes into contact with the aluminum article.
  • the resin composition of the present invention includes a heat-resistant resin, a graphite yarn (A) having a crystallite size in the c-axis direction of 100 ⁇ or less, and a graphite yarn (B) having a crystallite size in the c-axis direction of more than 100 ⁇ . Since the resin composition of the present invention has the above-described configuration, the wear coefficient is small, and when the resin composition comes into contact with the aluminum article, the surface of the aluminum article is hardly damaged. Moreover, since the said heat resistant resin is included, it can be used also at the temperature exceeding 150 degreeC. It seemed difficult to provide a resin composition that is less likely to damage soft aluminum articles despite having a low wear coefficient.
  • the reason why the resin composition of the present invention exhibits the above-described excellent effect is that the graphite yarn having a small crystallite size makes it difficult to wear the resin composition, and at the same time, the graphite yarn having a large crystallite size is the resin composition. This is considered to be because heat generated by friction with the aluminum article is released to the outside by improving the heat dissipation of the aluminum article, thereby reducing damage to the aluminum article.
  • the heat-resistant resin may be any resin that is generally recognized as having heat resistance, but preferably has a melting point of 150 ° C. or higher, for example. More preferably, it is 170 degreeC or more.
  • the heat resistant resin is preferably at least one selected from the group consisting of a thermoplastic resin and a thermosetting resin, and the thermoplastic resin of the heat resistant resin includes a fluororesin, a polyamideimide resin, and a polyimide resin.
  • polyethersulfone resin Selected from the group consisting of: polyethersulfone resin, polyetherimide resin, polyetherketone resin, aromatic polyester resin, polyarylene sulfide resin, polyethernitrile resin, aromatic thermoplastic polyimide resin, and polyamide 4-6 resin
  • polyether ketone resin examples include polyether ketone, polyether ether ketone, polyether ketone ketone, and polyether ether ketone ketone.
  • a phenol resin etc. are mentioned as a thermosetting resin.
  • the heat resistant resin is preferably at least one selected from the group consisting of a fluororesin, a polyether ketone resin, a polyarylene sulfide resin, and a phenol resin.
  • fusing point is the value calculated
  • fluororesin examples include polytetrafluoroethylene [PTFE], tetrafluoroethylene [TFE] / perfluoro (alkyl vinyl ether) [PAVE] copolymer [PFA], and TFE / hexafluoropropylene [HFP] copolymer [FEP].
  • PTFE polytetrafluoroethylene
  • TFE tetrafluoroethylene
  • PAVE perfluoro (alkyl vinyl ether)
  • HFP hexafluoropropylene
  • examples thereof include a polymer, polyvinylidene fluoride [PVDF], and polyvinyl fluoride [PVF].
  • PTFE, PFA, FEP, ETFE, Et / TFE / HFP copolymer, PCTFE, CTFE / TFE copolymer, Et / CTFE copolymer and PVDF At least selected from the group consisting of PTFE, PFA, FEP and ETFE is more preferred, and PTFE is still more preferred from the viewpoint of sealing properties and sliding properties.
  • the PTFE may be homo-PTFE containing only TFE units or modified PTFE containing TFE units and modified monomer units based on a modified monomer copolymerizable with TFE.
  • the PTFE may be high molecular weight PTFE having non-melt processability and fibrillation property, or may be low molecular weight PTFE having melt processability and no fibrillation property. High molecular weight PTFE having melt processability and fibrillation properties is preferred.
  • the modifying monomer is not particularly limited as long as it can be copolymerized with TFE.
  • perfluoroolefin such as hexafluoropropylene [HFP]; chlorofluoroolefin such as chlorotrifluoroethylene [CTFE];
  • HFP hexafluoropropylene
  • CTFE chlorofluoroolefin
  • examples thereof include hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; perfluorovinyl ether; perfluoroalkylethylene; ethylene; fluorine-containing vinyl ether having a nitrile group.
  • denatured monomer to be used may be 1 type, and multiple types may be sufficient as it.
  • Rf 1 represents a perfluoro organic group
  • the “perfluoro organic group” means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms.
  • the perfluoro organic group may have ether oxygen.
  • perfluorovinyl ether examples include perfluoro (alkyl vinyl ether) [PAVE] in which Rf 1 represents a perfluoroalkyl group having 1 to 10 carbon atoms in the general formula (1).
  • the perfluoroalkyl group preferably has 1 to 5 carbon atoms.
  • perfluoroalkyl group in the PAVE examples include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.
  • Purple propyl vinyl ether [PPVE] whose group is a perfluoropropyl group is preferred.
  • Rf 1 is a perfluoro (alkoxyalkyl) group having 4 to 9 carbon atoms, Rf 1 is represented by the following formula:
  • Rf 1 is a group represented by the following formula:
  • n represents an integer of 1 to 4
  • the perfluoroalkylethylene is not particularly limited, and examples thereof include perfluorobutylethylene [PFBE], perfluorohexylethylene, (perfluorooctyl) ethylene, and the like.
  • CF 2 CFORf 2 CN (wherein Rf 2 represents an alkylene group having 2 to 7 carbon atoms in which an oxygen atom may be inserted between two carbon atoms. ) Is more preferable.
  • the modified monomer in the modified PTFE is preferably at least one selected from the group consisting of HFP, CTFE, VDF, PPVE, PFBE, and ethylene. More preferably, it is at least one monomer selected from the group consisting of PPVE, HFP and CTFE.
  • the modified PTFE preferably has a modified monomer unit in the range of 0.001 to 2 mol%, and more preferably in the range of 0.001 to 1 mol%.
  • the PTFE preferably has a melt viscosity (MV) of 1.0 ⁇ 10 2 Pa ⁇ s or more, more preferably 1.0 ⁇ 10 2 Pa ⁇ s or more, and 1.0 ⁇ 10 3 Pa ⁇ s. It is still more preferable that it is above.
  • the melt viscosity is in accordance with ASTM D 1238, and a 2 g sample that had been heated for 5 minutes at a measurement temperature (380 ° C.) in advance using a flow tester (manufactured by Shimadzu Corporation) and a 2 ⁇ -8L die was set to 0.000. The measurement can be performed while maintaining the above temperature with a load of 7 MPa.
  • the PTFE preferably has a standard specific gravity (SSG) of 2.130 to 2.230, more preferably 2.140 or more, and more preferably 2.190 or less.
  • SSG standard specific gravity
  • ASTM D 4895-89 ASTM D 4895-89.
  • the PTFE preferably has a melting point of 324 to 360 ° C.
  • the melting point of the fluororesin is a value obtained as a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimetry (DSC) apparatus. .
  • the copolymer whose molar ratio (TFE unit / PAVE unit) of a TFE unit and a PAVE unit is 70/30 or more and less than 99/1 is preferable.
  • a more preferable molar ratio is 70/30 or more and 98.9 / 1.1 or less, and a still more preferable molar ratio is 80/20 or more and 98.5 / 1.5 or less.
  • monomer units derived from monomers copolymerizable with TFE and PAVE are 0.1 to 10 mol%, and TFE units and PAVE units are 90 to 99.9 mol% in total.
  • a copolymer is also preferred.
  • the PFA preferably has a melting point of 180 to 340 ° C, more preferably 230 to 330 ° C, and still more preferably 280 to 320 ° C.
  • the PFA preferably has a melt flow rate (MFR) of 0.1 to 100 g / 10 minutes, more preferably 0.5 to 90 g / 10 minutes, and 1.0 to 85 g / 10 minutes. More preferably.
  • MFR is a value obtained by measuring at a temperature of 372 ° C. and a load of 5 kg in accordance with ASTM D 1238.
  • the PFA preferably has a standard specific gravity of 2.12 to 2.18.
  • the copolymer whose molar ratio (TFE unit / HFP unit) of a TFE unit and a HFP unit is 70/30 or more and less than 99/1 is preferable.
  • a more preferable molar ratio is 70/30 or more and 98.9 / 1.1 or less, and a still more preferable molar ratio is 80/20 or more and 97/3 or less.
  • FEP has a monomer unit derived from a monomer copolymerizable with TFE and HFP in an amount of 0.1 to 10 mol%, and a total of 90 to 99.9 mol% of TFE units and HFP units.
  • a polymer is also preferred.
  • monomers copolymerizable with TFE and HFP include PAVE and alkyl perfluorovinyl ether derivatives.
  • the FEP preferably has a melting point of 150 to 320 ° C, more preferably 200 to 300 ° C, and still more preferably 240 to 280 ° C.
  • the FEP preferably has an MFR of 0.01 to 100 g / 10 minutes, more preferably 0.1 to 80 g / 10 minutes, still more preferably 1 to 60 g / 10 minutes. Particularly preferred is 50 g / 10 min.
  • the FEP preferably has a standard specific gravity of 2.12 to 2.18.
  • the ETFE is preferably a copolymer having a molar ratio of TFE units to ethylene units (TFE units / ethylene units) of 20/80 or more and 90/10 or less. A more preferable molar ratio is 37/63 or more and 85/15 or less, and a further preferable molar ratio is 38/62 or more and 80/20 or less.
  • ETFE may be a copolymer composed of TFE, ethylene, and a monomer copolymerizable with TFE and ethylene.
  • the monomer copolymerizable with TFE and ethylene may be an aliphatic unsaturated carboxylic acid such as itaconic acid or itaconic anhydride.
  • the monomer copolymerizable with TFE and ethylene is preferably from 0.1 to 10 mol%, more preferably from 0.1 to 5 mol%, particularly preferably from 0.2 to 4 mol%, based on the fluoropolymer. preferable.
  • the ETFE preferably has a melting point of 140 to 340 ° C, more preferably 160 to 300 ° C, and still more preferably 195 to 275 ° C.
  • the ETFE preferably has an MFR of 1 to 100 g / 10 minutes, more preferably 2 to 50 g / 10 minutes, and still more preferably 4 to 40 g / 10 minutes.
  • the ETFE preferably has a standard specific gravity of 1.70 to 1.90.
  • each monomer unit constituting the fluororesin can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.
  • the graphite yarn (A) has a crystallite size in the c-axis direction of 100 mm or less.
  • the resin composition of the present invention uses the graphite yarn (A) having a specific crystallite size and the graphite yarn (B) in combination, so that the aluminum can be contacted with an aluminum article even when the wear coefficient is small.
  • the surface of the manufactured article can be made difficult to be damaged.
  • the crystallite size in the c-axis direction is preferably 90 mm or less, and more preferably 60 mm or less.
  • the lower limit of the crystallite size in the c-axis direction is not particularly limited, but is, for example, 10 mm.
  • the crystallite size in the c-axis direction is obtained by the Gakushin method using an X-ray diffractometer, measuring reflection from the (002) plane appearing in X-ray diffraction. Specifically, the crystallite size in the c-axis direction is measured by X-ray diffraction measurement using an X-ray diffractometer (Rigaku, Ultima III), and the measurement substance is packed flat in a concave portion of a quartz sample holder.
  • the X-ray source is set to Cu-K ⁇ ray
  • the output is set to 40 kV, 20 mA
  • the reflection from the (002) plane appearing in the X-ray diffraction is measured, and it can be obtained by the Gakushin method.
  • the graphite yarn (A) is preferably other than pitch-based anisotropic graphite yarn.
  • the graphite yarn (A) is a graphite yarn other than the pitch-based anisotropic graphite yarn, a resin composition having a small wear coefficient can be obtained.
  • the graphite yarn other than the pitch-based anisotropic graphite yarn include pitch-based isotropic graphite yarn, pitch-based isotropic carbon yarn, PAN-based carbon yarn, and PAN-based graphite yarn. Among these, although not particularly limited, pitch-based isotropic graphite yarn is more preferable.
  • the graphite yarn (A) preferably has an average fiber length of 5 to 1000 ⁇ m, more preferably 5 to 500 ⁇ m, from the viewpoint of maintaining mechanical strength and mixing with the resin. More preferably.
  • the average fiber length a 200-magnification image of a scanning electron microscope is arbitrarily taken for 10 fields of view, 200 fiber lengths are measured, and a number average fiber length is obtained.
  • the graphite yarn (A) preferably has an average fiber diameter of 1 to 25 ⁇ m, more preferably 1 to 20 ⁇ m, from the viewpoint of maintaining mechanical strength and mixing with the resin. More preferably.
  • the average fiber diameter is obtained by arbitrarily photographing 10 field images of a scanning electron microscope for 10 fields of view, measuring the length of 200 fibers, and determining the number average fiber diameter.
  • the graphite yarn (A) has a half width of the diffraction peak of the (002) plane observed by X-ray diffraction and the (111) plane of standard silicon (NBS, 640) observed by X-ray diffraction under the same conditions.
  • the half-value width ratio of the half-value width of the diffraction peak of (graphite yarn) / (standard silicon) standard silicon is preferably 10 or more.
  • the half width ratio is more preferably 12 or more.
  • the upper limit of the half width ratio is not particularly limited, but may be 100, for example.
  • the X-ray diffraction is measured by the same method as the crystallite size in the c-axis direction.
  • the graphite yarn (A) preferably has a specific gravity of 1.3 or more and less than 2.0, and more preferably 1.4 to 1.9.
  • the specific gravity can be determined according to the butanol substitution method (JIS R 7222).
  • Examples of the graphite yarn (A) include Kureha Corporation Kureka Chop M2007S (crystallite size: 16.5 mm), M-201S (crystallite size: 17.4 mm), M-207S, M-1009S, M-101S, Donakabo SC249 (crystallite size: 13.9 mm), SG-249 (crystallite size: 17.6 mm), SC-2404N (crystallite size: 13.9 mm), SG manufactured by Osaka Gas Chemical Co., Ltd.
  • the graphite yarn (B) has a crystallite size in the c-axis direction of more than 100 mm.
  • the resin composition of the present invention uses the graphite yarn (A) having a specific crystallite size and the graphite yarn (B) in combination, so that the aluminum can be contacted with an aluminum article even when the wear coefficient is small.
  • the surface of the manufactured article can be made difficult to be damaged.
  • the crystallite size in the c-axis direction is preferably 120 mm or more, and more preferably 140 mm or more.
  • the upper limit of the crystallite size in the c-axis direction is not particularly limited, but is, for example, 500 mm.
  • the crystallite size in the c-axis direction is determined by the same method as for the graphite yarn (A).
  • the graphite yarn (B) is preferably a pitch-based anisotropic graphite yarn.
  • the graphite yarn (B) is a pitch-based anisotropic graphite yarn, the surface of the aluminum article can be hardly damaged when it comes into contact with the aluminum article.
  • the graphite yarn (B) has a half-value width of the diffraction peak of the (002) plane observed by X-ray diffraction and a half of the diffraction peak of the (111) plane of standard silicon observed by X-ray diffraction under the same conditions. It is preferable that the half width ratio of the full width at half width (graphite yarn) / (standard silicon) to standard silicon is less than 10. More preferably, it is 7 or less. The lower limit of the half width ratio is not particularly limited, but may be 1, for example.
  • the X-ray diffraction is measured by the same method as the crystal size in the c-axis direction.
  • the graphite yarn (B) preferably has an average fiber length of 5 to 1000 ⁇ m, more preferably 5 to 500 ⁇ m, from the viewpoint of maintaining mechanical strength and mixing with the resin. More preferably.
  • the average fiber length was obtained by arbitrarily photographing 10-fold images of a scanning electron microscope for 10 fields of view, measuring the length of 200 fibers, and obtaining the number average fiber length.
  • the graphite yarn (B) preferably has an average fiber diameter of 1 to 25 ⁇ m, more preferably 1 to 20 ⁇ m, from the viewpoint of maintaining mechanical strength and miscibility with the resin. More preferably.
  • the average fiber diameter 200-magnification images of a scanning electron microscope were arbitrarily taken for 10 fields of view, 200 fiber diameters were measured, and the number average fiber diameter was obtained.
  • the graphite yarn (B) preferably has a specific gravity of 2.0 to 2.4, more preferably 2.0 to 2.3, from the viewpoint of attacking the counterpart material.
  • the specific gravity can be determined according to the butanol substitution method (JIS R 7222).
  • Examples of the graphite yarn (B) include XN-100-05M (crystallite size: 234.0 mm), XN-100-10M, and XN-100-15M (crystallite size: 243) manufactured by Nippon Graphite Fiber Co., Ltd. .8 cm), HC-600-15M (crystallite size: 230.7 mm), ZY-300-15M (crystallite size: 312.9 mm), K223HM manufactured by Mitsubishi Rayon Co., Ltd. (crystallite size: 211.0 cm) , K6331M (crystallite size: 130.6 ⁇ ) and the like.
  • the total content of the graphite yarn (A) and the graphite yarn (B) is preferably 3 to 40% by mass with respect to the resin composition. If it is less than 3% by mass, the filler filling effect may not be exhibited. If it exceeds 40% by mass, mechanical properties tend to be remarkably lowered.
  • the mass ratio (A / B) of the content of the graphite yarn (A) and the graphite yarn (B) is 1.0 / 9.0 to 9.9 / 0.1. Is preferred. More preferably, it is 3.0 / 7.0 to 9.9 / 0.1.
  • the mass ratio (A / B) is preferably 7.0 / 3.0 to 9.9 / 0.1.
  • the resin composition of the present invention preferably contains a graphite yarn (A) that is other than the pitch-based anisotropic graphite yarn and a graphite yarn (B) that is the pitch-based anisotropic graphite yarn.
  • the resin composition of the present invention may be composed only of a heat resistant resin and graphite yarns (A) and (B), but is necessary in addition to the heat resistant resin and graphite yarns (A) and (B).
  • other components may be included.
  • various additives such as metal, inorganic or organic reinforcing fillers, compatibilizers, lubricants (carbon fluoride, carbon graphite, molybdenum disulfide), stabilizers, and the like may be combined.
  • the resin composition of the present invention can be produced by a known method.
  • heat-resistant resin, graphite yarn (A) and graphite yarn (B), and other components added as necessary such as V-type blender, tumbler, Henschel mixer, ball mixer, Redige mixer, etc.
  • melt-kneading apparatuses such as a single screw extruder and a twin screw extruder.
  • a method of supplying the graphite yarns (A) and (B) to the heat resistant resin melted in the melt kneading apparatus in the middle is also possible.
  • the resin composition of the present invention has excellent sliding properties and can be used as a sliding material that can be used in a high temperature and high heat generation environment.
  • the products including the sliding material include various gears, sliding friction or rolling friction mechanism bearings, bearings, brakes, clutch parts, piston rings, various seal members, and the like.
  • Suitable applications include seal rings used in various hydraulic devices such as automobile automatic transmissions and continuously variable transmissions. That is, the present invention is also a seal ring formed by molding the resin composition.
  • a seal ring used in contact with an aluminum article is preferable.
  • the seal ring is particularly useful as a seal ring for automobiles, particularly as a seal ring for automobile automatic transmissions.
  • the seal ring can be formed by a usual method according to the heat-resistant resin used.
  • Examples of the molding method include injection molding, extrusion molding, and compression molding.
  • PTFE is used as the heat resistant resin
  • PTFE, graphite yarns (A) and (B) are mixed with the above mixer to obtain a resin composition, and then molded by a molding method such as compression molding.
  • the obtained fired body may be processed by cutting or the like to obtain a desired molded body (such as a seal ring).
  • compressor seals chip seals, piston rings
  • high-pressure seals for high-rise buildings, trucks, buses, automobiles, and other power steering systems that use carbon dioxide, natural gas, alternative chlorofluorocarbon, air, helium gas, etc. It can also be used as a seal bearing for construction machines such as seal rings, excavators, forklifts, bulldozers or nailers.
  • Base polymer (heat resistant resin) Polytetrafluoroethylene (PTFE), trade name: Polyflon M-18F, manufactured by Daikin Industries, Ltd., standard specific gravity (SSG): 2.164, melting point: 344.9 ° C.
  • Pitch-based anisotropic graphite yarn Product name: GRANOC, Grade: XN-100-15M, manufactured by Nippon Graphite Fiber Co., Ltd., half-value width ratio with standard silicon: 3, crystallite size in the c-axis direction 244 ⁇
  • Pitch-based isotropic graphite yarn Product name: Kureka chop, grade: M2007S, manufactured by Kureha Co., Ltd., half-value width ratio with standard silicon: 46, crystallite size in the c-axis direction 17 mm
  • the SSG and melting point of the PTFE, the half width ratio of the graphite yarns (A) and (B) with the standard silicon, and the crystallite size in the c-axis direction are values obtained by the above-de
  • Relative material surface roughness change rate (%) The rate of change in surface roughness of the mating material was calculated by the following equation: surface roughness of the mating material sliding surface before the frictional wear test (before Ra) and mating material sliding surface surface roughness after the test (after Ra).
  • Relative material surface roughness change rate (%) (after Ra-before Ra) ⁇ 100 / Ra
  • the surface roughness of the mating material sliding surface after the pre-test is 3 hours in the electric furnace at 410 ° C. after the test. By heating and allowing to cool in a desiccator for 2 hours, the sliding surface of this mating material is measured according to JIS B 0601-1994 using a surface roughness measuring machine SURFTEST SV-600 manufactured by Mitutoyo. Obtained.
  • Comparative Example 1 90 parts by mass of polytetrafluoroethylene resin powder (Polyflon PTFE M-18F, manufactured by Daikin Industries, Ltd.) obtained by suspension polymerization, and pitch-based anisotropic graphite yarn (GRANOC XN-100-15M) as a filler, 10 parts by mass of Nippon Graphite Fiber Co., Ltd.) was mixed using a Henschel mixer to obtain a polytetrafluoroethylene composition.
  • Polytetrafluoroethylene resin powder Polyflon PTFE M-18F, manufactured by Daikin Industries, Ltd.
  • pitch-based anisotropic graphite yarn GRANOC XN-100-15M
  • Example 1 90 parts by mass of polytetrafluoroethylene resin powder (Polyflon PTFE M-18F, manufactured by Daikin Industries, Ltd.) obtained by suspension polymerization, and pitch-based anisotropic graphite yarn (GRANOC XN-100-15M) as a filler, 9 parts by mass of Nippon Graphite Fiber Co., Ltd. and 1 part by mass of pitch-based isotropic graphite yarn (Kureka Chop M2007S, Kureha Co., Ltd.) were mixed using a Henschel mixer to obtain a polytetrafluoroethylene composition. .
  • Example 2 to Example 8 In the same manner as in Example 1, the blending amounts shown in Table 1 were mixed.
  • Comparative Example 2 90 parts by mass of polytetrafluoroethylene resin powder (polyflon PTFE M-18F, manufactured by Daikin Industries, Ltd.) obtained by suspension polymerization, and pitch-based isotropic graphite yarn (Kureka Chop M2007S, Kureha Co., Ltd.) as a filler 10 parts by mass) were mixed using a Henschel mixer to obtain a polytetrafluoroethylene composition.
  • polytetrafluoroethylene resin powder polyflon PTFE M-18F, manufactured by Daikin Industries, Ltd.
  • pitch-based isotropic graphite yarn Kureka Chop M2007S, Kureha Co., Ltd.
  • the wear coefficient is reduced by using a graphite thread having a crystallite size in the c-axis direction of 100 mm or less and a graphite thread having a crystallite size in the c-axis direction exceeding 100 mm.
  • a molded body that hardly damages the surface of the aluminum article is obtained.
  • the wear coefficient can be reduced without increasing the mating material surface roughness change rate as compared with Comparative Example 1.

Landscapes

  • 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 qui présente un faible coefficient de frottement et qui ne tend pas à endommager la surface d'un article en aluminium quand elle entre en contact avec l'article en aluminium. La composition de résine est caractérisée en ce qu'elle comprend : une résine résistant à la chaleur ; un fil de graphite (A) présentant une grosseur des cristallites dans la direction de l'axe c de 100 Å ou moins ; et un fil de graphite (B) présentant une grosseur des cristallites dans la direction de l'axe c supérieure à 100 Å.
PCT/JP2017/039768 2016-11-28 2017-11-02 Composition de résine WO2018096908A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016230423A JP6520899B2 (ja) 2016-11-28 2016-11-28 樹脂組成物
JP2016-230423 2016-11-28

Publications (1)

Publication Number Publication Date
WO2018096908A1 true WO2018096908A1 (fr) 2018-05-31

Family

ID=62195490

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/039768 WO2018096908A1 (fr) 2016-11-28 2017-11-02 Composition de résine

Country Status (2)

Country Link
JP (1) JP6520899B2 (fr)
WO (1) WO2018096908A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019225435A1 (fr) * 2018-05-22 2019-11-28 ダイキン工業株式会社 Composition de résine

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6838627B2 (ja) * 2019-07-25 2021-03-03 ダイキン工業株式会社 樹脂組成物、成型品及びオートマチックトランスミッション
CN114829142A (zh) * 2019-12-18 2022-07-29 Ａｇｃ株式会社 被覆基材、热交换器、被覆基材的制造方法及液态组合物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62170528A (ja) * 1986-01-22 1987-07-27 Nitto Boseki Co Ltd 炭素繊維とその製造方法
JPH02275759A (ja) * 1989-01-17 1990-11-09 Toyota Motor Corp 摺動部材
JPH09194626A (ja) * 1996-01-23 1997-07-29 Osaka Gas Co Ltd 樹脂複合摺動材
JPH1129830A (ja) * 1997-07-11 1999-02-02 Agency Of Ind Science & Technol 微細構造の制御された繊維を用いた繊維強化複合材料
JP2000136310A (ja) * 1998-10-30 2000-05-16 Osaka Gas Co Ltd 高分子材料用導電性調整材および導電性高分子材料
JP2011037919A (ja) * 2009-08-06 2011-02-24 Teijin Ltd 熱伝導性棒状樹脂成形体

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62170528A (ja) * 1986-01-22 1987-07-27 Nitto Boseki Co Ltd 炭素繊維とその製造方法
JPH02275759A (ja) * 1989-01-17 1990-11-09 Toyota Motor Corp 摺動部材
JPH09194626A (ja) * 1996-01-23 1997-07-29 Osaka Gas Co Ltd 樹脂複合摺動材
JPH1129830A (ja) * 1997-07-11 1999-02-02 Agency Of Ind Science & Technol 微細構造の制御された繊維を用いた繊維強化複合材料
JP2000136310A (ja) * 1998-10-30 2000-05-16 Osaka Gas Co Ltd 高分子材料用導電性調整材および導電性高分子材料
JP2011037919A (ja) * 2009-08-06 2011-02-24 Teijin Ltd 熱伝導性棒状樹脂成形体

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019225435A1 (fr) * 2018-05-22 2019-11-28 ダイキン工業株式会社 Composition de résine
US11168210B2 (en) 2018-05-22 2021-11-09 Daikin Industries, Ltd. Resin composition

Also Published As

Publication number Publication date
JP6520899B2 (ja) 2019-05-29
JP2018087271A (ja) 2018-06-07

Similar Documents

Publication Publication Date Title
JP5702385B2 (ja) 樹脂組成物および成形品
JP5472689B2 (ja) 改質ふっ素樹脂組成物及び成形体
JPWO2013088964A1 (ja) 樹脂組成物及び成形品
WO2006120882A1 (fr) Composition de polytetrafluorethylene reticulable, poudre de polytetrafluorethylene reticulable, moulages en polytetrafluorethylene, compositions de melange de resines et moulages en melange de resines
WO2018096908A1 (fr) Composition de résine
WO2012070401A1 (fr) Élément coulissant pour un détachement de matière d'enregistrement en forme de feuille, bague d'étanchéité pour automobile et bague d'étanchéité et élément coulissant pour un compresseur de gaz industriels
JP5249580B2 (ja) 芳香族ポリイミド組成物及びそれから製造される物品
JP6645606B2 (ja) 樹脂組成物
TW202016199A (zh) 樹脂組成物及成形品
JP3235223B2 (ja) ポリフェニレンサルファイド樹脂組成物の製法
EP2707425A1 (fr) Composite à base de polymère fluoré à faible taux d'usure
JP5751347B2 (ja) 歯車
JPH0425310B2 (fr)
JP5365939B2 (ja) 自動車用シールリング、産業ガス圧縮機用シールリング及び摺動部品
CN112154183B (zh) 聚四氟乙烯组合物
JP2002128981A (ja) 耐圧摺動性四フッ化エチレン樹脂組成物
JP2011016956A (ja) 架橋性ｐｔｆｅ組成物、およびその成形体
JP2014129465A (ja) 組成物、成形体及び繊維
JPH0881608A (ja) フッ素樹脂組成物
JP6838627B2 (ja) 樹脂組成物、成型品及びオートマチックトランスミッション
JP2010156398A (ja) 摺動材
JPH0465866B2 (fr)
JPH05117475A (ja) 含フツ素溶融樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17874535

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17874535

Country of ref document: EP

Kind code of ref document: A1