WO2025063049A1 - Polyether ether ketone resin composition and molded article - Google Patents
Polyether ether ketone resin composition and molded article Download PDFInfo
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- WO2025063049A1 WO2025063049A1 PCT/JP2024/031850 JP2024031850W WO2025063049A1 WO 2025063049 A1 WO2025063049 A1 WO 2025063049A1 JP 2024031850 W JP2024031850 W JP 2024031850W WO 2025063049 A1 WO2025063049 A1 WO 2025063049A1
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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
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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
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- 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 polyether ketone resin composition and a molded article.
- Fully aromatic ether ketone resin is also known by the abbreviation PAEK (polyaryl ether ketone), and products on the market include PEEK (polyether ether ketone), PEK (polyether ketone), PEKK (polyether ketone ketone), and PEKEKK (polyether ketone ether ketone ketone).
- PAEK polyaryl ether ketone
- PEEK polyether ether ketone
- PEK polyether ketone
- PEKK polyether ketone ketone
- PEKEKK polyether ketone ether ketone ketone
- the resin composition containing PEEK of Patent Document 1 is characterized by excellent fluidity, but such resin compositions with excellent fluidity are prone to burrs during molding, making post-processing such as deburring necessary after molding. Furthermore, in order to maintain sliding properties, precise surface finishing and other processes are required, which poses the problem of significantly reducing productivity.
- the present invention was made in consideration of the above-mentioned problems with the conventional technology, and its objective is to provide a polyether ketone resin composition and molded product that have excellent sliding properties and little burr generation.
- One aspect of the present invention that solves the above problems is as follows. (1) (A) 40 to 80% by mass of a polyether ketone resin, (B) 5 to 30 mass% carbon fiber, (C) a polyether ketone resin composition containing 5 to 25 mass% of graphite, and (D) 5 to 25 mass% of polytetrafluoroethylene.
- polyetherketone resin composition according to any one of (1) to (3), wherein the polyetherketone resin (A) has a fluoride ion concentration of 80 ⁇ g/g or less as measured by combustion ion chromatography.
- the present invention provides a polyether ketone resin composition that has excellent sliding properties and produces little burrs.
- the polyetherketone resin composition of this embodiment contains (A) 40 to 80 mass% polyetherketone resin, (B) 5 to 30 mass% carbon fiber, (C) 5 to 25 mass% graphite, and (D) 5 to 25 mass% polytetrafluoroethylene.
- a resin composition having excellent fluidity has the disadvantage of being prone to burrs, while being excellent in fluidity.
- the (A) polyetherketone resin has a faster crystallization rate than PEEK (polyetheretherketone), and is therefore less likely to generate burrs during molding compared to PEEK.
- the (A) polyetherketone resin has excellent sliding properties and contains (B) carbon fiber, (C) graphite, and (D) polytetrafluorotoluene in a predetermined ratio, a resin composition having excellent sliding properties and less burrs can be obtained. That is, by containing all of the (A) component to the (D) component in a predetermined ratio, the roles of each component work together to exert the above-mentioned effect. Each component will be described in detail below.
- the polyetherketone resin composition of the present embodiment contains 40 to 80 mass% of (A) polyetherketone resin as a base resin.
- (A) Polyetherketone resin is a resin having a phenylketone structure and a phenylether structure as main structures. Polyetherketone resin is excellent in heat resistance, mechanical strength, moldability, etc., and has a faster crystallization rate than PEEK (polyetheretherketone), so that burrs are less likely to occur during molding.
- the polyether ketone resin (A) is contained at 40 to 80 mass %, but if it is less than 40 mass %, the continuous layer of the resin becomes relatively small, and in a situation where repeated stress is applied, such as in a sliding field, the force holding the other components is insufficient, causing them to fall off and preventing the improvement of sliding characteristics. If it exceeds 80 mass %, the amount of other components that improve the sliding characteristics must be reduced, and the sliding characteristics cannot be improved.
- the content of the polyether ketone resin (A) is preferably 42.5 to 77.5 mass %, more preferably 45 to 75 mass %, and even more preferably 47.5 to 72.5 mass %.
- the polyether ketone resin (A) preferably has a fluoride ion concentration of 80 ⁇ g/g or less, more preferably 60 ⁇ g/g or less, and even more preferably 40 ⁇ g/g or less, as measured by combustion ion chromatography.
- a fluoride ion concentration of 80 ⁇ g/g or less it is possible to reduce the generation of hydrofluoric acid during melt kneading, etc.
- the polyetherketone resin can generally be obtained by reacting 4,4'-difluorobenzophenone with an excess amount of a bisphenol compound.
- the polyetherketone resin can be obtained by reacting a mixture of terephthalic acid dichloride and isophthalic acid dichloride with diphenyl ether in the presence of hydrogen fluoride and boron fluoride.
- a synthesis method causes fluorine compounds to be mixed into the product, which causes the generation of hydrofluoric acid. Therefore, it is preferable to synthesize the polyetherketone resin by the method described in JP 2009-227961 A. According to this method, since no compound containing fluorine is used in the synthesis process, it is possible to suppress the mixing of fluorine compounds into the product. That is, as described above, a polyetherketone resin can be obtained in which the concentration of fluoride ions measured by combustion ion chromatography is 80 ⁇ g/g or less.
- the polyether ketone resin preferably has a melt viscosity of 100 to 300 Pa ⁇ s, as measured in accordance with ISO 11443 using a capillary rheometer at a cylinder temperature of 400°C and a shear rate of 1000/sec.
- melt viscosity can be adjusted to any desired value by controlling the reaction time in the above method for synthesizing polyether ketone resin.
- the polyether ketone resin composition of the present embodiment contains 5 to 30 mass % of (B) carbon fiber.
- (B) Carbon fiber contributes to improving sliding properties.
- (B) Carbon fiber may be either pitch-based or PAN-based, as classified based on the raw material. Pitch-based carbon fiber, which has high sliding properties, is preferable as the (B) carbon fiber. There are no particular limitations on the firing temperature of the (B) carbon fiber, but it is preferable that the (B) carbon fiber is fired at a high temperature of 2000°C or higher to be graphitized, as this is less likely to cause wear and damage to the mating material.
- (B) carbon fiber can be obtained by melt-kneading a carbon fiber raw material having, for example, a fiber length of 3 to 10 mm and a fiber diameter of 2 to 10 ⁇ m together with other components.
- (B) carbon fiber is contained at 5 to 30 mass %, but if it is less than 5 mass %, the sliding properties of the carbon fiber are not fully expressed, and if it exceeds 30 mass %, friction and wear increase due to collisions between the carbon fibers, making it impossible to obtain excellent sliding properties.
- the content of (B) carbon fiber is preferably 5 to 27.5 mass %, more preferably 7.5 to 25 mass %, and even more preferably 7.5 to 22.5 mass %.
- the polyether ketone resin composition of the present embodiment contains 5 to 25 mass % of (C) graphite.
- (C) Graphite contributes to improving the sliding properties.
- the graphite (C) is not particularly limited, and examples thereof include flake graphite, scaly graphite, artificial graphite, and amorphous graphite, and any of these can be used.
- the median diameter (D50) of graphite is preferably 30 to 80 ⁇ m, more preferably 35 to 75 ⁇ m, and even more preferably 40 to 70 ⁇ m. When the median diameter is 30 to 80 ⁇ m, the sliding characteristics can be further improved.
- the median diameter (D50) means the particle diameter (D50) at 50% volume accumulation in the particle size distribution of graphite determined by a laser diffraction scattering method.
- (C) graphite is contained at 5 to 25 mass%, but if it is less than 5 mass%, the sliding properties of the graphite are not fully expressed, and if it exceeds 25 mass%, excessive graphite falls off and excellent sliding properties cannot be obtained.
- the content of (C) graphite is preferably 5 to 22.5 mass%, and more preferably 7.5 to 22.5 mass%.
- the polyether ketone resin composition of the present embodiment contains 5 to 25 mass % of polytetrafluoroethylene (D). By including polytetrafluoroethylene (D), it is possible to impart sliding properties.
- the weight loss rate of (D) polytetrafluoroethylene is 0.5% by mass or less when heated from 30°C to 400°C at a temperature increase rate of 10°C/min in an air flow. If the weight loss rate is 0.5% by mass or less, the heat resistance is high and the generation of hydrofluoric acid can be suppressed.
- the weight loss rate is more preferably 0 to 0.3% by mass, and even more preferably 0 to 0.1% by mass.
- (D) polytetrafluoroethylene is contained at 5 to 25 mass%, but if it is less than 5 mass%, the sliding properties of polytetrafluoroethylene are not fully expressed, and if it exceeds 25 mass%, excessive loss of polytetrafluoroethylene occurs and excellent sliding properties cannot be obtained.
- the content of (D) polytetrafluoroethylene is preferably 5 to 22.5 mass%, and more preferably 7.5 to 22.5 mass%.
- thermoplastic resins such as a lubricant, a release agent, an antistatic agent, a surfactant, a flame retardant, an organic polymer material, or an inorganic or organic powder-like or plate-like filler, may be added.
- the polyether ketone resin composition of this embodiment has excellent sliding properties and is therefore suitable for use as a sliding member.
- the molded product described below will be used as an example of such a sliding member.
- the molded article of the present embodiment contains the polyether ketone resin composition of the present embodiment described above, and therefore has the effects of excellent sliding properties and reduced burr generation.
- the method for producing the molded product of this embodiment is not particularly limited, and any known method can be used.
- the polyether ketone resin composition of this embodiment can be fed into an extruder, melt-kneaded and pelletized, and the pellets can be fed into an injection molding machine equipped with a specified mold and injection molded to produce the molded product.
- the molded product of this embodiment has excellent sliding properties and can be suitably used as a sliding member.
- sliding members include gears, thrust bearings, bearings, seal rings, etc. in parts such as engines, motors, brakes, transmissions, clutches, and dampers.
- PEK1 Polyetherketone resin produced by the production method described in JP 2009-227961 A (melt viscosity: 220 Pa s, fluoride ion: not detected)
- PEK2 Victrex, PEK, G22 (melt viscosity: 190 Pa s, fluoride ion: 759 ⁇ g / g)
- A' Polyether ether ketone resin PEEK: Victrex, PEEK, 450G (melt viscosity: 400 Pa s)
- B Carbon fiber CF: SGL Carbon Fibers, carbon fiber, SIGRAFIL (registered trademark) C C6-4.0 / 240-T190 (chopped strand, fiber length: 6 mm, fiber diameter: 7 ⁇ m)
- C Graphite GP1: Fuji Graphite Industry Co., Ltd., artificial graphite, G70 (median diameter (D50): 66 ⁇ m)
- melt Viscosity The melt viscosity of polyether ketone resins and polyether ether ketone resins was measured using a capillary rheometer ("Capilograph 1D" manufactured by Toyo Seiki Seisakusho, Ltd.) under the following conditions in accordance with ISO 11443 using an orifice having an inner diameter of 2 mm and a length of 60 mm.
- (4) Presence or absence of burrs The obtained pellets of the examples and comparative examples were molded under the following molding conditions using an injection molding machine (" ⁇ -S100iA" manufactured by Fanuc Corporation) to obtain flat test pieces of 80 mm x 80 mm x 3 mm. The obtained flat test pieces were visually observed for the presence or absence of burrs.
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Abstract
Description
本発明は、ポリエーテルケトン樹脂組成物及び成形品に関する。 The present invention relates to a polyether ketone resin composition and a molded article.
全芳香族エーテルケトン樹脂は、ＰＡＥＫ（ポリアリールエーテルケトン）の略語でも知られ、ＰＥＥＫ（ポリエーテルエーテルケトン）、ＰＥＫ（ポリエーテルケトン）、ＰＥＫＫ（ポリエーテルケトンケトン）、ＰＥＫＥＫＫ（ポリエーテルケトンエーテルケトンケトン）等が製品として上市されている。全芳香族エーテルケトン樹脂は、機械的性質、耐熱性、耐薬品等に優れ、そのような性質が要求される分野において広く用いられている。 Fully aromatic ether ketone resin is also known by the abbreviation PAEK (polyaryl ether ketone), and products on the market include PEEK (polyether ether ketone), PEK (polyether ketone), PEKK (polyether ketone ketone), and PEKEKK (polyether ketone ether ketone ketone). Fully aromatic ether ketone resin has excellent mechanical properties, heat resistance, and chemical resistance, and is widely used in fields where such properties are required.
一方、上記のように優れた特性を有する全芳香族エーテルケトン樹脂であっても、摺動部材に適用する場合、摩耗することがあった。そこで、特にＰＥＥＫ（ポリエーテルエーテルケトン）においては摺動性が付与された樹脂組成物が提案されている（特許文献１参照）。 On the other hand, even fully aromatic ether ketone resins with the excellent properties described above can suffer from wear when used in sliding components. Therefore, resin compositions that impart sliding properties, particularly to PEEK (polyether ether ketone), have been proposed (see Patent Document 1).
特許文献１のＰＥＥＫを含む樹脂組成物は流動性に優れる特徴を有する一方で、そのような流動性に優れる樹脂組成物は成形時にバリが発生し易く、成形後、バリ取りなどの後加工が必要となる。さらには摺動性を保持するために、精密な面出しなどが加わり、著しく生産性を低下させるという問題がある。 The resin composition containing PEEK of Patent Document 1 is characterized by excellent fluidity, but such resin compositions with excellent fluidity are prone to burrs during molding, making post-processing such as deburring necessary after molding. Furthermore, in order to maintain sliding properties, precise surface finishing and other processes are required, which poses the problem of significantly reducing productivity.
本発明は、上記従来の問題点に鑑みなされたものであり、その課題は、摺動特性に優れ、バリの発生が少ないポリエーテルケトン樹脂組成物及び成形品を提供することにある。 The present invention was made in consideration of the above-mentioned problems with the conventional technology, and its objective is to provide a polyether ketone resin composition and molded product that have excellent sliding properties and little burr generation.
前記課題を解決する本発明の一態様は以下の通りである。
（１）（Ａ）ポリエーテルケトン樹脂を４０～８０質量％、
（Ｂ）炭素繊維を５～３０質量％、
（Ｃ）黒鉛を５～２５質量％、及び
（Ｄ）ポリテトラフルオロエチレンを５～２５質量％含有する、ポリエーテルケトン樹脂組成物。
One aspect of the present invention that solves the above problems is as follows.
(1) (A) 40 to 80% by mass of a polyether ketone resin,
(B) 5 to 30 mass% carbon fiber,
(C) a polyether ketone resin composition containing 5 to 25 mass% of graphite, and (D) 5 to 25 mass% of polytetrafluoroethylene.
（２）前記（Ｄ）ポリテトラフルオロエチレンは、空気気流下、昇温速度１０℃／分で３０℃から４００℃まで加熱したときの重量減少率が０．５質量％以下である、前記（１）に記載のポリエーテルケトン樹脂組成物。 (2) The polyether ketone resin composition according to (1) above, in which the (D) polytetrafluoroethylene has a weight loss rate of 0.5% by mass or less when heated from 30°C to 400°C at a heating rate of 10°C/min in an air flow.
（３）前記（Ｃ）黒鉛のメディアン径（Ｄ５０）は、３０～８０μｍである、前記（１）又は（２）に記載のポリエーテルケトン樹脂組成物。 (3) The polyether ketone resin composition according to (1) or (2), wherein the median diameter (D50) of the graphite (C) is 30 to 80 μm.
（４）前記（Ａ）ポリエーテルケトン樹脂は、燃焼イオンクロマトグラフィによって測定されるフッ化物イオンの濃度が８０μｇ／ｇ以下である、前記（１）～（３）のいずれかに記載のポリエーテルケトン樹脂組成物。 (4) The polyetherketone resin composition according to any one of (1) to (3), wherein the polyetherketone resin (A) has a fluoride ion concentration of 80 μg/g or less as measured by combustion ion chromatography.
（５）摺動部材用である、前記（１）～（４）のいずれかに記載のポリエーテルケトン樹脂組成物。 (5) A polyether ketone resin composition according to any one of (1) to (4) above, which is for use in sliding members.
（６）前記（１）～（５）のいずれかに記載のポリエーテルケトン樹脂組成物を成形してなる、成形品。 (6) A molded article obtained by molding the polyether ketone resin composition described in any one of (1) to (5).
（７）摺動部材である、前記（６）に記載の成形品。 (7) The molded product described in (6) above, which is a sliding member.
本発明によれば、摺動特性に優れ、バリの発生が少ないポリエーテルケトン樹脂組成物を提供することができる。 The present invention provides a polyether ketone resin composition that has excellent sliding properties and produces little burrs.
本実施形態のポリエーテルケトン樹脂組成物は、（Ａ）ポリエーテルケトン樹脂を４０～８０質量％、（Ｂ）炭素繊維を５～３０質量％、（Ｃ）黒鉛を５～２５質量％、及び（Ｄ）ポリテトラフルオロエチレンを５～２５質量％含有する。 The polyetherketone resin composition of this embodiment contains (A) 40 to 80 mass% polyetherketone resin, (B) 5 to 30 mass% carbon fiber, (C) 5 to 25 mass% graphite, and (D) 5 to 25 mass% polytetrafluoroethylene.
流動性に優れる樹脂組成物は流動性に優れる一方で、バリが発生しやすいという欠点を抱えている。本実施形態においては、（Ａ）ポリエーテルケトン樹脂は、ＰＥＥＫ（ポリエーテルエーテルケトン）よりも結晶化速度が速いため、ＰＥＥＫと比較して成形時においてバリが発生しにくい。また、（Ａ）ポリエーテルケトン樹脂は摺動特性に優れること、並びに（Ｂ）炭素繊維、（Ｃ）黒鉛、及び（Ｄ）ポリテトラフルオロトルエンを所定の割合で含有することから、摺動特性に優れ、かつ、バリの発生が少ない樹脂組成物が得られる。すなわち、（Ａ）成分～（Ｄ）成分のすべてを所定の割合で含むことで、各成分の役割が相まって上記効果を発揮する。
以下、各成分について詳述する。
A resin composition having excellent fluidity has the disadvantage of being prone to burrs, while being excellent in fluidity. In this embodiment, the (A) polyetherketone resin has a faster crystallization rate than PEEK (polyetheretherketone), and is therefore less likely to generate burrs during molding compared to PEEK. In addition, since the (A) polyetherketone resin has excellent sliding properties and contains (B) carbon fiber, (C) graphite, and (D) polytetrafluorotoluene in a predetermined ratio, a resin composition having excellent sliding properties and less burrs can be obtained. That is, by containing all of the (A) component to the (D) component in a predetermined ratio, the roles of each component work together to exert the above-mentioned effect.
Each component will be described in detail below.
［（Ａ）ポリエーテルケトン樹脂］
本実施形態のポリエーテルケトン樹脂組成物においては、ベース樹脂として（Ａ）ポリエーテルケトン樹脂を４０～８０質量％含有する。（Ａ）ポリエーテルケトン樹脂は、フェニルケトン構造と、フェニルエーテル構造とを主構造として有する樹脂である。ポリエーテルケトン樹脂は、耐熱性、機械強度、成形性等に優れ、ＰＥＥＫ（ポリエーテルエーテルケトン）よりも結晶化速度が速いため、成形時においてバリが発生しにくい。
[(A) Polyetherketone resin]
The polyetherketone resin composition of the present embodiment contains 40 to 80 mass% of (A) polyetherketone resin as a base resin. (A) Polyetherketone resin is a resin having a phenylketone structure and a phenylether structure as main structures. Polyetherketone resin is excellent in heat resistance, mechanical strength, moldability, etc., and has a faster crystallization rate than PEEK (polyetheretherketone), so that burrs are less likely to occur during molding.
本実施形態において、（Ａ）ポリエーテルケトン樹脂を４０～８０質量％含むが、４０質量％未満であると樹脂の連続層が相対的に少なくなり、摺動場のように繰り返し応力が掛かる状況において他の成分を保持する力が不足して脱落を起こし、摺動特性の向上が図れない。８０質量％を超えると摺動特性を向上させる他の成分の量を減らさざるを得ず、摺動特性の向上を図ることができない。（Ａ）ポリエーテルケトン樹脂の含有量は４２．５～７７．５質量％が好ましく、４５～７５質量％がより好ましく、４７．５～７２．５質量％がさらに好ましい。 In this embodiment, the polyether ketone resin (A) is contained at 40 to 80 mass %, but if it is less than 40 mass %, the continuous layer of the resin becomes relatively small, and in a situation where repeated stress is applied, such as in a sliding field, the force holding the other components is insufficient, causing them to fall off and preventing the improvement of sliding characteristics. If it exceeds 80 mass %, the amount of other components that improve the sliding characteristics must be reduced, and the sliding characteristics cannot be improved. The content of the polyether ketone resin (A) is preferably 42.5 to 77.5 mass %, more preferably 45 to 75 mass %, and even more preferably 47.5 to 72.5 mass %.
（Ａ）ポリエーテルケトン樹脂は、燃焼イオンクロマトグラフィによって測定されるフッ化物イオンの濃度が８０μｇ／ｇ以下であることが好ましく、６０μｇ／ｇ以下であることがより好ましく、４０μｇ／ｇであることがさらに好ましい。フッ化物イオンの濃度が８０μｇ／ｇ以下であることにより、溶融混練時等においてフッ酸の発生を減じることができる。
ここで、ポリエーテルケトン樹脂は、一般に、４，４’－ジフルオロベンゾフェノンと過剰量のビスフェノール化合物を反応させることにより得ることができる。あるいは、テレフタル酸ジクロライドとイソフタル酸ジクロライドとの混合物と、ジフェニルエーテルとをフッ化水素及びフッ化ホウ素の存在下に反応させることで得ることができる。しかし、そのような合成法であると、生成物にフッ素化合物が混入し、フッ酸の発生の原因となる。そこで、ポリエーテルケトン樹脂の合成は、特開２００９－２２７９６１号公報に記載の方法により行うことが好ましい。当該方法によると、合成過程においてフッ素を含む化合物を用いないため、生成物のフッ素化合物の混入を抑えることができる。すなわち、上記のように、燃焼イオンクロマトグラフィによって測定されるフッ化物イオンの濃度が８０μｇ／ｇ以下のポリエーテルケトン樹脂を得ることができる。
The polyether ketone resin (A) preferably has a fluoride ion concentration of 80 μg/g or less, more preferably 60 μg/g or less, and even more preferably 40 μg/g or less, as measured by combustion ion chromatography. By having a fluoride ion concentration of 80 μg/g or less, it is possible to reduce the generation of hydrofluoric acid during melt kneading, etc.
Here, the polyetherketone resin can generally be obtained by reacting 4,4'-difluorobenzophenone with an excess amount of a bisphenol compound. Alternatively, the polyetherketone resin can be obtained by reacting a mixture of terephthalic acid dichloride and isophthalic acid dichloride with diphenyl ether in the presence of hydrogen fluoride and boron fluoride. However, such a synthesis method causes fluorine compounds to be mixed into the product, which causes the generation of hydrofluoric acid. Therefore, it is preferable to synthesize the polyetherketone resin by the method described in JP 2009-227961 A. According to this method, since no compound containing fluorine is used in the synthesis process, it is possible to suppress the mixing of fluorine compounds into the product. That is, as described above, a polyetherketone resin can be obtained in which the concentration of fluoride ions measured by combustion ion chromatography is 80 μg/g or less.
（Ａ）ポリエーテルケトン樹脂は、キャピラリーレオメーターを使用し、シリンダー温度４００℃、剪断速度１０００／秒の条件で、ＩＳＯ１１４４３に準拠して測定される溶融粘度が１００～３００Ｐａ・ｓであることが好ましい。なお、溶融粘度を調整する方法は特に限定されないが、上記のポリエーテルケトン樹脂の合成の方法において、反応時間を制御することによって任意の溶融粘度に調整することができる。 (A) The polyether ketone resin preferably has a melt viscosity of 100 to 300 Pa·s, as measured in accordance with ISO 11443 using a capillary rheometer at a cylinder temperature of 400°C and a shear rate of 1000/sec. There are no particular limitations on the method for adjusting the melt viscosity, but the melt viscosity can be adjusted to any desired value by controlling the reaction time in the above method for synthesizing polyether ketone resin.
［（Ｂ）炭素繊維］
本実施形態のポリエーテルケトン樹脂組成物においては、（Ｂ）炭素繊維を５～３０質量％含有する。（Ｂ）炭素繊維は、摺動特性の向上に寄与する。
[(B) Carbon fiber]
The polyether ketone resin composition of the present embodiment contains 5 to 30 mass % of (B) carbon fiber. (B) Carbon fiber contributes to improving sliding properties.
（Ｂ）炭素繊維としては、原材料から分類されるピッチ系及びＰＡＮ系のいずれであってもよい。（Ｂ）炭素繊維は、高摺動性を有するピッチ系炭素繊維の方が好ましい。（Ｂ）炭素繊維の焼成温度は特に限定するものではないが、２０００℃またはそれ以上の高温で焼成されて黒鉛（グラファイト）化されたものであると、相手材を摩耗損傷しにくいので好ましい。 (B) Carbon fiber may be either pitch-based or PAN-based, as classified based on the raw material. Pitch-based carbon fiber, which has high sliding properties, is preferable as the (B) carbon fiber. There are no particular limitations on the firing temperature of the (B) carbon fiber, but it is preferable that the (B) carbon fiber is fired at a high temperature of 2000°C or higher to be graphitized, as this is less likely to cause wear and damage to the mating material.
本実施形態において、（Ｂ）炭素繊維は、例えば、繊維長が３～１０ｍｍであり、繊維径が２～１０μｍである炭素繊維原料を用いて、他の成分とともに溶融混練することにより得ることができる。 In this embodiment, (B) carbon fiber can be obtained by melt-kneading a carbon fiber raw material having, for example, a fiber length of 3 to 10 mm and a fiber diameter of 2 to 10 μm together with other components.
本実施形態において、（Ｂ）炭素繊維を５～３０質量％含むが、５質量％未満であると炭素繊維が持つ摺動特性を十分に発現せず、３０質量％を超えると炭素繊維同士の衝突により摩擦及び摩耗が増え、優れた摺動特性が得られなくなる。（Ｂ）炭素繊維の含有量は５～２７．５質量％が好ましく、７．５～２５質量％がより好ましく、７．５～２２．５質量％がさらに好ましい。 In this embodiment, (B) carbon fiber is contained at 5 to 30 mass %, but if it is less than 5 mass %, the sliding properties of the carbon fiber are not fully expressed, and if it exceeds 30 mass %, friction and wear increase due to collisions between the carbon fibers, making it impossible to obtain excellent sliding properties. The content of (B) carbon fiber is preferably 5 to 27.5 mass %, more preferably 7.5 to 25 mass %, and even more preferably 7.5 to 22.5 mass %.
［（Ｃ）黒鉛］
本実施形態のポリエーテルケトン樹脂組成物においては、（Ｃ）黒鉛を５～２５質量％含有する。（Ｃ）黒鉛は、摺動特性の向上に寄与する。
[(C) Graphite]
The polyether ketone resin composition of the present embodiment contains 5 to 25 mass % of (C) graphite. (C) Graphite contributes to improving the sliding properties.
（Ｃ）黒鉛としては、特に限定されず、鱗片状黒鉛、鱗状黒鉛、人造黒鉛、土状黒鉛、等があり、いずれも使用することができる。
（Ｃ）黒鉛のメディアン径（Ｄ５０）は、３０～８０μｍであることが好ましく、３５～７５μｍであることがより好ましく、４０～７０μｍであることがさらに好ましい。当該メディアン径が３０～８０μｍであると、摺動特性をより向上させることができる。
なお、メディアン径（Ｄ５０）は、レーザー回折散乱法によって求めた黒鉛の粒度分布において、体積積算が５０％での粒径（Ｄ５０）を意味する。
The graphite (C) is not particularly limited, and examples thereof include flake graphite, scaly graphite, artificial graphite, and amorphous graphite, and any of these can be used.
(C) The median diameter (D50) of graphite is preferably 30 to 80 μm, more preferably 35 to 75 μm, and even more preferably 40 to 70 μm. When the median diameter is 30 to 80 μm, the sliding characteristics can be further improved.
The median diameter (D50) means the particle diameter (D50) at 50% volume accumulation in the particle size distribution of graphite determined by a laser diffraction scattering method.
本実施形態において、（Ｃ）黒鉛を５～２５質量％含むが、５質量％未満であると黒鉛が持つ摺動特性を十分に発現せず、２５質量％を超えると黒鉛の脱落が過剰となり優れた摺動特性が得られなくなる。（Ｃ）黒鉛の含有量は５～２２．５質量％が好ましく、７．５～２２．５質量％がより好ましい。 In this embodiment, (C) graphite is contained at 5 to 25 mass%, but if it is less than 5 mass%, the sliding properties of the graphite are not fully expressed, and if it exceeds 25 mass%, excessive graphite falls off and excellent sliding properties cannot be obtained. The content of (C) graphite is preferably 5 to 22.5 mass%, and more preferably 7.5 to 22.5 mass%.
［（Ｄ）ポリテトラフルオロエチレン］
本実施形態のポリエーテルケトン樹脂組成物においては、（Ｄ）ポリテトラフルオロエチレンを５～２５質量％含有する。（Ｄ）ポリテトラフルオロエチレンを含有させることにより摺動特性を付与することができる。
[(D) Polytetrafluoroethylene]
The polyether ketone resin composition of the present embodiment contains 5 to 25 mass % of polytetrafluoroethylene (D). By including polytetrafluoroethylene (D), it is possible to impart sliding properties.
本実施形態においては、（Ｄ）ポリテトラフルオロエチレンは、空気気流下、昇温速度１０℃／分で３０℃から４００℃まで加熱したときの重量減少率が０．５質量％以下であることが好ましい。当該重量減少率が０．５質量％以下であると耐熱性が高く、フッ酸の発生を抑制することができる。当該重量減少率は０～０．３質量％がより好ましく、０～０．１質量％がさらに好ましい。 In this embodiment, it is preferable that the weight loss rate of (D) polytetrafluoroethylene is 0.5% by mass or less when heated from 30°C to 400°C at a temperature increase rate of 10°C/min in an air flow. If the weight loss rate is 0.5% by mass or less, the heat resistance is high and the generation of hydrofluoric acid can be suppressed. The weight loss rate is more preferably 0 to 0.3% by mass, and even more preferably 0 to 0.1% by mass.
本実施形態において、（Ｄ）ポリテトラフルオロエチレンを５～２５質量％含むが、５質量％未満であるとポリテトラフルオロエチレンが持つ摺動特性を十分に発現せず、２５質量％を超えるとポリテトラフルオロエチレンの脱落が過剰となり優れた摺動特性が得られなくなる。（Ｄ）ポリテトラフルオロエチレンの含有量は５～２２．５質量％が好ましく、７．５～２２．５質量％がより好ましい。 In this embodiment, (D) polytetrafluoroethylene is contained at 5 to 25 mass%, but if it is less than 5 mass%, the sliding properties of polytetrafluoroethylene are not fully expressed, and if it exceeds 25 mass%, excessive loss of polytetrafluoroethylene occurs and excellent sliding properties cannot be obtained. The content of (D) polytetrafluoroethylene is preferably 5 to 22.5 mass%, and more preferably 7.5 to 22.5 mass%.
［他の成分］
本実施形態においては、必要に応じて、熱可塑性樹脂に対する一般的な添加剤、例えば、滑剤、離型剤、帯電防止剤、界面活性剤、難燃剤、又は、有機高分子材料、無機若しくは有機の粉体状、板状の充填材等を１種又は２種以上添加することができる。
[Other ingredients]
In the present embodiment, if necessary, one or more types of general additives for thermoplastic resins, such as a lubricant, a release agent, an antistatic agent, a surfactant, a flame retardant, an organic polymer material, or an inorganic or organic powder-like or plate-like filler, may be added.
以上の本実施形態のポリエーテルケトン樹脂組成物は、摺動特性に優れることから、摺動部材用として好適である。当該摺動部材としては、後記の成形品について説明する。 The polyether ketone resin composition of this embodiment has excellent sliding properties and is therefore suitable for use as a sliding member. The molded product described below will be used as an example of such a sliding member.
＜成形品＞
本実施形態の成形品は、以上説明した本実施形態のポリエーテルケトン樹脂組成物を含む。従って、摺動特性に優れ、バリの発生が少ないという効果を奏する。
<Molded products>
The molded article of the present embodiment contains the polyether ketone resin composition of the present embodiment described above, and therefore has the effects of excellent sliding properties and reduced burr generation.
本実施形態の成形品を作製する方法としては特に限定はなく、公知の方法を採用することができる。例えば、本実施形態のポリエーテルケトン樹脂組成物を押出機に投入して溶融混練してペレット化し、このペレットを所定の金型を装備した射出成形機に投入し、射出成形することで作製することができる。 The method for producing the molded product of this embodiment is not particularly limited, and any known method can be used. For example, the polyether ketone resin composition of this embodiment can be fed into an extruder, melt-kneaded and pelletized, and the pellets can be fed into an injection molding machine equipped with a specified mold and injection molded to produce the molded product.
本実施形態の成形品としては、摺動特性に優れることから、摺動部材として好適に用いることができる。当該摺動部材としては、一例として、エンジン、モーター、ブレーキ、トランスミッション、クラッチ及びダンパー等の部品において、ギア、スラスト、ベアリング軸受け、シールリングなどの形態で使用することができる。 The molded product of this embodiment has excellent sliding properties and can be suitably used as a sliding member. Examples of such sliding members include gears, thrust bearings, bearings, seal rings, etc. in parts such as engines, motors, brakes, transmissions, clutches, and dampers.
以下に、実施例により本実施形態をさらに具体的に説明するが、本実施形態は以下の実施例に限定されるものではない。 The present embodiment will be explained in more detail below using examples, but the present embodiment is not limited to the following examples.
［実施例１～１０、比較例１～１１］
各実施例・比較例において、表１～２に示す各原料成分を表１～２に示す割合で二軸押出機（（株）コペリオン製「ＺＳＫ２６ＭＥＧＡｃｏｍｐｏｕｎｄｅｒ」）を用いて、以下の押出条件で溶融混練し、ポリエーテルケトン樹脂組成物のペレットを得た。
（押出条件）
シリンダー温度：
４００℃（実施例１～１０、比較例１～７）
３８０℃（比較例８～１１）
スクリュー回転数：２００ｒｐｍ
[Examples 1 to 10, Comparative Examples 1 to 11]
In each of the Examples and Comparative Examples, the raw material components shown in Tables 1 and 2 were melt-kneaded in the ratios shown in Tables 1 and 2 using a twin-screw extruder ("ZSK26MEGA compounder" manufactured by Coperion Co., Ltd.) under the following extrusion conditions to obtain pellets of a polyether ketone resin composition.
(Extrusion conditions)
Cylinder Temperature:
400°C (Examples 1 to 10, Comparative Examples 1 to 7)
380°C (Comparative Examples 8 to 11)
Screw rotation speed: 200 rpm
使用した各原料成分の詳細を以下に示す。
（Ａ）ポリエーテルケトン樹脂
・ＰＥＫ１：特開２００９－２２７９６１号公報に記載の製造方法により製造したポリエーテルケトン樹脂（溶融粘度：２２０Ｐａ・ｓ、フッ化物イオン：不検出）
・ＰＥＫ２：Ｖｉｃｔｒｅｘ製、ＰＥＫ、Ｇ２２（溶融粘度：１９０Ｐａ・ｓ、フッ化物イオン：７５９μｇ／ｇ）
（Ａ’）ポリエーテルエーテルケトン樹脂
・ＰＥＥＫ：Ｖｉｃｔｒｅｘ製、ＰＥＥＫ、４５０Ｇ（溶融粘度：４００Ｐａ・ｓ）
（Ｂ）炭素繊維
・ＣＦ：ＳＧＬ Ｃａｒｂｏｎ Ｆｉｂｅｒｓ製、炭素繊維、ＳＩＧＲＡＦＩＬ（登録商標）Ｃ Ｃ６－４．０／２４０－Ｔ１９０（チョップドストランド、繊維長：６ｍｍ、繊維径：７μｍ）
（Ｃ）黒鉛
・ＧＰ１：富士黒鉛工業（株）製、人造黒鉛、Ｇ７０（メディアン径（Ｄ５０）：６６μｍ）
・ＧＰ２：富士黒鉛工業（株）製、鱗片状黒鉛、－１９９．５（メディアン径（Ｄ５０）：５７μｍ）
・ＧＰ３：富士黒鉛工業（株）製、人造黒鉛、Ｇ－４Ａ（メディアン径（Ｄ５０）：４μｍ）
（Ｄ）ポリテトラフルオロエチレン
・ＰＴＦＥ１：（株）喜多村製、ＰＴＦＥ、ＫＴ－６００Ｍ（重量減少率：０質量％）
・ＰＴＦＥ２：（株）喜多村製、ＰＴＦＥ、ＫＴＬ－６１０（重量減少率：０．９質量％）
Details of each raw material component used are shown below.
(A) Polyetherketone resin PEK1: Polyetherketone resin produced by the production method described in JP 2009-227961 A (melt viscosity: 220 Pa s, fluoride ion: not detected)
PEK2: Victrex, PEK, G22 (melt viscosity: 190 Pa s, fluoride ion: 759 μg / g)
(A') Polyether ether ketone resin PEEK: Victrex, PEEK, 450G (melt viscosity: 400 Pa s)
(B) Carbon fiber CF: SGL Carbon Fibers, carbon fiber, SIGRAFIL (registered trademark) C C6-4.0 / 240-T190 (chopped strand, fiber length: 6 mm, fiber diameter: 7 μm)
(C) Graphite GP1: Fuji Graphite Industry Co., Ltd., artificial graphite, G70 (median diameter (D50): 66 μm)
GP2: Fuji Graphite Industry Co., Ltd., flake graphite, -199.5 (median diameter (D50): 57 μm)
GP3: Fuji Graphite Industry Co., Ltd., artificial graphite, G-4A (median diameter (D50): 4 μm)
(D) Polytetrafluoroethylene PTFE1: Kitamura Co., Ltd., PTFE, KT-600M (weight loss rate: 0% by mass)
PTFE2: Kitamura Co., Ltd., PTFE, KTL-610 (weight reduction rate: 0.9% by mass)
＜原料成分の評価＞
（１）溶融粘度
キャピラリーレオメーター（（株）東洋精機製作所製「キャピログラフ１Ｄ」）を使用し、以下の条件で、内径２ｍｍ、長さ６０ｍｍのオリフィスを用いて、ＩＳＯ１１４４３に準拠して、ポリエーテルケトン樹脂及びポリエーテルエーテルケトン樹脂の溶融粘度を測定した。
（測定条件）
シリンダー温度：
４００℃（ＰＥＫ１、ＰＥＫ２）
３８０℃（ＰＥＥＫ）
剪断速度：１０００／秒
滞留時間：１０分
（２）フッ化物イオンの濃度
燃焼イオンクロマトグラフィによって、以下の条件で、ポリエーテルケトン樹脂及びポリエーテルエーテルケトン樹脂のフッ化物イオンの濃度を測定した。
（測定条件）
イオンクロマトグラフ：サーモフィッシャーサイエンティフィック製「ＩＣＳ１６００」
燃焼用前処理装置：（株）三菱ケミカルアナリテック製「ＡＱＦ－１００」
試料：５０ｍｇ
ヒーター：Ｉｎｌｅｔ Ｔｅｍｐ／９００℃、Ｏｕｔｌｅｔ Ｔｅｍｐ／１０００℃
吸収液：Ｈ２Ｏ２９００ｐｐｍ、内標準：ＰＯ４
３－ ２５ｐｐｍ
（３）重量減少率
示差熱熱重量同時測定装置（ＴＧ／ＤＴＡ、セイコーインスツル（株）製）を使用し、空気気流下、昇温速度１０℃／分で３０℃から４００℃まで加熱したときのポリテトラフルオロエチレンの重量減少率を測定した。
<Evaluation of raw material ingredients>
(1) Melt Viscosity The melt viscosity of polyether ketone resins and polyether ether ketone resins was measured using a capillary rheometer ("Capilograph 1D" manufactured by Toyo Seiki Seisakusho, Ltd.) under the following conditions in accordance with ISO 11443 using an orifice having an inner diameter of 2 mm and a length of 60 mm.
(Measurement conditions)
Cylinder Temperature:
400℃ (PEK1, PEK2)
380℃ (PEEK)
Shear rate: 1000/sec Residence time: 10 minutes (2) Fluoride ion concentration The fluoride ion concentrations of the polyether ketone resin and the polyether ether ketone resin were measured by combustion ion chromatography under the following conditions.
(Measurement conditions)
Ion chromatograph: Thermo Fisher Scientific "ICS1600"
Combustion pretreatment device: "AQF-100" manufactured by Mitsubishi Chemical Analytech Co., Ltd.
Sample: 50 mg
Heater: Input Temp/900°C, Output Temp/1000°C
Absorption solution: H 2 O 2 900 ppm, internal standard: PO 4 3- 25 ppm
(3) Weight Loss Rate The weight loss rate of polytetrafluoroethylene was measured when it was heated from 30° C. to 400° C. at a temperature increase rate of 10° C./min in an air flow using a thermogravimetric and differential thermal analyzer (TG/DTA, manufactured by Seiko Instruments Inc.).
＜樹脂組成物の評価＞
（１）フッ酸の発生量
押出機ダイの溶融樹脂出口から３０ｃｍ上部にて、気体採取器（（株）ガステック製「ＧＶ－１００型」）及びフッ酸検知管（（株）ガステック製「１７ＬＬ」）を使用し、溶融樹脂周辺のフッ酸の濃度を測定した。測定結果を表１及び表２に示す。なお、フッ酸の発生量３ｐｐｍ未満が「良」、３～１０ｐｐｍが「可」、１０ｐｐｍ超が「不可」である。
（２）摩擦係数
得られた実施例及び比較例のペレットを、成形機（ファナック（株）製「α－Ｓ１００ｉＡ」）を用いて、以下の成形条件で成形し、８０ｍｍ×８０ｍｍ×３ｍｍの平板状試験片を得た。得られた平板状試験片とＳＵＳ３０４製の円筒状試験片を用いて、摩擦摩耗試験機（（株）オリエンテック製「ＥＦＭ－ＩＩＩ－ＥＮ」）を使用し、以下の条件で、摩擦係数を測定した。測定結果を表１及び表２に示す。なお、摩擦係数が０．２５未満の場合が「良」であり、０．２５～０．３０の場合が「可」であり、０．３０超の場合が「不可」である。
（成形条件）
シリンダー温度：
４００℃（実施例１～１０、比較例１～７）
３８０℃（比較例８～１１）
金型温度：２００℃
射出速度：２０ｍｍ／ｓｅｃ
保圧：１２０ＭＰａ
（測定条件）
形態：スラスト
面圧：０．４９ＭＰａ
回転速度：３０ｃｍ／ｓ
時間：８時間
（３）比摩耗量
摩擦係数と同様にして、比摩耗量を測定した。測定結果を表１及び表２に示す。なお、比摩耗量が３．０×１０－３（ｍｍ３／（Ｎ・ｋｍ））未満の場合が「良」であり、３．０×１０－３～５．０×１０－３（ｍｍ３／（Ｎ・ｋｍ））の場合が「可」であり、５．０×１０－３（ｍｍ３／（Ｎ・ｋｍ））超の場合が「不可」である。
（４）バリ発生の有無
得られた実施例及び比較例のペレットを、射出成形機（ファナック（株）製「α－Ｓ１００ｉＡ」）を用いて、以下の成形条件で成形し、８０ｍｍ×８０ｍｍ×３ｍｍの平板状試験片を得た。得られた平板状試験片についてバリ発生の有無を目視観察した。バリが発生しなかった場合を「無」とし、バリが発生した場合を「有」として評価した。評価結果を表１及び表２に示す。なお、バリの発生「無」の場合が「良」であり、「有」の場合が「不可」である。
（成形条件）
シリンダー温度：
４００℃（実施例１～１０、比較例１～７）
３８０℃（比較例８～１１）
金型温度：２００℃
射出速度：２０ｍｍ／ｓｅｃ
保圧：１２０ＭＰａ
（５）総合評価
上記（１）～（４）の評価において、良：２、可：１、不可：－１と点数を付けたときにそれぞれの点数の合計が、７以上の場合をＡ、５～６の場合をＢ、２～４の場合をＣ、１以下の場合をＤとして評価した。
<Evaluation of Resin Composition>
(1) Amount of hydrofluoric acid generated The concentration of hydrofluoric acid around the molten resin was measured 30 cm above the molten resin outlet of the extruder die using a gas extractor (GV-100 type, manufactured by Gastec Corp.) and a hydrofluoric acid detector tube (17LL, manufactured by Gastec Corp.). The measurement results are shown in Tables 1 and 2. Amount of hydrofluoric acid generated of less than 3 ppm was rated as "good", 3 to 10 ppm as "passable", and more than 10 ppm as "unacceptable".
(2) Friction Coefficient The obtained pellets of the Examples and Comparative Examples were molded under the following molding conditions using a molding machine ("α-S100iA" manufactured by Fanuc Corporation) to obtain flat test pieces of 80 mm x 80 mm x 3 mm. Using the obtained flat test pieces and cylindrical test pieces made of SUS304, the friction coefficients were measured under the following conditions using a friction and wear tester ("EFM-III-EN" manufactured by Orientec Co., Ltd.). The measurement results are shown in Tables 1 and 2. A friction coefficient of less than 0.25 was "good", a coefficient of friction of 0.25 to 0.30 was "passable", and a coefficient of friction of more than 0.30 was "unacceptable".
(Molding conditions)
Cylinder Temperature:
400°C (Examples 1 to 10, Comparative Examples 1 to 7)
380°C (Comparative Examples 8 to 11)
Mold temperature: 200°C
Injection speed: 20mm/sec
Holding pressure: 120MPa
(Measurement conditions)
Form: Thrust Surface pressure: 0.49 MPa
Rotation speed: 30cm/s
Time: 8 hours (3) Specific wear rate The specific wear rate was measured in the same manner as the friction coefficient. The measurement results are shown in Tables 1 and 2. A specific wear rate of less than 3.0×10 -3 (mm 3 /(N-km)) was rated "good", a rate of 3.0×10 -3 to 5.0×10 -3 (mm 3 /(N-km)) was rated "passable", and a rate of more than 5.0×10 -3 (mm 3 /(N-km)) was rated "unacceptable".
(4) Presence or absence of burrs The obtained pellets of the examples and comparative examples were molded under the following molding conditions using an injection molding machine ("α-S100iA" manufactured by Fanuc Corporation) to obtain flat test pieces of 80 mm x 80 mm x 3 mm. The obtained flat test pieces were visually observed for the presence or absence of burrs. Cases where no burrs were generated were rated as "absent", and cases where burrs were generated were rated as "present". The evaluation results are shown in Tables 1 and 2. Note that cases where there were no burrs were rated as "good", and cases where there were burrs were rated as "not acceptable".
(Molding conditions)
Cylinder Temperature:
400°C (Examples 1 to 10, Comparative Examples 1 to 7)
380°C (Comparative Examples 8 to 11)
Mold temperature: 200°C
Injection speed: 20mm/sec
Holding pressure: 120MPa
(5) Overall Evaluation In the evaluation of (1) to (4) above, scores were assigned as follows: good: 2, fair: 1, and poor: -1. When the total of the scores was 7 or more, it was evaluated as A, when it was 5 to 6, when it was 2 to 4, it was evaluated as C, and when it was 1 or less, it was evaluated as D.
表１、２より、実施例１～１０においては、フッ酸発生量、摩耗係数、比摩耗量、及びバリの有無の評価において、いずれの評価結果も良好であった。これに対して、比較例１～１１は少なくとも１つの評価が不良であった。特に、比較例１～７を見ると、（Ｂ）炭素繊維、（Ｃ）黒鉛及び（Ｄ）ポリテトラフルオロエチレンのすべてを本実施形態において規定する通りに含まないと摺動特性に劣ることが分かる。 As can be seen from Tables 1 and 2, in Examples 1 to 10, the evaluation results for the amount of hydrofluoric acid generated, the wear coefficient, the specific wear rate, and the presence or absence of burrs were all good. In contrast, in Comparative Examples 1 to 11, at least one evaluation was bad. In particular, looking at Comparative Examples 1 to 7, it can be seen that the sliding properties are inferior unless all of (B) carbon fiber, (C) graphite, and (D) polytetrafluoroethylene are contained as specified in this embodiment.
Claims (7)
（Ｂ）炭素繊維を５～３０質量％、
（Ｃ）黒鉛を５～２５質量％、及び
（Ｄ）ポリテトラフルオロエチレンを５～２５質量％含有する、ポリエーテルケトン樹脂組成物。 (A) 40 to 80% by mass of a polyether ketone resin,
(B) 5 to 30 mass% carbon fiber,
(C) a polyether ketone resin composition containing 5 to 25 mass% of graphite, and (D) 5 to 25 mass% of polytetrafluoroethylene.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006266102A (en) * | 2005-03-22 | 2006-10-05 | Ntn Corp | Swash plate compressor and swash plate for same |
| JP2012077764A (en) * | 2010-09-30 | 2012-04-19 | Ntn Corp | Composite slide bearing |
| US20150080502A1 (en) * | 2012-03-30 | 2015-03-19 | Keki Hormusji Gharda | Polymeric blend |
| CN108752863A (en) * | 2018-05-07 | 2018-11-06 | 陈丽川 | A kind of composite modified polyetheretherketonematerials materials and its preparation method and application |
| CN111875924A (en) * | 2019-04-15 | 2020-11-03 | 上海普聚塑料科技有限公司 | Injection molding product and preparation raw material and method thereof |
| JP2023178194A (en) * | 2022-06-03 | 2023-12-14 | Ntn株式会社 | Sealing resin composition and seal |
| JP2024091169A (en) * | 2022-12-23 | 2024-07-04 | Ntn株式会社 | piston ring |
-
2024
- 2024-09-05 WO PCT/JP2024/031850 patent/WO2025063049A1/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006266102A (en) * | 2005-03-22 | 2006-10-05 | Ntn Corp | Swash plate compressor and swash plate for same |
| JP2012077764A (en) * | 2010-09-30 | 2012-04-19 | Ntn Corp | Composite slide bearing |
| US20150080502A1 (en) * | 2012-03-30 | 2015-03-19 | Keki Hormusji Gharda | Polymeric blend |
| CN108752863A (en) * | 2018-05-07 | 2018-11-06 | 陈丽川 | A kind of composite modified polyetheretherketonematerials materials and its preparation method and application |
| CN111875924A (en) * | 2019-04-15 | 2020-11-03 | 上海普聚塑料科技有限公司 | Injection molding product and preparation raw material and method thereof |
| JP2023178194A (en) * | 2022-06-03 | 2023-12-14 | Ntn株式会社 | Sealing resin composition and seal |
| JP2024091169A (en) * | 2022-12-23 | 2024-07-04 | Ntn株式会社 | piston ring |
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