WO2024203652A1 - Corps moulé de polyéther cétone aromatique et son procédé de production - Google Patents

Corps moulé de polyéther cétone aromatique et son procédé de production Download PDF

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Publication number
WO2024203652A1
WO2024203652A1 PCT/JP2024/010842 JP2024010842W WO2024203652A1 WO 2024203652 A1 WO2024203652 A1 WO 2024203652A1 JP 2024010842 W JP2024010842 W JP 2024010842W WO 2024203652 A1 WO2024203652 A1 WO 2024203652A1
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WO
WIPO (PCT)
Prior art keywords
polyether ketone
aromatic polyether
matrix phase
molded article
examples
Prior art date
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PCT/JP2024/010842
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English (en)
Japanese (ja)
Inventor
岳史 眞壁
愼 池田
太一 赤岡
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株式会社リケン
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Publication of WO2024203652A1 publication Critical patent/WO2024203652A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • 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
    • 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 an aromatic polyether ketone molded article that can be used for various parts.
  • Patent Document 1 discloses a technology for improving the mechanical strength of resin molded bodies. With this technology, the mechanical strength of resin molded bodies can be improved by increasing the crystallinity of the resin component and restricting the degree of freedom of molecular movement.
  • Sliding components such as gears are examples of parts that are being sought after to replace metal components with resin molded bodies.
  • sliding components it is advantageous for them to have high mechanical strength as well as high elongation in order to improve durability.
  • the present invention aims to provide an aromatic polyether ketone molded body that combines high mechanical strength and large elongation.
  • an aromatic polyether ketone molded article includes a matrix phase and a dispersed phase dispersed in the matrix phase.
  • the matrix phase is composed of aromatic polyetherketone and has a crystallite size greater than 63 ⁇ .
  • the dispersed phase is composed of at least one of carbon black and carbon nanotubes.
  • the matrix phase is composed of aromatic polyetherketone, which provides high mechanical strength.
  • the crystallite size of the matrix phase is large, which provides high elongation. In other words, this aromatic polyetherketone molded body can achieve both high mechanical strength and high elongation.
  • the aromatic polyether ketone constituting the matrix phase may have a molecular weight distribution with a maximum peak molecular weight in the range of 50,000 or more.
  • the dispersed phase may be composed of carbon black, and the area ratio of the region occupied by the dispersed phase having a particle size of 0.1 ⁇ m or more may be 0.6% or more.
  • the dispersed phase may be composed of carbon nanotubes, and the area ratio of the region occupied by the dispersed phase having a particle diameter of 0.1 ⁇ m or more may be 1.9% or more.
  • the matrix phase may be composed of polyether ether ketone.
  • the aromatic polyether ketone molded article may be configured as a sliding member.
  • the aromatic polyether ketone molded article may be configured as a gear member.
  • a molded article is produced by injection molding, in which a dispersed phase composed of at least one of carbon black and carbon nanotubes is dispersed in a matrix phase composed of aromatic polyether ketone having a molecular weight distribution with a maximum peak molecular weight in the range of 50,000 or more.
  • the molded body is annealed at a temperature higher than the intermediate temperature between the melting point and the glass transition point of the matrix phase and lower than the melting point of the matrix phase.
  • the present invention can provide an aromatic polyether ketone molded body that combines high mechanical strength and large elongation.
  • FIG. 1 is a flowchart showing a method for producing a resin molded body according to an embodiment of the present invention.
  • FIG. 11 is a plan view showing an example in which the resin molded body is configured as a gear member.
  • the present invention relates to an aromatic polyetherketone molded article, which is a resin molded article formed mainly from aromatic polyetherketone. More specifically, the resin molded article according to this embodiment includes a matrix phase made of aromatic polyetherketone and a dispersed phase made of carbon powder and dispersed in the matrix phase. The carbon powder constituting the dispersed phase is made of at least one of carbon black and carbon nanotubes.
  • the aromatic polyether ketone constituting the matrix phase is a resin composed of a benzene ring, an ether, and a ketone.
  • PEEK polyether ether ketone
  • the aromatic polyether ketone constituting the matrix phase has a large molecular weight, specifically, that it has a molecular weight distribution in which the maximum peak molecular weight is in the range of 50,000 or more.
  • the long molecular chains bind each other, resulting in high mechanical strength.
  • the crystallite size of the aromatic polyether ketone in the matrix phase is large, specifically, greater than 63 ⁇ .
  • the molecular chains that make up each crystallite are less likely to break, and large elongation can be obtained.
  • the matrix phase is composed of long molecular chains, and the crystallite size in the matrix phase is large, so that it is possible to achieve both high mechanical strength and large elongation.
  • the resin molded body according to this embodiment has high durability when used in applications such as sliding members.
  • gel permeation chromatography can be used to measure the molecular weight distribution of the aromatic polyether ketone that constitutes the matrix phase.
  • the maximum peak molecular weight refers to the molecular weight that corresponds to the number of molecules (frequency) that forms a peak value in the molecular weight distribution curve obtained by molecular weight measurement.
  • the crystallite size of the matrix phase can be measured using a diffraction pattern obtained by X-ray diffraction (XRD).
  • XRD X-ray diffraction
  • the crystallite size of the matrix phase needs to be greater than 63 ⁇ , and no disadvantages due to it being too large have been identified at this stage, but it is believed that there is a limit to how much mechanical strength can be improved by increasing the crystallite size of the matrix phase. From this perspective, the upper limit for the crystallite size of the matrix phase is assumed to be, for example, 250 ⁇ .
  • FIG. 1 is a flowchart showing the method for producing a resin molded body according to this embodiment.
  • step S01 raw materials are prepared.
  • the raw materials prepared in step S01 are prepared, for example, as a kneaded mixture of aromatic polyether ketone, which constitutes the matrix phase, and carbon powder, which constitutes the dispersed phase.
  • step S01 aromatic polyether ketone having a molecular weight distribution with a maximum peak molecular weight in the range of 50,000 or more is used. Also, in step S01, carbon powder having an appropriate particle size distribution can be used to obtain the effect described in step S03 below.
  • the raw material mixture can be obtained, for example, by kneading aromatic polyether ketone and carbon powder using a single-screw extruder or a twin-screw extruder.
  • the raw material mixture can also be prepared as a commercially available product in which aromatic polyether ketone and carbon powder are kneaded in advance.
  • step S02 the raw material prepared in step S01 is molded into a shape appropriate for the intended use.
  • the raw material can be molded using injection molding.
  • a dispersed phase made of carbon powder is dispersed in a matrix phase made of aromatic polyether ketone.
  • step S02 the grain growth of crystallites is difficult to proceed in the matrix phase with a large molecular weight, so it is difficult to obtain a large crystallite size in the matrix phase in the raw material compact obtained in step S02. For this reason, in this embodiment, step S03 is performed to increase the crystallite size of the matrix phase.
  • step S03 the raw material compact obtained in step S02 is annealed.
  • the holding temperature for the annealing in step S03 is generally higher than the temperature set in an annealing process aimed at relieving residual stress, specifically, a temperature higher than the midpoint between the melting point and the glass transition point of the matrix phase and lower than the melting point of the matrix phase.
  • step S03 the dispersion of carbon powder and the annealing treatment at a high temperature close to the melting point of the matrix phase work together to promote grain growth of crystallites in the matrix phase with a large molecular weight.
  • step S03 a resin molded body with a large crystallite size in the matrix phase is obtained.
  • the effect of promoting grain growth by becoming the nuclei of crystallites in the dispersed phase is believed to be obtained regardless of the size of the dispersed phase, but is more effective when the dispersed phase is made relatively large.
  • the area ratio of the region occupied by the dispersed phase having a particle size of 0.1 ⁇ m or more is 0.6% or more.
  • the area ratio of the region occupied by the dispersed phase having a particle size of 0.1 ⁇ m or more is 1.9% or more.
  • the area ratio of the region occupied by the dispersed phase having a particle size of 0.1 ⁇ m or more is preferably 20% or less, and more preferably 10% or less.
  • the area ratio of the dispersed phase of the resin molded body can be determined from a photograph of the resin molded body taken with a fluorescent microscope.
  • the annealing treatment of the raw material compact in step S03 can be performed using a known heating method, such as hot air heating, far-infrared heating, or near-infrared heating.
  • the annealing treatment of the raw material compact is typically performed in the atmosphere, but can also be performed in a low oxygen partial pressure or in an inert gas, for example.
  • the resin molded body according to this embodiment is particularly suitable for application to parts where stress is likely to concentrate locally.
  • Examples of such parts include sliding members such as gear members, seal rings, thrust washers, and bearings.
  • the resin molded body according to this embodiment configured as a sliding member has high durability.
  • a gear member is shown as an example of an application of the resin molded body according to this embodiment as a sliding member.
  • stress tends to concentrate at the base of the teeth T that are arranged in series along the outer periphery, but by configuring it as the resin molded body according to this embodiment, it is possible to effectively prevent chipping of the teeth T.
  • Example 1 to 4 and Comparative Examples 1 and 2 samples of resin molded bodies were prepared and each sample was evaluated. In all of Examples 1 to 4 and Comparative Example 2, carbon black was used as the carbon powder constituting the dispersed phase. Comparative Example 1 differs from the above embodiment in that no dispersed phase was used and no annealing treatment was performed. Comparative Example 2 differs from the above embodiment in that no annealing treatment was performed.
  • a common aromatic polyether ketone was used in both Examples 1 to 4 and Comparative Examples 1 and 2.
  • the aromatic polyether ketone used in both Examples 1 to 4 and Comparative Examples 1 and 2 was the polyether ether ketone "Vestakeep (registered trademark) 5000G" manufactured by Polypla Evonik.
  • Table 1 shows the holding temperature and holding time of the annealing treatment in Examples 1 to 4.
  • Table 1 also shows the area ratio of the region occupied by the dispersed phase with a particle size of 0.1 ⁇ m or more in the samples in Examples 1 to 4 and Comparative Examples 1 and 2, and the crystallite size of the matrix phase of the samples.
  • the area ratio of the dispersed phase for each sample was determined from photographs of each sample taken with an Olympus BX53M fluorescent microscope.
  • the crystallite size of the matrix phase for each sample was determined from the diffraction pattern of each sample obtained by measurement with a Rigaku Samartlab X-ray diffraction device.
  • a tensile test was conducted on each sample of Examples 1 to 4 and Comparative Examples 1 and 2 to evaluate the fracture properties.
  • Shimadzu Corporation's "AGX" was used for the tensile test.
  • each sample was cut into an A12 dumbbell shape conforming to JIS K7139 (2009), the tensile speed was 10 mm/min, and other conditions were the same.
  • Table 2 shows the yield strength, yield stroke, and tensile product for Examples 1 to 4 and Comparative Examples 1 and 2 as percentage changes compared to Comparative Example 1.
  • the yield strength and yield stroke were obtained from the stress-strain curve obtained in the tensile test, and the tensile product was calculated from the yield strength and yield stroke.
  • Table 2 shows the results of the gear durability test for Examples 1 to 4 and Comparative Examples 1 and 2. None of the samples relating to Examples 1 to 4 experienced chipped teeth, whereas all of the samples relating to Comparative Examples 1 and 2 experienced chipped teeth. This shows that Examples 1 to 4 provide high product characteristics as gear components.
  • Examples 5 to 7 In Examples 5 to 7, samples of resin molded bodies were prepared and each sample was evaluated. In all of Examples 5 to 7, carbon nanotubes were used as the carbon powder constituting the dispersed phase. In all of Examples 5 to 7, aromatic polyether ketone was used in common with Examples 1 to 4 and Comparative Examples 1 and 2.
  • Table 3 shows the holding temperature and holding time of the annealing treatment in Examples 5 to 7.
  • Table 3 also shows the area ratio of the region occupied by the dispersed phase with a particle size of 0.1 ⁇ m or more in the samples in Examples 5 to 7 and Comparative Example 1, and the crystallite size of the matrix phase of the samples.
  • the area ratio of the dispersed phase and the crystallite size of the matrix phase in each sample were determined using the same method as in Examples 1 to 4 and Comparative Examples 1 and 2.
  • Example 6 in which the area ratio of the dispersed phase was large, a significantly larger crystallite size was obtained. This confirmed that the effect of promoting grain growth of crystallites was obtained by having a large amount of carbon nanotubes with high thermal conductivity.
  • Example 6 which had a large area ratio of the dispersed phase, both the yield strength and yield stroke were the largest. This confirmed that a large tensile product can be obtained by increasing the crystallite size of the matrix phase.
  • the molecular weight of the aromatic polyether ketone constituting the matrix phase is not particularly limited as long as sufficient mechanical strength is obtained depending on the application.
  • the aromatic polyether ketone constituting the matrix phase may have a maximum peak molecular weight in any range in the molecular weight distribution.
  • the aromatic polyetherketone constituting the matrix phase of the resin molded article of the present invention may be other than polyetheretherketone (PEEK), and may be, for example, polyetherketone (PEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), polyetherketoneetherketoneketone (PEKEKK), etc.
  • the matrix phase of the resin molded article of the present invention may be a blend of multiple types of aromatic polyetherketones.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Gears, Cams (AREA)

Abstract

Ce corps moulé de polyéther cétone aromatique comprend une phase de matrice et des phases de dispersion qui sont dispersées dans la phase de matrice. La phase de matrice est composée d'une polyéther cétone aromatique et a une dimension de cristallite supérieure à 63Å. Les phases de dispersion sont composées d'au moins l'un parmi le noir de carbone et les nanotubes de carbone.
PCT/JP2024/010842 2023-03-27 2024-03-19 Corps moulé de polyéther cétone aromatique et son procédé de production WO2024203652A1 (fr)

Applications Claiming Priority (2)

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JP2023-049519 2023-03-27
JP2023049519A JP2024138820A (ja) 2023-03-27 2023-03-27 芳香族ポリエーテルケトン成形体、及びその製造方法

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04101827A (ja) * 1990-08-21 1992-04-03 Mitsui Toatsu Chem Inc 二軸延伸ポリエーテルエーテルケトンフィルムの製造方法
JPH05172212A (ja) * 1991-05-27 1993-07-09 Sutaaraito Kogyo Kk 歯車成形品
JPH0940864A (ja) * 1995-07-26 1997-02-10 Mitsui Toatsu Chem Inc 樹脂組成物
JPH10274897A (ja) * 1994-03-31 1998-10-13 Ntn Corp 複写機用分離爪
JP2019137863A (ja) * 2018-02-13 2019-08-22 日信工業株式会社 熱可塑性樹脂組成物の製造方法及び熱可塑性樹脂組成物
WO2022102277A1 (fr) * 2020-11-13 2022-05-19 株式会社リケン Corps moulé en peek et son procédé de production

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04101827A (ja) * 1990-08-21 1992-04-03 Mitsui Toatsu Chem Inc 二軸延伸ポリエーテルエーテルケトンフィルムの製造方法
JPH05172212A (ja) * 1991-05-27 1993-07-09 Sutaaraito Kogyo Kk 歯車成形品
JPH10274897A (ja) * 1994-03-31 1998-10-13 Ntn Corp 複写機用分離爪
JPH0940864A (ja) * 1995-07-26 1997-02-10 Mitsui Toatsu Chem Inc 樹脂組成物
JP2019137863A (ja) * 2018-02-13 2019-08-22 日信工業株式会社 熱可塑性樹脂組成物の製造方法及び熱可塑性樹脂組成物
WO2022102277A1 (fr) * 2020-11-13 2022-05-19 株式会社リケン Corps moulé en peek et son procédé de production

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