WO2022070695A1 - 耐ボールベアリング摺動摩耗部材用液晶性樹脂組成物及びそれを用いた耐ボールベアリング摺動摩耗部材 - Google Patents

耐ボールベアリング摺動摩耗部材用液晶性樹脂組成物及びそれを用いた耐ボールベアリング摺動摩耗部材 Download PDF

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WO2022070695A1
WO2022070695A1 PCT/JP2021/031164 JP2021031164W WO2022070695A1 WO 2022070695 A1 WO2022070695 A1 WO 2022070695A1 JP 2021031164 W JP2021031164 W JP 2021031164W WO 2022070695 A1 WO2022070695 A1 WO 2022070695A1
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Prior art keywords
ball bearing
sliding wear
granular filler
liquid crystal
resin composition
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PCT/JP2021/031164
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English (en)
French (fr)
Japanese (ja)
Inventor
真奈 中村
祐政 鄭
不二 酒井
昭宏 長永
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Polyplastics Co Ltd
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Polyplastics Co Ltd
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Priority to KR1020237008554A priority Critical patent/KR102532937B1/ko
Priority to CN202180063200.XA priority patent/CN116490572B/zh
Priority to JP2022501374A priority patent/JP7101323B1/ja
Publication of WO2022070695A1 publication Critical patent/WO2022070695A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides

Definitions

  • the present invention relates to a liquid crystal resin composition for a ball bearing sliding wear resistant member and a ball bearing sliding wear resistant member using the same.
  • Liquid crystal resin represented by liquid crystal polyester resin has excellent mechanical strength, heat resistance, chemical resistance, electrical properties, etc. in a well-balanced manner, and also has excellent dimensional stability, so it is widely used as a high-performance engineering plastic. It's being used. Recently, liquid crystal resins have come to be used for precision equipment parts by taking advantage of these features.
  • Patent Document 1 describes a liquid crystal resin and a talc having a specific volume average particle size as an object of providing a molded product made of a liquid crystal resin composition having an excellent surface appearance and excellent slidability.
  • a liquid crystal resin composition containing a specific ratio of the above is disclosed.
  • the silver streak is a phenomenon in which glittering silver-white streaks are generated on the surface of the molded product, and is a kind of molding defect that impairs the appearance of the molded product.
  • Patent Document 2 describes a part for a camera module used in a form of dynamically contacting with a ball bearing.
  • the present invention has been made to solve the above problems, and an object thereof is to suppress surface whitening, silver streak suppression, dimensional accuracy, and low dust generation in a well-balanced manner, and to have ball bearing sliding wear resistance.
  • the present inventors have conducted extensive research to solve the above problems.
  • the liquid crystal resin, the granular filler A, and the granular filler B are contained, and the median diameter of the granular filler A is in a predetermined range, and the median diameter of the granular filler B is in another predetermined range.
  • Granular Filler A, Granular Filler B, and a liquid crystal resin composition in which the content of each of these is in a predetermined range the above-mentioned problems can be solved, and the present invention is completed. I arrived. More specifically, the present invention provides the following.
  • (1) Contains (A) liquid crystal resin, (B) granular filler A, and (C) granular filler B, and the median diameter of (B) granular filler A is 0.3 ⁇ m or more and 2.5 ⁇ m.
  • the median diameter of the (C) granular filler B is more than 2.5 ⁇ m and 5.0 ⁇ m or less, and the content of the (B) granular filler A is 2.5 to 22.5% by mass.
  • the content of the (C) granular filler B is 2.5 to 22.5% by mass, and the total content of the (B) granular filler A and the (C) granular filler B is A liquid crystal resin composition for a ball bearing sliding wear resistant member having an amount of 12.5 to 32.5% by mass.
  • the (B) granular filler A is one or more selected from the group consisting of silica and barium sulfate
  • the (C) granular filler B is selected from the group consisting of silica and barium sulfate.
  • the composition according to (1) which is one or more kinds.
  • composition according to (1) or (2) further containing (D) an epoxy group-containing copolymer, wherein the content of the (D) epoxy group-containing copolymer is 1 to 5. Compositions that are% by weight.
  • a ball bearing sliding wear resistant member comprising the composition according to any one of (1) to (3).
  • a ball bearing sliding wear resistant member is manufactured using the liquid crystal resin composition for a ball bearing sliding wear resistant member of the present invention as a raw material, the balance between surface whitening suppression, silver streak suppression, dimensional accuracy, and low dust generation is achieved. It is possible to obtain a ball bearing sliding wear resistant member which is excellent in quality, has reduced ball bearing sliding wear resistance, and maintains impact resistance.
  • FIG. 1 (a) is a plan view showing a molded body molded for measuring the depth of a dent in an embodiment
  • FIG. 1 (b) is a partial vertical cross section showing a BB cross section of FIG. 1 (a). It is a figure. Unless otherwise specified, the unit of numerical values in the figure is mm.
  • FIG. 2A is a perspective view showing a U-shaped liquid crystal resin molded body used for the evaluation of inward tilt deformation performed in the examples
  • FIG. 2B is a U-shaped liquid crystal resin. It is a side view which shows the molded body.
  • FIG. 3 is a diagram for explaining a method of evaluating the amount of sliding wear.
  • the liquid crystal resin composition for a ball bearing sliding wear resistant member of the present invention contains (A) a liquid crystal resin, (B) a granular filler A, and (C) a granular filler B.
  • the liquid crystal resin (A) used in the present invention refers to a melt processable polymer having a property of forming an optically anisotropic melt phase.
  • the properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizing element. More specifically, the confirmation of the anisotropic molten phase can be carried out by observing the molten sample placed on the Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarizing microscope.
  • Liquid crystalline polymers applicable to the present invention normally transmit polarized light and are optically anisotropy when inspected between orthogonal modulators, even in a molten and stationary state.
  • the type of the liquid crystal resin (A) as described above is not particularly limited, and is preferably an aromatic polyester and / or an aromatic polyester amide. Further, polyesters partially containing aromatic polyesters and / or aromatic polyester amides in the same molecular chain are also in the range.
  • the liquid crystal resin (A) is preferably at least about 2.0 dl / g, more preferably 2.0 to 10.0 dl / g when dissolved in pentafluorophenol at 60 ° C. at a concentration of 0.1% by mass. Those having a logarithmic viscosity (IV) of are preferably used.
  • Aromatic polyester or aromatic polyester amide as a liquid crystal resin applicable to the present invention particularly preferably comprises a repeating unit derived from one or more of aromatic hydroxycarboxylic acid and its derivative. It is an aromatic polyester or an aromatic polyester amide having as.
  • Polyester consisting mainly of repeating units derived from one or more of aromatic hydroxycarboxylic acids and their derivatives; (2) Repeating units mainly derived from (a) one or more of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and one of their derivatives. Or polyester consisting of repeating units derived from two or more species; (3) Repeating units mainly derived from (a) one or more of aromatic hydroxycarboxylic acids and their derivatives, and (b) one of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives.
  • a polyester consisting of a repeating unit derived from two or more kinds and (c) a repeating unit derived from at least one kind or two or more kinds of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof; (4) Repeating units derived mainly from (a) one or more of aromatic hydroxycarboxylic acids and their derivatives, and (b) one or two of aromatic hydroxyamines, aromatic diamines, and their derivatives.
  • Polyester amides consisting of repeating units derived from species or more and (c) aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and repeating units derived from one or more of their derivatives; (5) Repeating units mainly derived from (a) one or more of aromatic hydroxycarboxylic acids and their derivatives, and (b) one or two of aromatic hydroxyamines, aromatic diamines, and their derivatives. Repeating units derived from species or higher, (c) aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and repeating units derived from one or more of their derivatives, and (d) aromatic diols, alicyclics.
  • polyesteramides composed of group diols, aliphatic diols, and repeating units derived from at least one or more of the derivatives thereof.
  • a molecular weight adjusting agent may be used in combination with the above-mentioned constituent components, if necessary.
  • Preferred examples of the specific compound constituting the (A) liquid crystal resin applicable to the present invention are aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; 2,6-dihydroxy.
  • Aromatic diols such as naphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcin, the compound represented by the following general formula (I), and the compound represented by the following general formula (II).
  • Aromas such as 1,4-phenylenedicarboxylic acid, 1,3-phenylenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III).
  • Dicarboxylic acids; aromatic amines such as p-aminophenol, p-phenylenediamine, N-acetyl-p-aminophenol and the like can be mentioned.
  • the liquid crystal resin (A) used in the present invention can be prepared by a known method using a direct polymerization method or an ester exchange method from the above-mentioned monomer compound (or a mixture of monomers), and is usually a melt polymerization method.
  • a melt polymerization method Solution polymerization method, slurry polymerization method, solid phase polymerization method, etc., or a combination of two or more thereof is used, and a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is preferably used.
  • the above compounds having an ester-forming ability may be used in the polymerization as they are, or may be modified from a precursor to a derivative having the ester-forming ability in the pre-polymerization stage.
  • Various catalysts can be used in these polymerizations, and typical ones are potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris (2). , 4-Pentandionato) Metal salt-based catalysts such as cobalt (III), and organic compound-based catalysts such as N-methylimidazole and 4-dimethylaminopyridine.
  • the amount of the catalyst used is generally preferably about 0.001 to 1% by mass, particularly preferably about 0.01 to 0.2% by mass, based on the total mass of the monomers. If necessary, the polymer produced by these polymerization methods can be further increased in molecular weight by a solid phase polymerization method in which the polymer is heated under reduced pressure or in an inert gas.
  • the melt viscosity of the liquid crystal resin (A) obtained by the above method is not particularly limited. Generally, those having a melt viscosity at a molding temperature of 1000 sec -1 and a shear rate of 3 Pa ⁇ s or more and 500 Pa ⁇ s or less can be used. However, the one having a very high viscosity by itself is not preferable because the fluidity is very deteriorated.
  • the liquid crystal resin (A) may be a mixture of two or more kinds of liquid crystal resins.
  • the content of the liquid crystal resin (A) is preferably 67.5 to 87.5% by mass or 66.5 to 82.5% by mass, and more preferably 73. It is 5 to 80% by mass or 71.5 to 76% by mass.
  • the content of the component (A) is within the above range, it is preferable in terms of fluidity, heat resistance and the like.
  • the component (B) is the granular filler A, and the median diameter of the component (B) is 0.3 ⁇ m or more and 2.5 ⁇ m or less.
  • the median diameter is preferably 0.5 ⁇ m or more and 2.5 ⁇ m or less, and more preferably 0.5 ⁇ m or more and 2.0 ⁇ m or less.
  • the median diameter means the median value of the volume standard measured by the laser diffraction / scattering type particle size distribution measurement method.
  • the median diameter of the component (B) in the liquid crystal resin composition was measured by applying the above method to the component (B) remaining after incineration of the liquid crystal resin composition by heating at 600 ° C. for 2 hours.
  • the component (B) may be used alone or in combination of two or more.
  • Examples of the granular filler A of the component (B) include silica salts such as silica, quartz powder, glass beads, glass powder, potassium aluminum silicate, and diatomaceous earth; metals such as iron oxide, titanium oxide, zinc oxide, and alumina. Oxides; Metallic carbonates such as calcium carbonate and magnesium carbonate; Metallic sulfates such as calcium sulfate and barium sulfate; Phosphates such as calcium pyrophosphate and anhydrous dicalcium phosphate; Be done.
  • silica salts such as silica, quartz powder, glass beads, glass powder, potassium aluminum silicate, and diatomaceous earth
  • metals such as iron oxide, titanium oxide, zinc oxide, and alumina. Oxides
  • Metallic carbonates such as calcium carbonate and magnesium carbonate
  • Metallic sulfates such as calcium sulfate and barium sulfate
  • Phosphates such as calcium pyrophosphate and anhydrous dicalcium phosphate
  • the present invention from the viewpoint of suppressing surface whitening of the molded body and low dust generation of the molded body, it is preferable to use at least one selected from the group consisting of silica and barium sulfate as the component (B). It is more preferable to use silica.
  • the content of the component (B) is 2.5 to 22.5% by mass in the liquid crystal composition of the present invention.
  • the content of the component (B) is 2.5% by mass or more, it is easy to obtain a molded product having reduced ball bearing sliding wear resistance.
  • the content of the component (B) is 22.5% by mass or less, the silver streak suppressing effect of the molded product tends to be high.
  • the preferable content of the component (B) is 5 to 15% by mass.
  • the component (C) is a granular filler B, and the median diameter of the component (C) is more than 2.5 ⁇ m and 5.0 ⁇ m or less.
  • the median diameter is more than 2.5 ⁇ m, the silver streak suppressing effect of the molded product tends to be high.
  • the median diameter is 5.0 ⁇ m or less, the effect of suppressing surface whitening of the molded product and the low dust generation property of the molded product tend to be high.
  • the median diameter is preferably 3.0 ⁇ m or more and 4.7 ⁇ m or less, and more preferably 3.5 ⁇ m or more and 4.5 ⁇ m or less.
  • the median diameter means the median value of the volume standard measured by the laser diffraction / scattering type particle size distribution measurement method.
  • the median diameter of the component (C) in the liquid crystal resin composition was measured by applying the above method to the component (C) remaining after incineration of the liquid crystal resin composition by heating at 600 ° C. for 2 hours.
  • the component (C) may be used alone or in combination of two or more.
  • Examples of the granular filler B of the component (C) include the same granular filler as exemplified for the granular filler A of the component (B).
  • the content of the component (C) is 2.5 to 22.5% by mass in the liquid crystal composition of the present invention.
  • the content of the component (C) is 2.5% by mass or more, it is easy to obtain a molded product having reduced ball bearing sliding wear resistance.
  • the content of the component (C) is 22.5% by mass or less, the effect of suppressing surface whitening of the molded product tends to be high.
  • the preferable content of the component (C) is 5 to 15% by mass.
  • the total content of the component (B) and the component (C) is 12.5 to 32.5% by mass, preferably 20 to 26.5% by mass in the liquid crystal resin composition of the present invention. Is. When the total content is 12.5% by mass or more, the dimensional accuracy of the molded product tends to be high, and the molded product having reduced ball bearing sliding wear resistance can be easily obtained. When the total content is 32.5% by mass or less, the low dust generation property of the molded product tends to be high, and the impact resistance of the molded product tends to be maintained.
  • the liquid crystal composition of the present invention may contain (D) an epoxy group-containing copolymer.
  • the epoxy group-containing copolymer can be used alone or in combination of two or more.
  • the (D) epoxy group-containing copolymer is not particularly limited, and is at least selected from the group consisting of (D1) epoxy group-containing olefin-based copolymer and (D2) epoxy group-containing styrene-based copolymer. One type can be mentioned.
  • the epoxy group-containing copolymer contributes to reducing the ball bearing sliding wear property of the molded product obtained from the liquid crystal resin composition of the present invention.
  • Examples of the (D1) epoxy group-containing olefin-based copolymer include a copolymer composed of a repeating unit derived from an ⁇ -olefin and a repeating unit derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid. Be done.
  • the ⁇ -olefin is not particularly limited, and examples thereof include ethylene, propylene, butene and the like, and ethylene is preferably used.
  • the glycidyl ester of ⁇ , ⁇ -unsaturated acid is represented by the following general formula (IV).
  • the glycidyl ester of ⁇ , ⁇ -unsaturated acid is, for example, acrylic acid glycidyl ester, methacrylic acid glycidyl ester, etacrylic acid glycidyl ester, itaconic acid glycidyl ester and the like, and methacrylic acid glycidyl ester is particularly preferable.
  • the content of the repeating unit derived from ⁇ -olefin is 87 to 98% by mass, and the content of the repeating unit derived from the glycidyl ester of ⁇ , ⁇ -unsaturated acid is contained.
  • the amount is preferably 13 to 2% by mass.
  • the (D1) epoxy group-containing olefin-based copolymer used in the present invention has acrylonitrile, acrylic acid ester, methacrylic acid ester, ⁇ -methylstyrene, and malean anhydride as a third component in addition to the above two components as long as the present invention is not impaired.
  • Repeating units derived from one or more of olefinically unsaturated esters such as acids may be contained in an amount of 0 to 48 parts by mass with respect to 100 parts by mass of the above two components.
  • the epoxy group-containing olefin-based copolymer which is the component (D1) of the present invention can be easily prepared by a usual radical polymerization method using a monomer corresponding to each component and a radical polymerization catalyst. More specifically, usually, the presence of a suitable solvent or chain transfer agent for ⁇ -olefin and glycidyl ester of ⁇ , ⁇ -unsaturated acid at 500 to 4000 atm and 100 to 300 ° C. in the presence of a radical generator. It can be produced by a method of copolymerizing under or in the absence. It can also be produced by a method in which an ⁇ -olefin, an ⁇ , ⁇ -unsaturated acid glycidyl ester and a radical generator are mixed and melt-grafted in an extruder.
  • Examples of the epoxy group-containing styrene-based copolymer (D2) include a copolymer composed of a repeating unit derived from styrenes and a repeating unit derived from a glycidyl ester of ⁇ , ⁇ -unsaturated acid. Be done. Since the glycidyl ester of ⁇ , ⁇ -unsaturated acid is the same as that described in the component (D1), the description thereof will be omitted.
  • styrenes examples include styrene, ⁇ -methylstyrene, brominated styrene, divinylbenzene and the like, and styrene is preferably used.
  • the (D2) epoxy group-containing styrene-based copolymer used in the present invention is a multidimensional copolymer containing a repeating unit derived from one or more of other vinyl monomers as a third component in addition to the above two components. There may be.
  • a suitable third component is a repeating unit derived from one or more of olefinically unsaturated esters such as acrylonitrile, acrylic acid ester, methacrylic acid ester, and maleic anhydride.
  • An epoxy group-containing styrene-based copolymer containing 40% by mass or less of these repeating units in the copolymer is preferable as the component (D2).
  • the content of the repeating unit derived from the glycidyl ester of ⁇ , ⁇ -unsaturated acid is 2 to 20% by mass, and the content of the repeating unit derived from styrenes is high. Is preferably 80 to 98% by mass.
  • the epoxy group-containing styrene-based copolymer can be prepared by a usual radical polymerization method using a monomer corresponding to each component and a radical polymerization catalyst. More specifically, styrenes and glycidyl esters of ⁇ , ⁇ -unsaturated acids are usually mixed in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. in the presence of a suitable solvent or chain transfer agent. Alternatively, it can be produced by a method of copolymerizing in the absence. It can also be produced by a method of mixing styrenes with an ⁇ , ⁇ -unsaturated acid glycidyl ester and a radical generator and subjecting them to melt graft copolymerization in an extruder.
  • the (D) epoxy group-containing copolymer the (D1) epoxy group-containing olefin-based copolymer is preferable in terms of heat resistance.
  • the ratio of these components can be appropriately selected according to the required characteristics.
  • the content of the (D) epoxy group-containing copolymer may be, for example, 0 to 5% by mass, preferably 1 to 5% by mass in the liquid crystal resin composition of the present invention.
  • the content of the component (D) is within the above range, it is easy to obtain a molded product having reduced ball bearing sliding wearability without impairing the fluidity of the liquid crystal resin composition.
  • a more preferable content is 2 to 4% by mass.
  • the carbon black (E) used as an optional component in the present invention is not particularly limited as long as it is generally available and is used for resin coloring. Normally, (E) carbon black contains lumps formed by agglomeration of primary particles, but unless a large amount of lumps having a size of 50 ⁇ m or more are contained, the resin composition of the present invention is molded. Many bumps (fine bumpy protrusions (fine irregularities) in which carbon black is aggregated) are unlikely to occur on the surface of the molded product. When the content of the particles having a mass particle diameter of 50 ⁇ m or more is 20 ppm or less, the effect of suppressing the raising of the surface of the molded product tends to be high. The preferred content is 5 ppm or less.
  • the component (E) may be used alone or in combination of two or more.
  • the blending amount of (E) carbon black may be, for example, 0 to 5% by mass, preferably 0.5 to 5% by mass in the liquid crystal resin composition.
  • the blending amount of carbon black is 0.5% by mass or more, the jet-blackness of the obtained resin composition is less likely to deteriorate, and the light-shielding property is less likely to be anxious. If the blending amount of carbon black is 5% by mass or less, it is less likely to be uneconomical and less likely to cause lumps.
  • the (F) mold release agent used as an optional component in the present invention is not particularly limited as long as it is generally available, and is, for example, fatty acid esters, fatty acid metal salts, fatty acid amides, and low. Examples thereof include molecular weight polyolefins, and fatty acid esters of pentaerythritol (for example, pentaerythritol tetrastearate) are preferable.
  • the component (F) may be used alone or in combination of two or more.
  • the amount of the release agent (F) to be blended may be, for example, 0 to 3% by mass, preferably 0.1 to 3% by mass in the liquid crystal resin composition.
  • the compounding amount of the mold release agent is 0.1% by mass or more, it is easy to obtain a molded product having improved mold releasability during molding and reduced ball bearing sliding wear resistance.
  • the blending amount of the mold release agent is 3% by mass or less, the mold deposit (that is, the deposit on the mold in molding, hereinafter also referred to as “MD”) is likely to be reduced.
  • the liquid crystal resin composition of the present invention contains other polymers, other fillers, and known substances generally added to synthetic resins, that is, antioxidants and ultraviolet absorbers, as long as the effects of the present invention are not impaired.
  • Other components such as stabilizers such as agents, antistatic agents, flame retardant agents, colorants such as dyes and pigments, lubricants, crystallization accelerators, and crystal nucleating agents can also be appropriately added depending on the required performance.
  • Other components may be used alone or in combination of two or more.
  • the other fillers are fillers other than (B) granular filler A, (C) granular filler B, and (E) carbon black, and are, for example, granules other than (B) component and (C) component.
  • Other fillers may be used alone or in combination of two or more.
  • Examples of the granular filler other than the component (B) and the component (C) include a granular filler having a median diameter of less than 0.3 ⁇ m or more than 5.0 ⁇ m.
  • Examples of the plate-shaped filler include mica and talc.
  • Examples of the fibrous filler include glass fiber and whiskers.
  • the liquid crystal resin composition of the present invention preferably does not contain a plate-like filler. Further, from the viewpoint of impact resistance of the molded body, low dust generation of the molded body, and the like, the liquid crystal resin composition of the present invention preferably does not contain a fibrous filler.
  • the method for preparing the liquid crystal resin composition for a ball bearing sliding wear resistant member of the present invention is not particularly limited. For example, at least one of the above components (A) to (C), and optionally at least one of the above (D) to (F) components and other components is blended, and these are blended using a single-screw or twin-screw extruder. By melt-kneading, a liquid crystal resin composition for a ball bearing sliding wear resistant member is prepared.
  • the liquid crystal resin composition of the present invention obtained as described above preferably has a melt viscosity of 90 Pa ⁇ sec or less, preferably 80 Pa ⁇ sec or less, from the viewpoint of fluidity at the time of melting and moldability. It is more preferable to have.
  • the melt viscosity a value obtained by a measuring method based on ISO 11443 is adopted under the conditions of a cylinder temperature 10 to 20 ° C. higher than the melting point of the liquid crystal resin and a shear rate of 1000 sec -1 .
  • a ball bearing sliding wear resistant member is manufactured using the liquid crystal resin composition of the present invention.
  • the ball bearing sliding wear resistant member of the present invention has excellent surface whitening suppression, silver streak suppression, dimensional accuracy, and low dust generation in a well-balanced manner, while reducing ball bearing sliding wear resistance and impact resistance. It is maintained.
  • the ball bearing sliding wear resistant member of the present invention can be used for a component that dynamically contacts the ball bearing during use, and specifically, for example, is used in a form that dynamically contacts the ball bearing. It can be used for camera module parts such as lens holders.
  • the stirring torque reached a predetermined value
  • nitrogen was introduced to bring the mixture into a pressurized state from a reduced pressure state through a normal pressure state
  • the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain pellets.
  • the obtained pellets were heat-treated at 300 ° C. for 2 hours under a nitrogen stream to obtain the desired polymer.
  • the melting point of the obtained polymer was 336 ° C, and the melt viscosity at 350 ° C was 19.0 Pa ⁇ s.
  • the melting point and the melt viscosity of the polymer were measured according to the method for measuring the melting point described later and the method for measuring the melt viscosity described later, respectively.
  • HBA 4-Hydroxybenzoic acid
  • HNA 2-Hydroxy-6-naphthoic acid
  • TA 1,4-phenylenedicarboxylic acid
  • BP 4,4'-dihydroxybiphenyl
  • APAP N-Acetyl-p-Aminophenol
  • APAP N-Acetyl-p-Aminophenol
  • Metal catalyst potassium acetate catalyst
  • 110 mg Acylating agent acetic anhydride
  • ⁇ Silver streak> The pellets of Examples and Comparative Examples were molded using a molding machine (“SE30DUZ” manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions, and a test piece for measurement (30 mm ⁇ 30 mm ⁇ 0.3 mm) was formed. Obtained. The surface of the test piece for measurement was visually observed. The silver streak of the test piece for measurement was evaluated according to the following criteria. The results are shown in Tables 1 and 2. ⁇ (Good): Of the 10 test pieces, the number of test pieces in which silver streak occurred was 3 or less. X (defective): Of the 10 test pieces, the number of test pieces in which silver streak occurred was more than 3. ⁇ Molding condition ⁇ Cylinder temperature: 350 ° C Mold temperature: 80 ° C Injection speed: 100 mm / sec
  • ⁇ Ball bearing sliding wear resistance> The pellets of Examples and Comparative Examples were molded using a molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions to obtain a test piece for measurement (80 mm ⁇ 80 mm ⁇ 1 mm). .. Using a light load reciprocating tester, as shown in FIG. 3, a load is applied to the ball 4 (diameter 5 mm, made of SUS) at the tip of the arm 3 on the measurement test piece 1 via the grease 2, and the following After performing a reciprocating sliding test under reciprocating sliding conditions, the width of the ball bearing sliding marks remaining on the measurement test piece 1 is measured using a stereomicroscope, and the ball bearing sliding wear resistance is determined according to the following criteria. evaluated.
  • SE100DU manufactured by Sumitomo Heavy Industries, Ltd.
  • the molded product of the example has excellent ball bearing sliding wear resistance in a well-balanced manner in terms of surface whitening suppression, silver streak suppression, dimensional accuracy, and low dust generation. It was confirmed that the impact was reduced and the impact resistance was maintained.

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  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2021/031164 2020-09-29 2021-08-25 耐ボールベアリング摺動摩耗部材用液晶性樹脂組成物及びそれを用いた耐ボールベアリング摺動摩耗部材 Ceased WO2022070695A1 (ja)

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