WO2022004553A1 - 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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WO2022004553A1
WO2022004553A1 PCT/JP2021/023996 JP2021023996W WO2022004553A1 WO 2022004553 A1 WO2022004553 A1 WO 2022004553A1 JP 2021023996 W JP2021023996 W JP 2021023996W WO 2022004553 A1 WO2022004553 A1 WO 2022004553A1
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Prior art keywords
ball bearing
sliding wear
resin composition
liquid crystal
whiskers
Prior art date
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Ceased
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PCT/JP2021/023996
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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 JP2022501375A priority Critical patent/JP7200435B2/ja
Priority to CN202180043329.4A priority patent/CN115702206B/zh
Priority to KR1020227043936A priority patent/KR102545958B1/ko
Publication of WO2022004553A1 publication Critical patent/WO2022004553A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • 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
    • 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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/02—Parts of sliding-contact bearings
    • F16C33/04—Brasses; Bushes; Linings
    • F16C33/20—Sliding surface consisting mainly of plastics

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.
  • 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-mentioned problems, and an object thereof is to have excellent ball bearing sliding wear resistance in a well-balanced manner in terms of surface whitening suppression, mechanical strength, dimensional accuracy, and low dust generation.
  • the present inventors have conducted extensive research to solve the above problems.
  • the liquid crystal resin, the granular filler, and the whiskers are contained, the median diameter of the granular filler is within a predetermined range, and the content of each of the granular filler, the whiskers, and the total of these is within a predetermined range.
  • the present invention provides the following.
  • composition according to (1) wherein the (B) granular filler is at least one selected from the group consisting of silica and barium sulfate.
  • 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, mechanical strength, 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, and (C) a whiskers.
  • the liquid crystal resin (A) used in the present invention refers to a melt-processable polymer having a property of forming an optically anisotropic molten 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.
  • the liquid crystalline polymer applicable to the present invention normally transmits polarized light and exhibits optical anisotropy when inspected between orthogonal modulators, even in a molten and resting 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 p-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).
  • Aromatic compounds 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 69 to 82.5% by mass. It is 84% by mass or 67-80% 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 a granular filler, and the median diameter of the component (B) is 0.3 to 5.0 ⁇ m.
  • the median diameter is preferably 0.5 to 5.0 ⁇ m, more preferably 0.5 to 4.0 ⁇ m.
  • the median diameter of the component (B) 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 of the component (B) include metal oxides such as silica, quartz powder, glass beads, glass powder, potassium aluminum silicate, diatomaceous earth, iron oxide, titanium oxide, zinc oxide, and alumina; calcium carbonate, Examples thereof include metal carbonates such as magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; phosphates such as calcium pyrophosphate and anhydrous dicalcium phosphate; fluorocarbons; silicon nitride; boron nitride and the like.
  • metal oxides such as silica, quartz powder, glass beads, glass powder, potassium aluminum silicate, diatomaceous earth, iron oxide, titanium oxide, zinc oxide, and alumina
  • calcium carbonate examples thereof include metal carbonates such as magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; phosphates such as calcium pyrophosphate and anhydrous dicalcium phosphate; fluor
  • 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 one or more 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 7.5 to 22.5% by mass in the liquid crystal composition of the present invention.
  • the content of the component (B) is 7.5% by mass or more, the dimensional accuracy of the molded body tends to be high, and it is easy to obtain a molded body having reduced ball bearing sliding wear resistance.
  • the content of the component (B) is 22.5% by mass or less, the effect of suppressing surface whitening of the molded product is likely to be high, and the impact resistance of the molded product is likely to be maintained.
  • the preferable content of the component (B) is 8.5 to 21% by mass.
  • the liquid crystal resin composition according to the present invention includes whiskers. By containing the whiskers in the liquid crystal resin composition according to the present invention, it is easy to improve the mechanical strength of the molded body and to obtain a molded body having reduced ball bearing sliding wear resistance.
  • whiskers refer to mineral fibers, and more specifically, needle-like single crystals. Whiskers can be used alone or in combination of two or more.
  • the average fiber length of the whiskers is preferably 5 to 200 ⁇ m, more preferably 7 to 170 ⁇ m, and even more preferably 9 to 150 ⁇ m. When the average fiber length is within the above range, the mechanical strength of the molded product is likely to be improved.
  • the average fiber length of (C) whiskers is 100 for each body microscope image by taking 10 whiskers body microscope images from a CCD camera into a PC and using an image processing method with an image measuring machine. The average of the measured fiber lengths of the book whiskers, that is, a total of 1000 whiskers, is adopted.
  • the average fiber length of the (C) whiskers in the liquid crystal resin composition is measured by applying the above method to the whiskers remaining after incineration of the liquid crystal resin composition by heating at 600 ° C. for 2 hours.
  • the average fiber diameter of the whiskers is preferably 0.2 to 15 ⁇ m or less, and more preferably 0.25 to 10 ⁇ m. When the average fiber diameter is within the above range, the mechanical strength of the molded product is likely to be improved.
  • the average fiber diameter of (C) whiskers the average of the values obtained by observing the whiskers with a scanning electron microscope and measuring the fiber diameters of 30 whiskers is adopted. The average fiber diameter of the (C) whiskers in the liquid crystal resin composition is measured by applying the above method to the whiskers remaining after incineration of the liquid crystal resin composition by heating at 600 ° C. for 2 hours.
  • the aspect ratio of the whiskers that is, the value of the average fiber length / the average fiber diameter is from the viewpoint of the mechanical strength of a molded body such as a ball bearing sliding wear resistant member made of the liquid crystal resin composition according to the present invention. Therefore, it is preferably 8 or more, more preferably 10 to 100, and even more preferably 15 to 75.
  • the whiskers are not particularly limited, and are, for example, potassium titanate whiskers, calcium silicate whiskers (wollastonite), calcium carbonate whiskers, zinc oxide whiskers, aluminum borate whiskers, silicon nitride whiskers, silicon trinitride whiskers. , Basic magnesium sulfate whiskers, barium whiskers titanate, silicon carbide whiskers, boron whiskers, and in terms of availability, potassium titanate whiskers, calcium silicate whiskers (wollastonite), calcium carbonate whiskers, zinc oxide. Whiskers, aluminum borate whiskers and the like are preferable, and potassium titanate whiskers, calcium silicate whiskers (wollastonite) and the like are more preferable.
  • the content of the component (C) is 2.5 to 17.5% by mass in the liquid crystal resin composition of the present invention.
  • the content of the component (C) is 2.5% by mass or more, it is easy to improve the mechanical strength and to obtain a molded product having reduced ball bearing sliding wear resistance.
  • the content of the component (C) is 17.5% by mass or less, the impact resistance of the molded product is likely to be maintained.
  • the content of the component (C) is preferably 4.5 to 14% by mass.
  • the total content of the component (B) and the component (C) is 12.5 to 32.5% by mass, preferably 16 to 31% by mass in the liquid crystal resin composition of the present invention. ..
  • the total content is 12.5% by mass or more, the dimensional accuracy of the molded body tends to be high, and it is easy to obtain a molded body having reduced ball bearing sliding wear resistance.
  • the total content is 32.5% by mass or less, the effect of suppressing surface whitening of the molded product and the low dust generation property of the molded product are likely to be high, and the impact resistance of the molded product is likely 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) an epoxy group-containing olefin-based copolymer and (D2) an 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 olefin 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 in which styrenes, an ⁇ , ⁇ -unsaturated acid glycidyl ester and a radical generator are mixed and melt-grafted 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 retardants, 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 fillers, (C) whiskers, and (E) carbon black, for example, granular fillers other than the component (B); plate-like fillers; ( C) Examples include fibrous fillers other than the components. Other fillers may be used alone or in combination of two or more. Examples of the granular filler other than the component (B) include granular fillers 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 other than the component (C) include glass fiber.
  • 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 property of the molded body, and the like, the liquid crystal resin composition of the present invention preferably does not contain a fibrous filler other than the component (C).
  • 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, mechanical strength, 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 from a reduced pressure state to a pressurized state through normal pressure
  • 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 melt viscosity of the polymer was measured in the same manner as the method for measuring the melt viscosity described later.
  • 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
  • ⁇ Bending test> 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 ISO test piece A type. This test piece was cut out to obtain a measurement test piece (80 mm ⁇ 10 mm ⁇ 4 mm). Using this measurement test piece, bending strength, bending strain, and flexural modulus were measured according to ISO 178. Of these, the measurement results of bending strength were evaluated according to the following criteria. The results are shown in Tables 1 to 3. ⁇ (good): The bending strength was 150 MPa or more. X (defective): The bending strength was less than 150 MPa. ⁇ Molding condition ⁇ Cylinder temperature: 350 ° C Mold temperature: 90 ° C Injection speed: 33 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 the reciprocating sliding test under the reciprocating sliding conditions, the width of the ball bearing sliding marks remaining on the measurement test piece 1 is measured using a stereoscopic microscope, 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, mechanical strength, dimensional accuracy, and low dust generation. It was confirmed that the impact was reduced and the impact resistance was maintained.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • General Engineering & Computer Science (AREA)
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JP2025084681A (ja) * 2023-11-22 2025-06-03 セ ヤン ポリマー カンパニー リミテッド 液晶ポリエステル樹脂組成物、成形品及びこれを含む電子部品素材

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JP7831868B2 (ja) 2023-11-22 2026-03-17 セ ヤン ポリマー カンパニー リミテッド 液晶ポリエステル樹脂組成物、成形品及びこれを含む電子部品素材

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