WO2021065416A1

WO2021065416A1 - Liquid crystalline resin composition for ball bearing anti-sliding abrasion member, and ball bearing anti-sliding abrasion member using same

Info

Publication number: WO2021065416A1
Application number: PCT/JP2020/034340
Authority: WO
Inventors: 不二酒井; 博樹深津; 昭宏長永
Original assignee: ポリプラスチックス株式会社
Priority date: 2019-10-03
Filing date: 2020-09-10
Publication date: 2021-04-08
Also published as: JP6906123B1; TWI836143B; CN114502657A; CN114502657B; KR20220045082A; TW202116893A; KR102506289B1; JPWO2021065416A1

Abstract

Provided are: a liquid crystalline resin composition for a ball bearing anti-sliding abrasion member, the composition being used to produce a ball bearing anti-sliding abrasion member which has reduced sliding abrasiveness of a ball bearing and improved impact resistance while ensuring excellent surface whitening suppression, low warpage properties, weld strength, and low dust generation in a good balance; and a ball bearing anti-sliding abrasion member using said liquid crystalline resin composition.　The liquid crystalline resin composition for a ball bearing anti-sliding abrasion member according to the present invention contains (A) a liquid crystalline resin, (B) a particulate filler, and (C) a plate-like filler, wherein the median diameter of (B) the particulate filler is 0.3-5.0 μm, the Mohs hardness of (B) the particulate filler is at least 2.5, the Mohs hardness of the plate-like filler is at least 2.0, the content of (B) the particulate filler is 2.5-22.5 mass%, the content of (C) the plate-like filler is 2.5-32.5 mass%, and the total content of (B) the particulate filler and (C) the plate-like filler is 22.5-37.5 mass%.

Description

Liquid crystal resin composition for ball bearing sliding wear member and ball bearing sliding wear member using it

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 resins represented by liquid crystal polyester resins have excellent mechanical strength, heat resistance, chemical resistance, electrical properties, etc. in a well-balanced manner, and also have excellent dimensional stability, so they are widely used as high-performance engineering plastics. It's being used. Recently, liquid crystal resins have come to be used for precision equipment parts by taking advantage of these features.

Examples of parts in which liquid crystal resin is used include connectors such as FPC connectors; sockets such as memory card sockets; camera module parts such as lens holders; relays. These parts are required to be excellent in surface whitening suppression, low warpage, wear strength, and low dust generation, and may be used in a form in which two or more members dynamically contact each other. Therefore, it is also required that the sliding wear property (that is, the ease of wear when two or more members are dynamically contacted) is reduced. For example, 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 excellent surface appearance and excellent slidability. A liquid crystal resin composition containing a specific ratio of the above is disclosed.

Among the above-mentioned parts, in the case of a part used in a form in which a molded body made of a liquid crystal resin composition and a ball bearing are in dynamic contact with each other, the ball bearing has sliding wear resistance (that is, the ball bearing). Ease of wear when dynamically contacted) is required to be reduced. Further, when the component is impacted, if the molded body is easily scratched, cracked, dented or the like, there is a possibility that a problem may occur in the dynamic contact between the molded body and the ball bearing. Therefore, it is also required that the above-mentioned parts have improved impact resistance, that is, characteristics that scratches, cracks, dents, etc. are unlikely to occur even when subjected to an impact. In addition, Patent Document 2 describes a part for a camera module used in a form of dynamically contacting a ball bearing.

Japanese Patent No. 5087958 European Patent No. 2938063

However, according to the studies by the present inventors, the conventional liquid crystal resin composition is insufficient in reducing the ball bearing sliding wear resistance and improving the impact resistance. The present invention has been made to solve the above problems, and an object of the present invention is to have a well-balanced excellent surface whitening suppression, low warpage property, weld strength, and low dust generation property, and to have ball bearing sliding wear resistance. A liquid crystal resin composition for a ball bearing sliding wear member used for manufacturing a ball bearing sliding wear member with reduced and improved impact resistance, and a ball bearing sliding wear member using the liquid crystal resin composition. Is to provide.

The present inventors have conducted extensive research to solve the above problems. As a result, a liquid crystal resin, a granular filler having a specific median diameter and a specific Mohs hardness, and a plate-shaped filler having a specific Mohs hardness are contained, and the granular filler, the plate-shaped filler, and the total of these are contained. It has been found that the above-mentioned problems can be solved by using a liquid crystal resin composition in which the content of each of the above is in a predetermined range, and the present invention has been completed. More specifically, the present invention provides the following.

(1) Contains (A) liquid crystal resin, (B) granular filler, and (C) plate-like filler, and the median diameter of the (B) granular filler is 0.3 to 5.0 μm. The moth hardness of the (B) granular filler is 2.5 or more, the moth hardness of the (C) plate-shaped filler is 2.0 or more, and the content of the (B) silica is The content of the (C) plate-shaped filler is 2.5 to 22.5% by mass, and the content of the (B) granular filler and the (C) plate is 2.5 to 32.5% by mass. A liquid crystal resin composition for a ball bearing sliding wear resistant member having a total content of 22.5 to 37.5% by mass with the filler.

(2) The composition according to (1), wherein the (C) plate-like filler is mica.

(3) The composition according to (1) or (2), wherein the (B) granular filler is at least one selected from the group consisting of silica and barium sulfate.

(4) The composition according to any one of (1) to (3) further containing (D) an epoxy group-containing copolymer, wherein the content of the (D) epoxy group-containing copolymer is A composition which is 1 to 5% by mass.

(5) A ball bearing sliding wear resistant member made of the composition according to any one of (1) to (4).

If a ball bearing sliding wear member is manufactured using the liquid crystal resin composition for a ball bearing sliding wear member of the present invention as a raw material, a balance between surface whitening suppression, low warpage, weld strength, and low dust generation is achieved. It is possible to obtain a ball bearing sliding wear resistant member which is excellent, has reduced ball bearing sliding wear resistance, and has improved impact resistance.

FIG. 1 is a diagram for explaining a method of evaluating the amount of sliding wear. FIG. 2A is a diagram showing a camera module type molded product used for the warp deformation evaluation, and FIG. 2B is a diagram showing a measurement point in the warp deformation evaluation. The unit of the numerical value in the figure is mm. FIG. 3 is a diagram showing a molded product used in the weld strength evaluation. The unit of the numerical value in the figure is mm.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments.

<Liquid crystal resin composition for ball bearing sliding wear member>
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 plate-like filler.

[(A) Liquid crystal resin]
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 anisotropic molten phase can be confirmed 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 polarizers, even in the 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. The range also includes polyesters that partially contain aromatic polyesters and / or aromatic polyester amides in the same molecular chain. The liquid crystal resin (A) 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.

The aromatic polyester or aromatic polyesteramide as the (A) liquid crystal resin applicable to the present invention is particularly preferably at least one selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines. An aromatic polyester or aromatic polyester amide having a repeating unit derived from a species compound as a constituent.

More specifically
(1) Polyester composed of repeating units mainly derived from one or more aromatic hydroxycarboxylic acids and their derivatives;
(2) Repeating units mainly derived from (a) one or more aromatic hydroxycarboxylic acids and their derivatives, 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 kinds of aromatic hydroxycarboxylic acids and their derivatives, and (b) one kind of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives. Or 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 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. Polyester amides consisting of repeating units derived from species or higher 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, aliphatic dicarboxylic acids, and repeating units derived from one or more of their derivatives, and (d) aromatic diols, alicyclics. Examples thereof include polyesteramides composed of group diols, aliphatic diols, and repeating units derived from at least one or more of the derivatives thereof. Further, 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, a compound represented by the following general formula (I), and a compound represented by the following general formula (II). Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III); p-aminophenol, p- Examples include aromatic amines such as phenylenediamine.

(X: _{A group selected from alkylene (C 1} to C ₄ ), alkylidene, -O-, -SO-, -SO _2- , -S-, and -CO-)

(Y:-(CH ₂ ) _n- (n = 1 to 4) and -O (CH ₂ ) _n O- (n = 1 to 4).)

The liquid crystal resin (A) used in the present invention can be prepared from the above-mentioned monomer compound (or mixture of monomers) by a known method using a direct polymerization method or a transesterification method, and is usually a melt polymerization method. , Solution polymerization method, slurry polymerization method, solid phase polymerization method, etc., or a combination of two or more of these 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 step. Various catalysts can be used for 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 monomer. 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.

In the liquid crystal resin composition of the present invention, the content of the liquid crystal resin (A) is preferably 62.5 to 77.5% by mass or 61.5 to 72.5% by mass, and more preferably 65 to 72.5% by mass. It is 75% by mass or 63.5 to 72.5% by mass. When the content of the component (A) is within the above range, it is preferable in terms of fluidity, heat resistance and the like.

[(B) Granular filler]
The component (B) is a granular filler, the median diameter of the component (B) is 0.3 to 5.0 μm, and the Mohs hardness of the component (B) is 2.5 or more. When the median diameter is 0.3 μm or more, the weld strength of the molded product tends to be high. When the median diameter is 5.0 μm or less, the effect of suppressing surface whitening of the molded product tends to be high. The median diameter is preferably 0.5 to 5.0 μm, more preferably 0.5 to 4.0 μm. In the present specification, the median diameter means the median value of the volume standard measured by the laser diffraction / scattering type particle size distribution measurement method. The Mohs hardness is preferably 2.7 or more, more preferably 3.0 or more. When the Mohs hardness is 2.5 or more, the surface hardness of the molded product tends to be high, so that the molded product is less likely to be scratched, cracked, dented or the like even when subjected to an impact, and the impact resistance is likely to be improved. The upper limit of the Mohs hardness is not particularly limited, and may be 10 or less, 8 or less, or 7 or less. The component (B) may be used alone or in combination of two or more.

Examples of the granular filler of the component (B) include silica (Mohs hardness 6), quartz powder (Mohs hardness 7), glass beads (Mohs hardness 5), glass powder (Mohs hardness 5), and potassium aluminum silicate (Mohs). Mohs scales such as hardness 6), Mohs clay (Mohs hardness 6-7), Mohs scale (Mohs hardness 4.5-5); iron oxide (Mohs hardness 6), titanium oxide (Mohs hardness 6.5), oxidation Metal oxides such as zinc (Mohs hardness 4) and alumina (Mohs hardness 9); metal carbonates such as calcium carbonate (Mohs hardness 3) and magnesium carbonate (Mohs hardness 3.5); calcium sulfate (Mohs hardness 3.5) ), Metal sulfates such as barium sulfate (Mohs hardness 3 to 3.5); phosphates such as calcium pyrophosphate (Mohs hardness 5) and anhydrous dicalcium phosphate (Mohs hardness 3.5); 9); Mohs hardness (Mohs hardness 9); Mohs hardness 9) and the like (Mohs hardness 9). In the present invention, one or more selected from the group consisting of silica and barium sulfate as the component (B) from the viewpoints of suppressing surface whitening of the molded product, low dust generation of the molded product, and weld strength of the molded product. It is preferable to use, and 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. When the content of the component (B) is 2.5% by mass or more, the weld strength 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 content of the component (B) 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 (B) is 5 to 20% by mass.

[(C) Plate-shaped filler]
The component (C) is a plate-like filler, and the Mohs hardness of the component (C) is 2.0 or more, preferably 2.2 or more, and more preferably 2.5 or more. When the Mohs hardness of the component (C) is 2.0 or more, the surface hardness of the molded product tends to be high, so that the molded product is less likely to be scratched, cracked, dented, etc. even when subjected to an impact, and has impact resistance. Easy to improve. The upper limit of the Mohs hardness is not particularly limited, and may be 10 or less, 8 or less, or 7 or less. The component (C) can be used alone or in combination of two or more.

In the liquid crystal resin composition of the present invention, the content of the (C) plate-like filler is 2.5 to 32.5% by mass. When the content of the component (C) is 2.5% by mass or more, firstly, the surface hardness of the molded product tends to be high, so that the molded product is scratched, cracked, dented or the like even when it receives an impact. It is difficult and the impact resistance is easily improved, and secondly, it is easy to obtain a molded product having reduced ball bearing sliding wear resistance. When the content of the component (C) 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 tend to be high. The content of the component (C) is preferably 5 to 30% by mass.

Examples of the component (C) include mica (Mohs hardness 2 to 3), glass flakes (Mohs hardness 5), and various metal foils. Mica is preferable in that it suppresses warpage deformation of the molded product obtained from the liquid crystal resin composition without deteriorating the fluidity of the liquid crystal resin composition. The median diameter of the plate-shaped filler is not particularly limited, and a smaller diameter is desirable in consideration of the fluidity of the liquid crystal resin composition. On the other hand, in order to reduce the warp deformation of the molded product obtained from the liquid crystal resin composition, it is necessary to maintain a constant size. Specifically, 1 to 100 μm is preferable, and 5 to 50 μm is more preferable.

[Mica]
Mica is a pulverized product of silicate minerals containing aluminum, potassium, magnesium, sodium, iron and the like. Examples of mica that can be used in the present invention include muscovite, phlogopite, biotite, and artificial mica. Of these, muscovite is preferable because it has a good hue and is inexpensive.

Further, in the production of mica, a wet pulverization method and a dry pulverization method are known as methods for pulverizing minerals. The wet pulverization method is a method in which rough mica is roughly pulverized by a dry pulverizer, water is added, and the main pulverization is performed by wet pulverization in a slurry state, and then dehydration and drying are performed. Although the dry pulverization method is a low-cost and general method as compared with the wet pulverization method, it is easier to pulverize the mineral thinly and finely by using the wet pulverization method. In the present invention, it is preferable to use a thin and fine pulverized product because mica having a preferable average particle size and thickness described later can be obtained. Therefore, in the present invention, it is preferable to use mica produced by the wet pulverization method.

Further, since the wet pulverization method requires a step of dispersing the object to be crushed in water, a coagulation sedimentation agent and / or a sedimentation aid is added to the object to be pulverized in order to improve the dispersion efficiency of the object to be pulverized. Is common. Examples of the coagulation sedimentation agent and sedimentation aid that can be used in the present invention include polyaluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, copper chloride, polyiron sulfate, ferric chloride, and iron-silica inorganic high. Examples thereof include ferric chloride-silica inorganic polymer flocculant, slaked lime (Ca (OH) ₂ ), caustic soda (NaOH), soda ash (Na ₂ CO ₃ ) and the like. These coagulation sedimentation agents and sedimentation aids have an alkaline or acidic pH. The mica used in the present invention is preferably one that does not use a coagulation sedimentation agent and / or a sedimentation aid during wet pulverization. When mica that has not been treated with a coagulation sedimentation agent and / or a sedimentation aid is used, decomposition of the polymer in the liquid crystal resin composition is unlikely to occur, and a large amount of gas is less likely to be generated or the molecular weight of the polymer is less likely to decrease. It is easy to maintain better performance.

The median diameter of mica that can be used in the present invention is preferably 10 to 100 μm, particularly preferably 20 to 80 μm. When the median diameter of mica is 10 μm or more, the effect of improving the rigidity of the molded product is likely to be sufficient, which is preferable. When the median diameter of mica is 100 μm or less, the rigidity of the molded product is likely to be sufficiently improved, and the weld strength is also likely to be sufficient, which is preferable. Further, when the median diameter of mica is 100 μm or less, it is easy to secure sufficient fluidity for molding the molded product.

The thickness of mica that can be used in the present invention is preferably 0.01 to 1 μm, particularly preferably 0.03 to 0.3 μm, as measured by observation with an electron microscope. When the thickness of the mica is 0.01 μm or more, the mica is less likely to crack during the melt processing of the liquid crystal resin composition, and the rigidity of the molded product may be easily improved, which is preferable. When the thickness of mica is 1 μm or less, the effect of improving the rigidity of the molded product is likely to be sufficient, which is preferable.

The mica that can be used in the present invention may be surface-treated with a silane coupling agent or the like, and / or may be granulated with a binder to form granules.

Further, the total content of the component (B) and the component (C) is 22.5 to 37.5% by mass, preferably 25 to 35% by mass in the liquid crystal resin composition of the present invention. .. When the total content of the above is 22.5% by mass or more, firstly, the low warpage property of the molded body tends to be high, and secondly, the surface hardness of the molded body tends to be high. Even if it receives an impact, scratches, cracks, dents, etc. are less likely to occur, the impact resistance is likely to be improved, and thirdly, it is easy to obtain a molded product having reduced ball bearing sliding wear resistance. When the total content is 37.5% by mass or less, the effect of suppressing surface whitening of the molded product and the low dust generation property of the molded product tend to be high.

[(D) Epoxy group-containing copolymer]
The liquid crystal composition of the present invention may contain (D) an epoxy group-containing copolymer. (D) 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. (D) 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 α-olefin and a repeating unit derived from a glycidyl ester of an α, β-unsaturated acid. Be done.

The α-olefin is not particularly limited, and examples thereof include ethylene, propylene, butene, etc. Among them, ethylene is preferably used. The glycidyl ester of α, β-unsaturated acid is represented by the following general formula (IV). The glycidyl ester of α, β-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.

(D1) In the epoxy group-containing olefin-based copolymer, the content of the repeating unit derived from α-olefin is 87 to 98% by mass, and the content of the repeating unit derived from the glycidyl ester of α, β-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, α-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 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 and a radical polymerization catalyst corresponding to each component. More specifically, usually, the presence of a suitable solvent or chain transfer agent for α-olefin and glycidyl ester of α, β-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 α-olefin, an α, β-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 α, β-unsaturated acid. Be done. The description of the glycidyl ester of α, β-unsaturated acid is omitted because it is the same as that described in the component (D1).

Examples of styrenes include styrene, α-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 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).

(D2) In the epoxy group-containing styrene-based copolymer, the content of the repeating unit derived from the glycidyl ester of α, β-unsaturated acid is 2 to 20% by mass, and the content of the repeating unit derived from styrenes. Is preferably 80 to 98% by mass.

(D2) 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 α, β-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 α, β-unsaturated acid glycidyl ester and a radical generator are mixed and melt-grafted in an extruder.

As the (D) epoxy group-containing copolymer, the (D1) epoxy group-containing olefin-based copolymer is preferable in terms of heat resistance. When the component (D1) and the component (D2) are used in combination, the ratio of these components can be appropriately selected according to the required characteristics.

The content of the epoxy group-containing copolymer (D) 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. When the content of the component (D) is within the above range, it is easy to obtain a molded product having reduced ball bearing sliding wear without impairing the fluidity of the liquid crystal resin composition. The content is more preferably 1.5 to 4.5% by mass, and even more preferably 3.5 to 4.5% by mass.

[(E) Carbon Black]
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 μm or more is contained, the resin composition of the present invention is molded. Many bumps (fine bumpy protrusions (fine irregularities) in which carbon black is agglomerated) are unlikely to occur on the surface of the molded product. When the content of the particles having a particle size of 50 μm 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 blending amount of the carbon black (E) may be, for example, 0 to 5% by mass, preferably 0.5 to 5% by mass in the liquid crystal resin composition. When the blending amount of carbon black is 0.5% by mass or more, the jet-blackness of the resin composition is unlikely to decrease, 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 unlikely to be uneconomical and lumps are unlikely to occur.
[(F) Release agent]
The release agent (F) 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 amount of the release agent (F) to be blended in the liquid crystal resin composition may be, for example, 0 to 3% by mass, preferably 0.1 to 3% by mass. When the amount of the release agent compounded 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. When the blending amount of the 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.

[Other ingredients]
The liquid crystal resin composition of the present invention includes 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 (B) granular fillers, (C) plate-shaped fillers, and (E) fillers other than carbon black, for example, granular fillers other than the component (B); Plate-like fillers less than 2.0; fibrous fillers can be mentioned. Other fillers may be used alone or in combination of two or more. Examples of the granular filler other than the component (B) include gypsum (calcium sulfate / dihydrate) and the like. Examples of the plate-like filler having a Mohs hardness of less than 2.0 include talc. Examples of the fibrous filler include whiskers. However, from the viewpoint of impact resistance of the molded product, the liquid crystal resin composition of the present invention preferably does not contain a plate-like filler having a Mohs hardness of less than 2.0, such as talc. Similarly, from the viewpoint of impact resistance of the molded product and the like, the liquid crystal resin composition of the present invention preferably does not contain a granular filler other than the component (B) such as gypsum. Further, from the viewpoint of the weld strength of the molded product and the like, the liquid crystal resin composition of the present invention preferably does not contain a fibrous filler.

[Method of preparing liquid crystal resin composition for ball bearing sliding wear member]
The method for preparing the liquid crystal resin composition for a ball bearing sliding wear member of the present invention is not particularly limited. For example, the above-mentioned components (A) to (C), and optionally at least one of the above-mentioned (D) to (F) components and other components are blended, and these are blended using a single-screw or twin-screw extruder. The liquid crystal resin composition for a ball bearing sliding wear member is prepared by melt-kneading.

[Liquid crystal resin composition for ball bearing sliding wear member]
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. More preferably. In the present specification, as 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.

<Ball bearing sliding wear resistant member>
A ball bearing sliding wear resistant member is manufactured using the liquid crystal resin composition of the present invention. The ball bearing sliding wear member of the present invention has excellent surface whitening suppression, low warpage, weld strength, and low dust generation in a well-balanced manner, while reducing ball bearing sliding wear resistance and impact resistance. It is improving. 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, it is used in a form that dynamically contacts the ball bearing. It can be used for camera module parts such as lens holders.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples.

<Liquid crystal resin>
-After charging the following raw materials into a liquid crystal polyesteramide resin polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised to 340 ° C. over 4.5 hours, and then the pressure is reduced to 10 Torr (that is, 1330 Pa) over 15 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points. Melt polymerization was performed. After 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.
(I) 4-Hydroxybenzoic acid (HBA); 1380 g (60 mol%)
(II) 2-Hydroxy-6-naphthoic acid (HNA); 157 g (5 mol%)
(III) Terephthalic acid (TA); 484 g (17.5 mol%)
(IV) 4,4'-dihydroxybiphenyl (BP); 388 g (12.5 mol%)
(V) 4-acetoxyaminophenol (APAP); 126 g (5 mol%)
Metal catalyst (potassium acetate catalyst); 110 mg
Acylating agent (acetic anhydride); 1659 g

<Materials other than liquid crystal resin>
-Silica 1: Admafine SO-C2 (manufactured by Admatex Co., Ltd., silica, median diameter 0.5 μm, Mohs hardness 6)
-Silica 2: Admafine SO-C6 (manufactured by Admatex Co., Ltd., silica, median diameter 2.0 μm, Mohs hardness 6)
-Silica 3: Denka fused silica FB-5SDC (manufactured by Denka Co., Ltd., silica, median diameter 4.0 μm, Mohs hardness 6)
-Silica 4: Denka fused silica FB-7SDC (manufactured by Denka Co., Ltd., silica, median diameter 7.0 μm, Mohs hardness 6)
-Glass beads: EGB731 (manufactured by Potters Barotini Co., Ltd., glass beads, median diameter 20.0 μm, Mohs hardness 5)
-Mica: AB-25S (manufactured by Yamaguchi Mica Co., Ltd., mica, median diameter 25.0 μm, Mohs hardness 2.8)
-Talc: Crown talc PP (manufactured by Matsumura Sangyo Co., Ltd., talc, median diameter 14.6 μm, Mohs hardness 1)
-Potato titanate: Tismo N-102 (manufactured by Otsuka Chemical Co., Ltd., potassium titanate fiber, average fiber diameter 0.3-0.6 μm, average fiber length 10-20 μm)
-Wollastonite: NYGLOS 8 (manufactured by NYCO Materials, calcium silicate whiskers (Wollastonite), number average fiber length 136 μm, average fiber diameter 8 μm)
-Epoxy group-containing olefin copolymer: Bond First 2C (manufactured by Sumitomo Chemical Co., Ltd., ethylene-glycidyl methacrylate copolymer, glycidyl methacrylate content 6% by mass)
-Carbon black: VULCAN XC305 (manufactured by Cabot Japan Co., Ltd., average particle size 20 nm, proportion of particles with a particle size of 50 μm or more is 20 ppm or less)
-Release agent: Pentaerythritol tetrastearate (manufactured by Emery Oleo Chemicals Japan Co., Ltd.)

<Manufacturing of liquid crystal resin composition for ball bearing sliding wear member>
The above components are melt-kneaded at a cylinder temperature of 350 ° C. using a twin-screw extruder (TEX30α type manufactured by Japan Steel Works, Ltd.) at the ratios (unit: mass%) shown in Tables 1 to 5, and ball bearing resistance. Liquid crystal resin composition pellets for sliding wear members were obtained.

<Surface whitening>
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 (12.5 mm × 120 mm × 0.8 mm). ) Was obtained. The test piece for measurement was subjected to an ultrasonic cleaner (output 300 W, frequency 45 kHz) in water (80 ml) at room temperature for 3 minutes. Then, the surface of the test piece for measurement was visually observed. The surface whitening of the test piece for measurement was evaluated according to the following criteria. The results are shown in Tables 1-5.
○ (Good): No whitening is observed on the entire surface of the test piece.
◯-(Slightly good): Slight whitening is observed near the gate and / or near the ejector pin marks.
X (defective): Clear whitening is observed on the smooth part of the test piece.
〔Molding condition〕
Cylinder temperature: 350 ℃
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. 1, a load is applied to the ball 4 (diameter 5 mm, made of SUS) at the tip of the arm 3 via the grease 2 on the measurement test piece 1, 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 stereomicroscope, and the ball bearing sliding wear resistance is determined according to the following criteria. evaluated. The results are shown in Tables 1-5.
◯ (Good): The width of the ball bearing sliding marks was 540 μm or less.
X (defective): The width of the ball bearing sliding mark was more than 540 μm.
〔Molding condition〕
Cylinder temperature: 350 ℃
Mold temperature: 80 ° C
Injection speed: 33 mm / sec
[Reciprocating sliding conditions]
Slip speed: 5 cm / sec
Stroke: 20mm
Load: 29.6N (3kg weight)
Number of round trips: 1000 times Grease: Made by Toray Dow Corning Co., Ltd., Moricoat EM-30L

<Sledding>
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 10.0 mm × as shown in FIG. 2 (a). A camera module type molded product having a size of 10.0 mm × 1.0 mm was obtained. The obtained camera module type molded product was allowed to stand on a horizontal desk, and the height of the camera module type molded product was measured by a Mitutoyo Quick Vision 404PROCNC image measuring machine. At that time, the heights were measured at a plurality of positions indicated by black circles in FIG. 2B, and the difference between the maximum height and the minimum height from the least squares plane was defined as the warp deformation. The warpability was evaluated according to the following criteria. The results are shown in Tables 1-5.
◯ (Good): The warp deformation was 0.020 mm or less.
Δ (Slightly good): The warp deformation was more than 0.020 mm and 0.025 mm or less.
X (defective): The warp deformation was more than 0.025 mm.
〔Molding condition〕
Cylinder temperature: 350 ℃
Mold temperature: 80 ° C
Injection speed: 100 mm / sec
Holding pressure: 50 MPa

<Weld strength>
The pellets of Examples and Comparative Examples were injection-molded under the following molding conditions, and as shown in FIG. 3, a perforated test piece 10 having a film gate 11 and a hole 12 (perforated flat plate 30 mm × 30 mm × 0.3 mm, hole diameter). 7 mm) was obtained. From the obtained perforated test piece 10, a portion having a width of 4.5 mm on the gate side and a portion having a width of 4.5 mm on the anti-gate side were cut out with the hole 12 in between to obtain

test pieces

13a and 13b for measurement, respectively. The bending strength of each of the

measurement test pieces

13a and 13b was measured under the following measurement conditions, and the value obtained by dividing the bending strength of the measurement test piece 13b on the opposite side by the bending strength of the measurement test piece 13a on the gate side was obtained by welding. As the strength retention rate, the weld strength was evaluated according to the following criteria. The results are shown in Tables 1-5.
◯ (Good): The weld strength retention rate was 55% or more.
Δ (Slightly good): The weld strength retention rate was 45% or more and less than 55%.
X (defective): Weld strength retention rate was less than 45%.
[Molding condition]
Molding machine; Sumitomo Heavy Industries SE30DUZ
Cylinder temperature; 350 ° C-350 ° C-350 ° C-340 ° C-330 ° C
Mold temperature; 90 ° C
Injection speed; 200 mm / sec
Holding pressure; 50 MPa
Holding time; 2 sec
Cooling time; 8 sec
Screw rotation speed; 150 rpm
Screw back pressure; 1 MPa
[Measurement condition]
Measuring machine: RTM-100 manufactured by Orientec Tencilon Universal Testing Machine
Load cell; 100 kg
Span: 4.8 mm
Bending speed: 2 mm / min

<Surface hardness>
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 (12.5 mm × 120 mm × 0.8 mm). ) Was obtained. For the test piece for measurement, use a Rockwell hardness tester (Toyo Seiki Seisakusho Co., Ltd.) to determine the surface hardness under M scale conditions (reference load: 10 kg, test load: 100 kg, steel ball indenter diameter: 1/2 in). It was measured and evaluated according to the following criteria. The results are shown in Tables 1-5.
◯ (Good): The surface hardness was 60 or more.
Δ (Slightly good): The surface hardness was 55 or more and less than 60.
X (defective): The surface hardness was less than 55.
〔Molding condition〕
Cylinder temperature: 350 ℃
Mold temperature: 80 ° C
Injection speed: 100 mm / sec

<Number of dust generated>
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 to obtain a molded product of 12.5 mm × 120 mm × 0.8 mm. It was. This molded product was used as a test piece.
〔Molding condition〕
Cylinder temperature: 350 ℃
Mold temperature: 80 ° C
Injection speed: 100 mm / sec
[Evaluation]
The test piece was subjected to an ultrasonic cleaner (output 300 W, frequency 45 kHz) in water (80 ml) at room temperature for 3 minutes. Then, the number of particles of 2 μm or more present in the water was measured with a particle counter (RION Co., Ltd. liquid particle counter KL-11A (PARTICLE COUNTER)) and evaluated as the number of dust generated. The results are shown in Tables 1-5.

As is clear from the results shown in Tables 1 to 5, the molded product of the example has excellent ball bearing sliding wear resistance in a well-balanced manner in terms of surface whitening suppression, low warpage, weld strength, and low dust generation. It was confirmed that it was reduced and the impact resistance was improved.

1 Measurement test piece 2 Grease 3 Arm 4 Ball 10 Perforated test piece 11 Film gate 11
12

holes

13a, 13b Measurement test piece

Claims

(A) Liquid crystal resin,
Contains (B) granular filler and (C) plate-like filler,
The median diameter of the granular filler (B) is 0.3 to 5.0 μm.
The Mohs hardness of the granular filler (B) is 2.5 or more.
The Mohs hardness of the plate-shaped filler (C) is 2.0 or more.
The content of the granular filler (B) is 2.5 to 22.5% by mass.
The content of the plate-shaped filler (C) is 2.5 to 32.5% by mass.
A liquid crystal resin composition for a ball bearing sliding wear member, wherein the total content of the (B) granular filler and the (C) plate-shaped filler is 22.5 to 37.5% by mass.
The composition according to claim 1, wherein the (C) plate-shaped filler is mica.
The composition according to claim 1 or 2, wherein the (B) granular filler is at least one selected from the group consisting of silica and barium sulfate.
The composition according to any one of claims 1 to 3, further comprising (D) an epoxy group-containing copolymer.
The composition in which the content of the epoxy group-containing copolymer (D) is 1 to 5% by mass.
A ball bearing sliding wear resistant member comprising the composition according to any one of claims 1 to 4.