JP6545416B1 - Liquid crystalline resin composition for sliding wear resistant member and sliding wear resistant member using the same - Google Patents

Abstract

Liquid crystalline resin composition for sliding wear-resistant member used for producing a sliding wear-resistant member having reduced adhesion and sliding wear while having adhesiveness, mechanical strength and heat resistance equivalent to conventional ones And providing a sliding wear resistant member using the same. The liquid crystalline resin composition for sliding wear-resistant members according to the present invention contains (A) a liquid crystalline resin, (B1) talc, (B2) a fibrous filler, and (C) an epoxy group-containing copolymer. The median diameter of the (B1) talc is 50 μm or less, the weight average fiber length of the (B2) fibrous filler is 200 μm or less, and the content of the (C) epoxy group-containing copolymer is And 2.0 to 6.5% by mass.

Description

  The present invention relates to a liquid crystalline resin composition for a sliding wear resistant member and a sliding wear resistant member using the same.

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

  Examples of parts in which a liquid crystalline resin is used include connectors such as FPC connectors; sockets such as memory card sockets; parts for camera modules such as lens holders; relays. These parts are required to be excellent in adhesion and impact resistance, and may be used in a form in which two or more members are in dynamic contact, so sliding abrasion (ie, 2 It is also sought to reduce the ease of wear when one or more members are in dynamic contact. For example, Patent Document 1 deals with a liquid crystalline resin and a talc having a specific volume average particle diameter, with the object of providing a molded article comprising a liquid crystalline resin composition excellent in surface appearance and excellent in slidability. A liquid crystalline resin composition is disclosed, which contains at a specific ratio.

Patent No. 5087 958

  However, according to the study of the present inventors, in the conventional liquid crystalline resin composition, the reduction of the sliding wear resistance is insufficient. The present invention has been made to solve the above-mentioned problems, and its object is to provide a slide resistance that is reduced in sliding abrasion while having the same adhesiveness, mechanical strength, and heat resistance as conventional. It is an object of the present invention to provide a liquid crystalline resin composition for a sliding wear resistant member used for producing a dynamic wear member, and a sliding wear resistant member using the same.

  The present inventors have intensively studied to solve the above problems. As a result, it contains a liquid crystalline resin, talc having a specific median diameter, a fibrous filler having a specific weight average fiber length, and an epoxy group-containing copolymer, and the content of the epoxy group-containing copolymer is predetermined. It has been found that the above-mentioned problems can be solved by using a liquid crystalline resin composition which falls within the above range, and the present invention has been completed. More specifically, the present invention provides the following.

  (1) A liquid crystalline resin (A), (B1) talc, (B2) a fibrous filler, and (C) an epoxy group-containing copolymer are contained, and the median diameter of the (B1) talc is 50 μm or less The weight average fiber length of the (B2) fibrous filler is 200 μm or less, and the content of the (C) epoxy group-containing copolymer is 2.0 to 6.5 mass%. Liquid crystalline resin composition for dynamic wear members.

  (2) The content of the (B1) talc is 20 to 42% by mass, the content of the (B2) fibrous filler is 8 to 15% by mass, and the (B1) talc and the B2) The composition according to (1), wherein the total content with the fibrous filler is 35 to 50% by mass.

  (3) A sliding wear resistant member comprising the composition according to (1) or (2).

  When a sliding wear resistant member is produced using the liquid crystalline resin composition for a sliding wear resistant member of the present invention as a raw material, the sliding wear is obtained while having the same adhesiveness, mechanical strength and heat resistance as before. It is possible to obtain a sliding wear resistant member with reduced elasticity.

Fig.1 (a) is a figure for demonstrating the manufacturing method of the sample for epoxy adhesiveness evaluation, and FIG.1 (b) is a figure for demonstrating the method of epoxy adhesiveness evaluation. FIG. 2 is a diagram for explaining a method of sliding wear evaluation.

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

<Liquid crystalline resin composition for sliding wear resistant members>
The liquid crystalline resin composition for a sliding wear resistant member of the present invention comprises (A) a liquid crystalline resin, (B1) talc, (B2) a fibrous filler, and (C) an epoxy group-containing copolymer. .

[(A) Liquid crystalline resin]
The (A) liquid crystalline resin used in the present invention refers to a melt-processable polymer having a property capable of forming an optically anisotropic melt phase. The properties of the anisotropic melt phase can be confirmed by a conventional polarization inspection method using crossed polarizers. More specifically, confirmation of the anisotropic melting phase can be performed by observing the molten sample mounted on the Leitz hot stage under a nitrogen atmosphere at a magnification of 40 using a Leitz polarization microscope. The liquid crystalline polymer applicable to the present invention, when inspected between crossed polarizers, normally transmits polarized light and exhibits optical anisotropy even in the melt stationary state.

  It does not specifically limit as a kind of above (A) liquid crystalline resin, It is preferable that it is aromatic polyester and / or aromatic polyester amide. In addition, polyesters partially containing aromatic polyesters and / or aromatic polyester amides in the same molecular chain are within the scope. The liquid crystalline 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 (I.V.) of are preferably used.

  The aromatic polyester or aromatic polyesteramide as the liquid crystalline resin (A) applicable to the present invention is particularly preferably at least one selected from the group consisting of aromatic hydroxycarboxylic acid, aromatic hydroxyamine and aromatic diamine. It is an aromatic polyester or aromatic polyester amide which has a repeating unit derived from a compound of a kind as a component.

More specifically,
(1) A polyester comprising repeating units mainly derived from one or more of aromatic hydroxycarboxylic acids and their derivatives;
(2) A repeating unit mainly derived from one or two or more of (a) aromatic hydroxycarboxylic acid and its derivative, and (b) one kind of aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and their derivatives Or a polyester comprising a repeating unit derived from two or more species and a repeating unit derived from (c) at least one species or two or more species of an aromatic diol, an alicyclic diol, an aliphatic diol, and derivatives thereof;
(3) A repeating unit mainly derived from one or two or more of (a) aromatic hydroxycarboxylic acids and their derivatives, and (b) one or two of aromatic hydroxyamines, aromatic diamines, and their derivatives A polyesteramide comprising a repeating unit derived from a species or more and a repeating unit derived from (c) an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and one or more of derivatives thereof;
(4) A repeating unit mainly derived from one or two or more of (a) aromatic hydroxycarboxylic acid and its derivative, and (b) one or two of aromatic hydroxyamine, aromatic diamine, and their derivatives Repeating units derived from species or more, (c) repeating units derived from one or more kinds of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof, (d) aromatic diols, alicyclics And polyesteramides composed of repeating units derived from at least one or more of aliphatic diols, aliphatic diols, and derivatives thereof. If necessary, a molecular weight modifier may be used in combination with the above-mentioned components.

（Ｘ：アルキレン（Ｃ_１〜Ｃ_４）、アルキリデン、−Ｏ−、−ＳＯ−、−ＳＯ_２−、−Ｓ−、及び−ＣＯ−より選ばれる基である）

（Ｙ：−（ＣＨ_２）_ｎ−（ｎ＝１〜４）及び−Ｏ（ＣＨ_２）_ｎＯ−（ｎ＝１〜４）より選ばれる基である。）Preferred examples of the specific compound constituting the liquid crystalline resin (A) applicable to the present invention include 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, resorcine, compounds represented by the following general formula (I), and compounds 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- Aromatic amines such as phenylenediamine can be mentioned.

(X: a group selected from alkylene (C ₁ -C ₄ ), alkylidene, -O-, -SO-, -SO _2- , -S-, and -CO-)

_{(Y :-( CH 2) n -} (n = 1~4) and _{-O (CH} 2) a n O- (n = 1~4) from the group selected).

The preparation of the liquid crystalline resin (A) used in the present invention can be carried out from the above-mentioned monomer compound (or mixture of monomers) by a direct polymerization method or a transesterification method by a known method, and usually a melt polymerization method And slurry polymerization. The above compounds having an ester forming ability may be used for polymerization as they are, or may be those which are converted from a precursor into a derivative having the ester forming ability at a stage prior to polymerization. In the polymerization, various catalysts can be used, and typical ones are dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, alkali of carboxylic acid And alkaline earth metal salts, Lewis acid salts such as BF _{3 and} the like. The amount of catalyst used is generally preferably about 0.001 to 1% by weight, in particular about 0.01 to 0.2% by weight, based on the total weight of the monomers. If necessary, the polymers produced by these polymerization methods can be increased in molecular weight by solid phase polymerization heated under reduced pressure or in an inert gas.

The melt viscosity of the liquid crystalline resin (A) obtained by the above method is not particularly limited. In general, one having a melt viscosity at molding temperature of 10 MPa or more and 600 MPa or less at a shear rate of 1000 sec ⁻¹ can be used. However, those having too high viscosity are not preferable because the flowability is extremely deteriorated. The liquid crystalline resin (A) may be a mixture of two or more liquid crystalline resins.

  In the liquid crystalline resin composition of the present invention, the preferable content of the (A) liquid crystalline resin is 43.5 to 63% by mass. The content of the component (A) is preferably 43.5% by mass or more from the viewpoint of fluidity, and the content of the component (A) is preferably 63% by mass or less from the viewpoint of heat resistance. The content of the component (A) is more preferably 48 to 60.5% by mass, still more preferably 51 to 59% by mass, and particularly preferably 53 to 57% by mass.

[(B1) talc]
By using talc (B1) in combination with the (C) epoxy group-containing copolymer, the adhesion of the molded product obtained from the liquid crystalline resin composition of the present invention is improved, and the sliding of the molded product is caused. It contributes to reducing wear resistance. (B1) talc can be used singly or in combination of two or more.

  (B1) The median diameter of talc is 50 μm or less. When the median diameter is more than 50 μm, the melt viscosity of the obtained liquid crystalline resin composition tends to increase, and when the liquid crystalline resin composition is molded, mold deposit (hereinafter also referred to as “MD”) is generated. It's easy to do. The median diameter is preferably 10 to 25 μm, more preferably 11 to 20 μm, and still more preferably 12 to 16 μm because melt viscosity and MD are easily reduced. In addition, in this specification, a median diameter means the median value of the volume reference | standard measured by laser diffraction / scattering type particle size distribution measuring method. Moreover, a mold deposit means the deposit | attachment to the metal mold | die in shaping | molding.

  The content of the component (B1) in the liquid crystal composition of the present invention is preferably 20 to 42% by mass. Melt viscosity and MD are easy to reduce that the said content is 20-42 mass%. The content is more preferably 21 to 40% by mass, still more preferably 23 to 37% by mass, and particularly preferably 25 to 35% by mass because adhesion is easily improved and melt viscosity and MD are more easily reduced. %.

[(B2) fibrous filler]
The liquid crystalline resin composition of the present invention can give a molded article excellent in heat resistance, for example, heat resistance as evaluated by high temperature rigidity, by containing the (B2) fibrous filler. The fibrous filler (B2) can be used singly or in combination of two or more. In addition, high temperature rigidity is evaluated by measuring deflection temperature under load (hereinafter, also referred to as "DTUL") in accordance with ISO 75-1, 2.

  (B2) The weight average fiber length of the fibrous filler is 200 μm or less, preferably 25 to 170 μm, and more preferably 30 to 150 μm. When the weight average fiber length is more than 200 μm, the flowability of the liquid crystalline resin composition is unlikely to be sufficient. The mechanical strength and heat resistance of the molded product obtained from the liquid crystalline resin composition of the present invention tend to be improved when the weight average fiber length is 25 μm or more. In addition, an average fiber length takes in a stereomicroscope image from a CCD camera to PC, and adopts a value measured by an image processing method by an image measuring machine.

  The preferable average fiber diameter of the (B2) fibrous filler is 20 μm or less, and the more preferable average fiber diameter is 5 to 15 μm. When the average fiber diameter is 20 μm or less, raising of the surface of the molded body can be easily suppressed. In addition, an average fiber diameter takes in a stereomicroscope image from a CCD camera to PC, and adopts a value measured by an image processing method by an image measuring machine.

  Any fiber can be used as long as it is a fibrous filler satisfying the above-mentioned shape, but as the fibrous filler (B2), for example, glass fiber, milled fiber, carbon fiber, asbestos fiber, silica fiber And inorganic fibrous materials such as silica-alumina fibers, zirconia fibers, boron nitride fibers, boron nitride fibers, boron fibers, potassium titanate fibers, and further fibrous materials of metals such as stainless steel, aluminum, titanium, copper, brass and the like Be In the present invention, it is preferable to use a milled fiber as the component (B2). In addition, the shape of (B2) component in the liquid crystalline resin composition of this invention and the shape of (B2) component before it mix | blends differ. The shape of the above-mentioned (B2) component is a shape before it is mix | blended. If the shape before being compounded is as above-mentioned, it will be easy to obtain the molded object which is excellent in heat resistance.

  The content of the component (B2) in the liquid crystalline resin composition of the present invention is preferably 8 to 15% by mass, more preferably 8.5 to 13% by mass, and still more preferably 9 to 11% by mass. When the content of the component (B2) is within the above range, the flowability of the liquid crystalline resin composition is sufficiently ensured, and the mechanical strength and the heat resistance of the molded body obtained from the liquid crystalline resin composition are improved. Cheap.

  The total content of (B1) talc and (B2) fibrous filler is preferably 35 to 50% by mass, more preferably 37 to 46% by mass, and still more preferably in the liquid crystalline resin composition of the present invention Is 38 to 44% by mass. When the content of the component (B2) is within the above range, the flowability of the liquid crystalline resin composition is sufficiently ensured, and the mechanical strength and the heat resistance of the molded body obtained from the liquid crystalline resin composition are improved. Cheap.

[(C) epoxy group-containing copolymer]
The liquid crystalline composition of the present invention contains (C) an epoxy group-containing copolymer. The epoxy group-containing copolymer (C) can be used singly or in combination of two or more. The (C) epoxy group-containing copolymer is not particularly limited, and, for example, at least one selected from the group consisting of (C1) epoxy group-containing olefin copolymer and (C2) epoxy group-containing styrene copolymer There is one kind. The sliding abrasion property of the molded object obtained from the liquid crystalline resin composition of this invention by using 2.0-6.5 mass% of (C) epoxy group containing copolymers in combination with (B) talc Contribute to reducing the

  Examples of the (C1) epoxy group-containing olefin copolymer include copolymers 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

The α-olefin is not particularly limited, and examples thereof include ethylene, propylene and butene. Among them, ethylene is preferably used. The glycidyl ester of the α, β-unsaturated acid is represented by the following general formula (IV). Glycidyl esters of α, β-unsaturated acids are, for example, acrylic acid glycidyl ester, methacrylic acid glycidyl ester, ethacrylic acid glycidyl ester, itaconic acid glycidyl ester and the like, with methacrylic acid glycidyl ester being particularly preferable.

  (C1) In the epoxy group-containing olefin 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 glycidyl ester of α, β-unsaturated acid The amount is preferably 13 to 2% by mass.

  The (C1) epoxy group-containing olefin copolymer used in the present invention is a third component other than the above two components within the range that does not impair the present invention, and acrylonitrile, acrylic ester, methacrylic ester, α-methylstyrene, and maleic anhydride The repeating unit derived from one or more of olefinic unsaturated esters such as acids may be contained in an amount of 0 to 48 parts by mass based on 100 parts by mass of the two components.

  The epoxy group-containing olefin copolymer, which is the component (C1) of the present invention, can be easily prepared by a conventional radical polymerization method using a monomer corresponding to each component and a radical polymerization catalyst. More specifically, the presence of a suitable solvent or chain transfer agent at a pressure of 500 to 4000 atm. At 100 to 300 ° C. in the presence of a radical generator, usually an α-olefin and a glycidyl ester of an α, β-unsaturated acid It can be produced by the method of copolymerization under or without. It can also be produced by a method in which an α-olefin, a glycidyl ester of an α, β-unsaturated acid and a radical generator are mixed and melt graft copolymerized in an extruder.

  Examples of the epoxy group-containing styrene-based copolymer of (C2) include copolymers composed of a repeating unit derived from styrenes and a repeating unit derived from a glycidyl ester of an α, β-unsaturated acid. Be About the glycidyl ester of the (alpha), (beta)-unsaturated acid, since it is the same as that of what was demonstrated by the (C1) component, description is abbreviate | omitted.

  Styrenes include styrene, α-methylstyrene, brominated styrene, divinylbenzene and the like, with styrene being preferably used.

  The (C2) epoxy group-containing styrenic copolymer used in the present invention is a multicomponent copolymer containing a repeating unit derived from one or more other vinyl monomers as a third component in addition to the above two components. It may be. Preferred as the third component are repeating units derived from one or more of olefinically unsaturated esters such as acrylonitrile, acrylic esters, methacrylic esters, 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 (C2).

  (C2) In the epoxy group-containing styrenic copolymer, the content of repeating units derived from glycidyl esters of α, β-unsaturated acids is 2 to 20% by mass, and the content of repeating units derived from styrenes It is preferable that it is 80-98 mass%.

  The (C2) epoxy group-containing styrenic copolymer can be prepared by a conventional radical polymerization method using a monomer corresponding to each component and a radical polymerization catalyst. More specifically, usually, styrenes and glycidyl esters of α, β-unsaturated acids in the presence of a radical generator at 500 to 4000 atm at 100 to 300 ° C. in the presence of a suitable solvent or chain transfer agent Or it can manufacture by the method of making it copolymerize in absence. It can also be produced by a method in which styrenes and a glycidyl ester of an α, β-unsaturated acid and a radical generator are mixed and melt graft copolymerized in an extruder.

  As the (C) epoxy group-containing copolymer, a (C1) epoxy group-containing olefin copolymer is preferable from the viewpoint of heat resistance. When the (C1) component and the (C2) component are used in combination, the ratio of these components can be appropriately selected in accordance with the required characteristics.

  The content of the (C) epoxy group-containing copolymer is 2.0 to 6.5% by mass in the liquid crystalline resin composition of the present invention. If the content of the component (C) is within the above range, it is easy to obtain a molded article with reduced sliding wear, without impairing the flowability. The more preferable content is 2.5 to 6.0 mass%, and the still more preferable content is 3.0 to 5.0 mass%.

[(D) carbon black]
The (D) carbon black used as an optional component in the present invention is not particularly limited as long as it is generally available for resin coloring. In general, (D) carbon black contains a lump formed by aggregation of primary particles, but the resin composition of the present invention is molded unless a large number of lumps having a size of 50 μm or more is contained. It is hard to generate many bumps (fine bumps (fine irregularities) in which carbon black is aggregated) on the surface of the resulting molded body. When the content of 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 body tends to be high. The preferred content is 5 ppm or less.

  As a compounding quantity of (D) carbon black, in a liquid crystalline resin composition, the range of 0.5-5 mass% is preferable. When the blending amount of carbon black is 0.5% by mass or more, the jettackiness of the obtained resin composition is unlikely to be lowered, and the light shielding property is less likely to be disturbed. When the amount of carbon black is 5% by mass or less, it is difficult to become uneconomical and it is difficult to generate bumps.

[(E) mold release agent]
The (E) mold release agent used as an optional component in the present invention is not particularly limited as long as it is generally available, and, for example, fatty acid esters, fatty acid metal salts, fatty acid amides, low Molecular weight polyolefin etc. are mentioned, and fatty acid ester of pentaerythritol (for example, pentaerythritol tetrastearate) is preferable.

  As a compounding quantity of (E) mold release agent, in a liquid crystalline resin composition, the range of 0.1-3 mass% is preferable. While the mold release property at the time of shaping | molding improves that the compounding quantity of a mold release agent is 0.1 mass% or more, it is easy to obtain the molded object by which sliding abrasion property was reduced. If the compounding amount of the release agent is 3% by mass or less, MD is easily reduced.

[Other ingredients]
The liquid crystalline resin composition of the present invention is a known substance generally added to other polymers, other fillers, and synthetic resins, as long as the effects of the present invention are not impaired. Stabilizers such as agents, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, crystallization accelerators, crystal nucleating agents, and the like can be appropriately added according to the required performance.

  The other fillers include fillers other than (B1) talc, (B2) fibrous fillers, and (D) carbon black, and examples thereof include particulate fillers such as silica. However, it is preferable that the liquid crystalline resin composition of the present invention does not contain mica, from the viewpoints of improvement of adhesion and reduction of melt viscosity, MD, and sliding abrasion resistance.

[Method of preparing liquid crystalline resin composition for sliding wear resistant member]
The preparation method of the liquid crystalline resin composition for a sliding wear resistant member of the present invention is not particularly limited. For example, by blending the components (A), (B1), (B2) and (C) and melt-kneading them using a single- or twin-screw extruder, for sliding wear resistant members Preparation of a liquid crystalline resin composition is performed.

[Liquid crystalline resin composition for sliding wear resistant members]

The liquid crystalline resin composition of the present invention obtained as described above preferably has a melt viscosity of less than 70 Pa · sec from the viewpoint of MD reduction. It is one of the features of the liquid crystalline resin composition of the present invention that it has high flowability at the time of melting and is excellent in moldability. The melt viscosity is more preferably 60 Pa · sec or less, still more preferably 55 Pa · sec or less. The lower limit of the melt viscosity is not particularly limited, and may be, for example, 30 Pa · sec or more, or 40 Pa · sec. In the present specification, as the melt viscosity, a value obtained by the measurement method according to ISO 11443 is adopted under the conditions of a cylinder temperature 10 to 20 ° C. higher than the melting point of the liquid crystalline resin and a shear rate of 1000 sec ⁻¹ .

<Sliding-resistant wear member>
A sliding wear resistant member is manufactured using the liquid crystalline resin composition of the present invention. The sliding wear resistant member according to the present invention has reduced sliding wear while having the same adhesiveness, mechanical strength and heat resistance as conventional ones. The sliding wear resistant member of the present invention can be used for parts in which two or more members are in dynamic contact during use. Specifically, for example, a connector such as an FPC connector; a memory card socket etc. It can be used for sockets, camera module parts such as lens holders, relays, etc.

  EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

<Liquid crystalline resin>
Liquid crystalline polyesteramide resin After charging the following raw materials in a polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and reaction was performed at 140 ° C. for 1 hour. Thereafter, the temperature is further raised to 340 ° C. over 4.5 hours, and then the pressure is reduced to 10 Torr (ie, 1330 Pa) over 15 minutes to distill off acetic acid, excess acetic anhydride, and other low boiling components. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced and pressure was applied from under reduced pressure to normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain pellets. The obtained pellet was heat-treated at 300 ° C. for 2 hours under a nitrogen stream to obtain a target 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 above-mentioned polymer was measured in the same manner as the method of 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
Acylation agent (acetic anhydride); 1659 g

<Materials other than liquid crystalline resin>
Talc: Crown Talc PP (manufactured by Matsumura Sangyo Co., Ltd., talc, median diameter 14.6 μm)
・ Fibrous filler 1: PF70E001 (manufactured by Nittobos Co., Ltd., milled fiber, average fiber diameter 10 μm, average fiber length 70 μm (manufacturer nominal value))
In addition, said maker nominal value is different from the value in Table 1 which is the measured value in a composition.
-Fibrous filler 2: ECS03T-786H (manufactured by Nippon Electric Glass Co., Ltd., glass fiber, chopped strand having an average fiber diameter of 10 μm and a length of 3 mm)
・ Epoxy group-containing olefin copolymer: Bond first 2C (manufactured by Sumitomo Chemical Co., Ltd., ethylene-glycidyl methacrylate copolymer, content of glycidyl methacrylate 6 mass%)
Carbon black: VULCAN XC 305 (manufactured by Cabot Japan Ltd., average particle diameter 20 nm, ratio of particles having a particle diameter of 50 μm or more is 20 ppm or less)
Releasing agent: Pentaerythritol tetrastearate (Emerie Oleo Chemicals Japan Co., Ltd.)

<Production of liquid crystalline resin composition for sliding wear resistant 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 a ratio shown in Table 1 to obtain a liquid crystalline resin composition for a sliding wear resistant member Pellets were obtained.

<Weight average fiber length>
The weight average fiber length of the fibrous filler in the liquid crystalline resin composition was measured by the following method.
5 g of liquid crystalline resin composition pellets were incinerated by heating at 600 ° C. for 2 hours. After the ashing residue was sufficiently dispersed in a 5% by mass aqueous polyethylene glycol solution, it was transferred to a petri dish with a syringe and the fibrous filler was observed with a microscope. At the same time, the weight average fiber length of the fibrous filler was measured using an image measurement device (LUZEXFS manufactured by Nireco Co., Ltd.).

Melt viscosity
The melt viscosity of the liquid crystalline resin composition of the example and the comparative example was measured using the above-mentioned pellet. Specifically, the apparent melt viscosity under the conditions of a cylinder temperature of 350 ° C. and a shear rate of 1000 sec ⁻¹ was conformed to ISO 11443 using a capillary rheometer (Capirograph 1 D: piston diameter 10 mm, manufactured by Toyo Seiki Seisakusho Co., Ltd.) Measured. For measurement, an orifice with an inner diameter of 1 mm and a length of 20 mm was used. The results are shown in Table 1.

<Bending test>
The pellets of Examples and Comparative Examples were molded using the molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions to produce 130 mm × 13 mm × 0.8 mm bending test pieces . Using this test piece, flexural strength, flexural modulus, and strain at break were measured in accordance with ASTM D790. Among these, the measurement results of flexural modulus and flexural strength are shown in Table 1.
〔Molding condition〕
Cylinder temperature: 350 ° C
Mold temperature: 90 ° C
Injection speed: 33 mm / sec
Holding pressure: 50MPa

[Load deflection temperature (DTUL)]
The pellets of Examples and Comparative Examples were molded using the molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions to obtain test pieces for measurement (4 mm × 10 mm × 80 mm) . The deflection temperature under load was measured by the method according to ISO 75-1, 2 using this test piece. In addition, 1.8 Mpa was used as bending stress. The results are shown in Table 1.
〔Molding condition〕
Cylinder temperature: 350 ° C
Mold temperature: 80 ° C
Injection speed: 33 mm / sec

<Epoxy adhesive property>
The pellets of Examples and Comparative Examples were molded using the molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions to obtain test pieces (ISO test piece Type 1A, thickness 4 mm) . The test piece was divided into two, and as shown in FIG. 1 (a), they were bonded with an epoxy adhesive (Loctite 3128 NH manufactured by Henkel Corp.) (curing conditions: 80 ° C. × 30 minutes). Thereafter, as shown in FIG. 1 (b), the bonded test pieces were placed, a load was applied in the direction of the arrow using a tensile tester, and the adhesive strength was evaluated from the load when peeled off. The results are shown in Table 1.
〔Molding condition〕
Cylinder temperature: 350 ° C
Mold temperature: 80 ° C
Injection speed: 33 mm / sec
[Tension test conditions]
Testing machine: Orientec, Tensilon RTC-1325A
Test speed: 10 mm / min

<Charpy impact test>
The pellets of Examples and Comparative Examples were molded into test specimens (4 mm × 10 mm × 80 mm) under the following molding conditions using a molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.). Using this test piece, the Charpy impact value was measured by the method according to ISO 179-1. The results are shown in Table 1.
〔Molding condition〕
Cylinder temperature: 350 ° C
Mold temperature: 80 ° C
Back pressure: 2.0MPa
Injection speed: 33 mm / sec

<Sliding wear amount>
The pellets of Examples and Comparative Examples were molded using the molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions, and used for measuring pins (diameter 10 mm, length 10 mm) and for measurement Test pieces (80 mm × 80 mm × 1 mm) were obtained. As shown in FIG. 2, a load is applied to the measuring pin on the measuring test piece, and after performing a reciprocal sliding test under the following reciprocating sliding conditions, the total mass loss of the measuring pin and the measuring specimen is The sliding wear amount was calculated. The results are shown in Table 1.
〔Molding condition〕
Cylinder temperature: 350 ° C
Mold temperature: 80 ° C
Injection speed: 33 mm / sec
[Reciprocating sliding condition]
Sliding speed: 5 cm / sec
Stroke: 20 mm
Load: 9.8 N (1 kg weight)
Number of round trips: 3000 times

注）−：樹脂温上昇及び粘度増加により押出不可

Note)-: Not extrudable due to resin temperature rise and viscosity increase

  As apparent from the results described in Table 1, it is confirmed that the molded articles of the examples have reduced sliding wear while having the same adhesiveness, mechanical strength, and heat resistance as conventional. It was done.

Claims (2)

(A) Liquid crystalline resin,
(B1) talc,
(B2) milled fiber , and (C) epoxy group-containing copolymer,
The median diameter of the (B1) talc is 50 μm or less,
The weight average fiber length of the (B2) milled fiber is 200 μm or less,
The content of the (B1) talc is 20 to 42% by mass,
The content of the (B2) milled fiber is 8 to 15% by mass,
The total content of the (B1) talc and the (B2) milled fiber is 35 to 50% by mass,
Content of the said (C) epoxy-group containing copolymer is 2.0-6.5 mass% liquid crystalline resin composition for sliding abrasion resistant members. A sliding wear resistant member comprising the composition according to claim 1.

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