TW201920480A - Liquid-crystalline resin composition for member with sliding/wear resistance, and member with sliding/wear resistance obtained from same - Google Patents

Abstract

Provided are: a liquid-crystalline resin composition for members with sliding/wear resistance which is for use in producing a member with sliding/wear resistance that has adhesive properties and impact resistance which are equal to those of conventional ones and is reduced in sliding wear; and a member with sliding/wear resistance obtained from the liquid-crystalline resin composition. The liquid-crystalline resin composition for members with sliding/wear resistance according to the present invention comprises (A) a liquid-crystalline resin, (B) talc, and (C) an epoxidized copolymer, wherein the talc (B) has a median diameter of 50 [mu]m or smaller and the epoxidized copolymer (C) is contained in an amount of 2.0-6.5 mass%.

Description

Liquid crystal resin composition for sliding wear-resistant member and sliding wear-resistant member using the same

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

Liquid crystalline resins typified by liquid crystalline polyester resins have excellent mechanical strength, heat resistance, chemical resistance, electrical properties, etc. and achieve a good balance, and also have excellent dimensional stability, so they are widely used as high Performance engineering plastic (engineering plastic) to use. Recently, liquid crystal resins have been used for precision instrument components using the above advantages.

Examples of components using liquid crystalline resin include connectors such as FPC connectors (flexible printed circuit connectors); slots such as memory card sockets; cameras such as lens holders Module (camera module) components; relay (relay). These parts are required to have excellent adhesion and impact resistance, and there are cases where two or more members are used in dynamic contact with each other, so sliding abrasion resistance is also reduced (that is, two or more members are dynamic with each other) Wear resistance when in contact). For example, Patent Document 1 proposes to provide a molded article composed of a liquid crystalline resin composition having a beautiful surface and excellent sliding properties, and discloses that a liquid crystal resin is contained in a specific ratio and a specific volume average particle diameter is included. Liquid crystal resin composition of talc.
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent No. 5087958

[Problems to be Solved by the Invention]

However, according to the study by the present inventors, the degree of reduction in sliding abrasion resistance of the conventional liquid crystalline resin composition is insufficient. The present invention has been made in order to solve the above-mentioned problems, and an object thereof is to provide a liquid crystal resistance for a sliding abrasion-resistant member used for producing a sliding abrasion-resistant member that has the same adhesion and impact resistance as the conventional one while reducing sliding abrasion resistance. Resin composition and sliding wear-resistant member using the same.
[Means for solving problems]

The present inventors have conducted intensive studies in order to solve the above problems. As a result, it was found that by using a liquid crystalline resin composition including a liquid crystalline resin, talc having a specific median particle size, and an epoxy group-containing copolymer, and the content of the epoxy group-containing copolymer is within a predetermined range, it is possible to The above problem is solved, and the present invention is completed. More specifically, the present invention provides the following.

(1) A liquid crystalline resin composition for a sliding abrasion-resistant member, comprising (A) a liquid crystalline resin, (B) talc, and (C) an epoxy-group-containing copolymer, wherein the medium number of the (B) talc The diameter is 50 μm or less, and the content of the (C) epoxy group-containing copolymer is 2.0 to 6.5% by mass.

(2) The composition according to (1), wherein the content of the (B) talc is 25 to 45% by mass.

(3) A sliding abrasion-resistant member composed of the composition described in (1) or (2).
[Effect of the present invention]

When the sliding abrasion resistant member is produced using the liquid crystalline resin composition for a sliding abrasion resistant member of the present invention as a raw material, a sliding abrasion resistant member having the same adhesion and impact resistance as before and having reduced sliding abrasion resistance can be obtained.

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 includes (A) a liquid crystalline resin, (B) talc, and (C) an epoxy group-containing copolymer.
[(A) Liquid crystalline resin]

The (A) liquid crystalline resin used in the present invention refers to a polymer having a melt processability capable of forming an optically anisotropic melt phase. The properties of the anisotropic molten phase can be confirmed by a conventional polarization measurement method using a cross polarizer. More specifically, a Leitz polarizing microscope was used to observe a molten test article placed on a Leitz hot stage at a magnification of 40 times in a nitrogen atmosphere to confirm an anisotropic molten phase. When the liquid crystalline polymer suitable for the present invention is detected between orthogonal polarizers, the polarized light normally passes through and exhibits optical anisotropy even in a molten still state.

The type of the (A) liquid crystalline resin is not particularly limited, and an aromatic polyester and / or an aromatic polyester amide is preferred. In addition, polyesters containing aromatic polyester and / or aromatic polyester amidine partially in the same molecular chain are also within this range. As the (A) liquid crystalline resin, a material having a logarithmic viscosity (IV) of at least about 2.0 centiliter / gram when dissolved in a concentration of 0.1% by mass in pentafluorophenol at 60 ° C is preferred, and 2.0 is preferably used. ~ 10.0 cents liters / gram is more preferred.

The (A) liquid crystalline resin suitable for the present invention is an aromatic polyester or an aromatic polyester amide, which is selected from the group consisting of an aromatic hydroxycarboxylic acid, an aromatic hydroxylamine, and an aromatic An aromatic polyester or an aromatic polyester amide that has a repeating unit derived from at least one compound in a group composed of a diamine as a constituent.

More specifically, (1) a polyester mainly composed of a repeating unit derived from one or more aromatic hydroxycarboxylic acids and derivatives thereof;
(2) Mainly consisting of (a) repeating units derived from one or more aromatic hydroxycarboxylic acids and their derivatives, (b) from aromatic dicarboxylic acids, cycloaliphatic dicarboxylic acids Acids, and repeating units derived from one or more of the foregoing derivatives, and (c) from aromatic diols, alicyclic diols, aliphatic diols, and Polyester consisting of 1 or more derived repeat units;
(3) Mainly consisting of (a) repeating units derived from one or more aromatic hydroxycarboxylic acids and their derivatives, (b) those derived from aromatic hydroxylamines, aromatic diamines, and the aforementioned derivatives One or two or more kinds of repeating units derived from the repeating unit derived from one or two or more kinds of aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and the aforementioned derivative Polyester amide
(4) Mainly consisting of (a) repeating units derived from one or more aromatic hydroxycarboxylic acids and their derivatives, (b) those derived from aromatic hydroxylamines, aromatic diamines, and the aforementioned derivatives One or two or more kinds of repeating units derived, (c) One or two or more kinds of repeating units derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and the aforementioned derivatives, and (d ) Polyesteramine and the like composed of repeating units derived from aromatic diols, alicyclic diols, aliphatic diols, and one or more of the foregoing derivatives.
Moreover, you may use a molecular weight modifier together with the said component as needed.

Preferred examples of specific compounds constituting the (A) liquid crystalline resin applicable to the present invention include p-hydroxybenzoic acid and 6-hydroxy-2 naphthoic acid. -naphthoic acid) and other aromatic hydroxycarboxylic acids, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxyl Benzene (4,4'-dihydroxybiphenyl), hydroquinone, resorcinol, compounds represented by the following general formula (I), and compounds represented by the following general formula (II) And other aromatic diols; terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and Aromatic dicarboxylic acids such as compounds represented by (III); aromatic amines such as p-aminophenol and p-phenylenediamine.
[Chemical 1]

(X: is a group selected from olefin groups (C ₁ to C ₄ ), alkylene groups, -O-, -SO-, -SO _2- , -S-, and -CO-)
[Chemical 2]

[Chemical 3]

(Y: is a group selected from-(CH ₂ ) _n- (n = 1 ~ 4) and -O (CH ₂ ) _n O- (n = 1 ~ 4))

The preparation of the (A) liquid crystalline resin used in the present invention can be performed by a known method from the above-mentioned monomer compound (or a mixture of monomers) using a direct polymerization method or a transesterification method, and usually, A melt polymerization method, a slurry polymerization method, or the like is used. The above-mentioned compounds having an ester-forming ability may also be directly used for polymerization, or may be modified from precursors into derivatives having an ester-forming ability at the initial stage of polymerization. During the above polymerization, various catalysts can be used. Representative examples include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicate, and titanium alcoholation. Titanium alcoholates, alkali metal and alkaline earth metal salts of carboxylic acid bases, such as the Lewis acid salt of BF ₃ and the like. The amount of the catalyst used is usually 0.001 to 1% by mass, and particularly preferably 0.01 to 0.2% by mass, based on the total weight of the monomers. The polymer produced by the above-mentioned polymerization method can be increased in molecular weight by solid-state polymerization by heating under reduced pressure or in an inert gas if necessary.

The melt viscosity of the (A) liquid crystalline resin obtained by the above method is not particularly limited. Generally, a liquid crystalline resin having a melt viscosity at a molding temperature of 10 MPa to 600 MPa at a shear rate of 1000 seconds ^-1 can be used. However, those liquid crystal resins which are too high in viscosity by themselves are not preferable because the fluidity is extremely deteriorated. The (A) liquid crystal resin may be a mixture of two or more liquid crystal resins.

In the liquid crystalline resin composition of the present invention, the content of the (A) liquid crystalline resin is preferably 38.5 to 83% by mass. From the viewpoint of fluidity, the content of the (A) component is preferably 38.5% by mass or more, and from the viewpoint of heat resistance, the content of the (A) component is preferably 83% by mass or less. The content of the component (A) is preferably 44 to 77.5 mass%, more preferably 50 to 72 mass%, and particularly preferably 55 to 67 mass%.
[(B) Talc]

The combined use of (B) talc and (C) an epoxy-group-containing copolymer contributes to improving the adhesion of a molded article obtained from the liquid crystalline resin composition of the present invention and reducing the sliding abrasion of the molded article. Sex. (B) Talc may be used alone or in combination of two or more.

(B) The median particle diameter of talc is 50 μm or less. When the median particle diameter exceeds 50 μm, the melt viscosity of the obtained liquid crystalline resin composition tends to increase, and mold deposition (hereinafter, also referred to as “MD”) easily occurs when the liquid crystalline resin composition is molded. Since the adhesiveness is easy to increase, and the melt viscosity and MD tend to decrease, the above median particle diameter is preferably 10 to 25 μm, more preferably 14 to 23 μm, and even more preferably 17 to 21 μm. In addition, in this specification, the median particle diameter refers to the volume-based median measured by a laser diffraction / scattering particle size distribution measurement method. Moreover, the so-called mold deposition refers to the deposits that are attached to the mold during molding.

In the liquid crystal composition of the present invention, the content of the component (B) is preferably from 15 to 55% by mass. When the content is 15 to 55% by mass, the tackiness tends to increase, and the melt viscosity and MD tend to decrease. Since the adhesiveness can be further improved, and the melt viscosity and MD can be further reduced, 20 to 50% by mass is preferable, 25 to 45% by mass is more preferable, and 30 to 40% by mass is more preferable.
[(C) Epoxy-containing copolymer]

The liquid crystal composition of the present invention contains (C) an epoxy group-containing copolymer. (C) An epoxy group-containing copolymer may be used individually by 1 type, and may be used in combination of 2 or more type. The (C) epoxy group-containing copolymer is not particularly limited, and examples thereof include those selected from the group consisting of (C1) epoxy group-containing olefin copolymers and (C2) epoxy group-containing styrene. (Styrene) -based copolymers in at least one of the groups. By using 2.0 to 6.5% by mass of the (C) epoxy group-containing copolymer and (B) talc in combination, the sliding abrasion resistance of a molded article obtained from the liquid crystalline resin composition of the present invention is reduced.

Examples of the (C1) epoxy-group-containing olefin copolymer include a repeating unit derived from an α-olefin and a repeating unit derived from a glycidyl ester of an α, β-unsaturated acid. Of copolymers.

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 an α, β-unsaturated acid is a compound represented by the following general formula (IV). Glycidyl esters of α, β-unsaturated acid are, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconic acid (Glycidyl itaconate) and the like, and glycidyl methacrylate is preferred.
[Chemical 4]

In the (C1) epoxy-group-containing olefin copolymer, the content of the repeating unit derived from an α-olefin is preferably 87 to 98% by mass, and the repeat derived from a glycidyl ester of an α, β-unsaturated acid. The unit is preferably 2 to 13% by mass.

The (C1) epoxy-group-containing olefin copolymer used in the present invention may contain acrylonitrile and acrylic acid in an amount of 0 to 48 parts by mass based on 100 parts by mass of the two components described above, within the scope of the present invention. The repeating unit derived from one or two or more of the olefinic unsaturated esters such as esters, methacrylates, α-methylstyrene, and maleic anhydride is used as a third component other than the above two components.

The epoxy group-containing olefin copolymer of the component (C1) of the present invention can be easily prepared by performing a general radical polymerization method using a monomer corresponding to each component and a radical polymerization catalyst. More specifically, it can usually be in the presence of a free radical initiator under the conditions of 500 to 4000 atmospheres and 100 to 300 ° C, and an appropriate solvent or a chain transfer agent may or may not be present by the α-olefin It is produced by copolymerizing with glycidyl ester of α, β-unsaturated acid. Furthermore, it is also possible to melt-graft copolymerize an α-olefin, an glycidyl ester of an α, β-unsaturated acid, and a radical initiator with each other and melt-graft copolymerize them in an extruder. Manufacturing.

Examples of the (C2) epoxy-group-containing styrenic copolymer include a copolymer composed of a repeating unit derived from a styrene and a repeating unit derived from a glycidyl ester of an α, β-unsaturated acid. Thing. Regarding the glycidyl ester of an α, β-unsaturated acid, its description is omitted because it is the same as that described in the (C1) component.

Examples of the styrenes include styrene, α-methylstyrene, brominated styrene, and divinylbenzene, and styrene is preferably used.

The (C2) epoxy-group-containing styrenic copolymer used in the present invention may be a repeating unit derived from one kind or two or more kinds containing other vinyl monomers as a third component other than the above two components. Multicomponent copolymers of various ingredients. The appropriate third component may be a repeating unit derived from one or two or more of olefinic unsaturated esters such as acrylonitrile, acrylate, methacrylate, and maleic anhydride. It is preferable that the epoxy group-containing styrenic copolymer containing the above-mentioned repeating unit in the copolymer as a component (C2) is 40% by mass or less.

In the (C2) epoxy-containing styrenic copolymer, the content of the repeating unit derived from the glycidyl ester of an α, β-unsaturated acid is 2 to 20% by mass, and the repeating unit derived from the styrene is The content is preferably 80 to 98% by mass.

(C2) An epoxy-group-containing styrene-based copolymer can be prepared by performing a general radical polymerization method using a monomer corresponding to each component and a radical polymerization catalyst. More specifically, it can usually be in the presence of a free radical initiator under the conditions of 500 to 4000 atmospheres and 100 to 300 ° C, and an appropriate solvent or chain transfer agent may or may not be present. It is produced by copolymerizing with glycidyl ester of α, β-unsaturated acid. Furthermore, it can also be manufactured by a method of mixing styrenes and glycidyl esters of α, β-unsaturated acids and a radical initiator with each other and melt-graft copolymerizing them in an extruder.

In addition, from the viewpoint of heat resistance, (C1) an epoxy-group-containing olefin-based copolymer is preferably (C) an epoxy-group-containing copolymer. In the case where the (C1) component and the (C2) component are used at the same time, the ratio of the above components to each other can be appropriately selected according to 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. When the content of the component (C) is within the above range, a molded article having reduced sliding abrasion resistance can be easily obtained without impairing fluidity. The content is preferably 2.5 to 6.0% by mass, and the content is more preferably 3.0 to 5.0% by mass.
[(D) Carbon black]

The carbon black (D) used as an optional component in the present invention is not particularly limited as long as it is a material that can be used for resin coloring and is generally available. Generally, (D) carbon black usually contains agglomerates formed by agglomeration of primary particles. However, as long as it does not contain a significant number of large agglomerates of 50 μm or more, the molding produced by the resin composition of the present invention is formed. There are almost no bumps on the surface of the product (carbon black condenses into small rash-like protrusions (fine unevenness)). When the content ratio of the particles having a particle diameter of 50 μm or more in the agglomerates is 20 ppm or less, the effect of suppressing burrs on the surface of the molded product is likely to be higher. The content ratio is preferably 5 ppm or less.

In the liquid crystalline resin composition, the blending amount of (D) carbon black is preferably in a range of 0.5 to 5% by mass. When the blending amount of the carbon black is 0.5% by mass or more, the blackness of the obtained resin composition is not easily lowered, and therefore there is almost no need to worry about light shielding properties. When the blending amount of the carbon black is 5% by mass or less, it is not easy to waste and almost no bumps are generated.
[(E) Release Agent]

The (E) release agent used as an optional component in the present invention is not particularly limited as long as it is a generally available material, and examples thereof include fatty acid esters, fatty acid metal salts, and fatty acids. Amines, low-molecular-weight polyolefins, and the like are preferably a fatty acid ester of pentaerythritol (for example, pentaerythritol tetrastearate).

In the liquid crystalline resin composition, the blending amount of the release agent (E) is preferably in a range of 0.1 to 3% by mass. When the compounding quantity of a mold release agent is 0.1 mass% or more, the mold release property at the time of shaping | molding can be improved and the molded article with which sliding abrasion resistance is reduced can be obtained easily. When the compounding quantity of a mold release agent is 3 mass% or less, MD will fall easily.
[Other ingredients]

In the liquid crystalline resin composition of the present invention, other polymers, other fillers, and known resins generally added to synthetic resins may be appropriately added in accordance with the required performance, as long as the effects of the present invention are not impaired. Substances, that is, stabilizers such as antioxidants or ultraviolet absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, crystallization accelerators, nucleating agents, and the like.

The other fillers refer to fillers other than (B) talc and (D) carbon black, and examples thereof include granular fillers such as silica. However, from the viewpoints of improvement in adhesiveness, melt viscosity, MD, and low sliding abrasion resistance, the liquid crystalline resin composition of the present invention preferably does not contain mica.
[Preparation method of liquid crystal resin composition for sliding wear-resistant member]

The method for producing the liquid crystalline resin composition for a sliding wear-resistant member of the present invention is not particularly limited. For example, the components (A) to (C) are blended and melt-kneaded using a uniaxial or biaxial extruder to prepare a liquid crystalline resin composition for a sliding wear-resistant member.

[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 · s from the viewpoint of reducing MD. The characteristics of high fluidity and excellent moldability during melting are also one of the characteristics of the liquid crystalline resin composition of the present invention. The melt viscosity is preferably 60 Pa · s or less, and more preferably 55 Pa · s or less. The lower limit of the melt viscosity is not particularly limited, and may be, for example, 30 Pa · s or more, or 40 Pa · s. In this specification, the value obtained by the measurement method of ISO 11443 under the condition that the cylinder temperature is 10 to 20 ° C. higher than the melting point of the liquid crystal resin and the shear rate is 1000 seconds ^-1 is used as the melt viscosity.
＜ Sliding wear-resistant member ＞

Using the liquid crystalline resin composition of the present invention, a sliding wear-resistant member is produced. The sliding abrasion-resistant member of the present invention has the same adhesion and impact resistance as before, while reducing sliding abrasion. The sliding wear-resistant member of the present invention can be applied to a member in which two or more members are in dynamic contact with each other during use, specifically, for example, a connector such as an FPC connector; a slot such as a memory card slot; a lens Parts for camera modules, such as stands; relays, etc.
[Example]

Examples are listed below to explain the present invention in more detail, but the present invention is not limited to these examples.
＜ Liquid crystal resin ＞
・ Liquid-crystalline polyester amidamine resin

After putting the following ingredients into the polymerization container, the temperature of the reaction system was raised to 140 ° C, and the reaction was allowed to react at 140 ° C for 1 hour. After that, the temperature was further increased to 340 ° C over 4.5 hours, and then the pressure was reduced to 10 Torr (that is, 1330 Pa) within 15 minutes. The acetic acid, excess acetic anhydride, and other low-boiling components were distilled while Melt polymerization. After the torque mixer reaches a predetermined value, nitrogen is introduced to change from a reduced pressure state to a pressurized state through normal pressure, the polymer is discharged from the bottom of the polymerization container, and the strand is pelletized to obtain pellets. ). The obtained pellets were subjected to a heat treatment at 300 ° C. for 2 hours under a stream of nitrogen 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. In addition, the melt viscosity of the polymer is measured by the same measurement method as the melt viscosity described later.
(I) 4-hydroxybenzoic acid (HBA); 1380 g (60 mole%)
(II) 2-hydroxy-6-naphthoic acid (HNA); 157 g (5 mole%)
(III) Terephthalic acid (TA); 484 g (17.5 mole%)
(IV) 4,4'-dihydroxybiphenyl (BP); 388 g (12.5 mole%)
(V) 4-Ethyloxy-aminophenol (APAP); 126 g (5 mole%)
Metal catalyst (potassium acetate catalyst); 110 mg amidine (acetic anhydride); 1659 g

<Material other than liquid crystalline resin>
・ Talc 1: Crown Talc PP (Matsumura Industry Co., Ltd., Talc, median particle size is 14.6 μm)
・ Talc 2: GH50 (manufactured by Linhuacheng Co., Ltd., talc, with a median particle size of 19.5 μm)
・ Talc 3: MS-KY (manufactured by Japan Talc Corporation, talc, with a median particle size of 22.4 μm)
・ Mica: AB-25S (manufactured by Yamaguchi Mica Co., Ltd., mica, with a median particle size of 25.0 μm)
・ Epoxy-containing olefin copolymer: BONDFAST 2C (manufactured by Sumitomo Chemical Co., Ltd., ethylene-glycidyl methacrylate copolymer, the content of glycidyl methacrylate is 6% by mass)
・ Carbon black: VULCAN XC305 (made by Cabot Japan Co., Ltd., average particle diameter is 20 nm, and the proportion of particles with a particle diameter of 50 μm or more is 20 ppm or less)
・ Releasing agent: Pentaerythritol tetrastearate (made by Emery Oleo Chemicals Japan)
<Manufacture of liquid crystal resin composition for sliding wear-resistant members>

The above ingredients were melt-kneaded in a ratio shown in Table 1 or Table 2 using a biaxial extruder (TEX30α type manufactured by Japan Steel Manufacturing Co., Ltd.) at a cylinder temperature of 350 ° C to obtain a liquid crystal for abrasion-resistant members. Of a resinous composition.
＜ Melting viscosity ＞

The above-mentioned particles were used to measure the melt viscosity of the liquid crystalline resin compositions of Examples and Comparative Examples. Specifically, a capillary rheometer (manufactured by Toyo Seiki Seisakusho Co., Ltd., Capirograph 1D: piston diameter 10 mm) was used at a cylinder temperature of 350 ° C and a shear rate of 1000 seconds Under the condition of ^-1 , the apparent melt viscosity is measured by the measurement method of ISO 11443. The measurement was performed using an orifice having an inner diameter of 1 mm and a length of 20 mm. The results are shown in Tables 1 and 2.
＜ Bend test ＞

The pellets of the examples and comparative examples were molded using a molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions to produce a 130 mm x 13 mm x 0.8 mm bending test piece. Using this test piece, flexural strength, flexural modulus, and strain at break were measured in accordance with ASTM D790. The measurement results of the flexural modulus are shown in Tables 1 and 2.
[Molding conditions]
Cylinder temperature: 350 ℃
Mold temperature: 90 ° C
Injection speed: 33 mm / sec. Holding pressure: 50 million Pa. <Epoxy adhesion>

The pellets of the examples and comparative examples were molded using a 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). This test piece was divided into two equal parts, as shown in Fig. 1 (a), and bonded with an epoxy-based adhesive (Lingerie 3128NH manufactured by Henkel) (curing conditions: 80 ° C x 30 minutes). . After that, as shown in FIG. 1 (b), the bonded test pieces were set, a load was applied in the direction of the arrow using a tensile tester, and the adhesive strength was evaluated by the load when peeling occurred. The results are shown in Tables 1 and 2.
[Molding conditions]
Cylinder temperature: 350 ℃
Mold temperature: 80 ℃
Injection speed: 33 mm / s
[Tensile test conditions]
Testing machine: Orientec, Tensilon RTC-1325A
Test speed: 10 mm / min <Charpy impact test>

The pellets of the examples and comparative examples were molded into measurement test pieces (4 mm × 10 mm × 80 mm) using a molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions. Using this test piece, the Charpy impact value was measured by the measurement method of ISO 179-1. The results are shown in Tables 1 and 2.
[Molding conditions]
Cylinder temperature: 350 ℃
Mold temperature: 80 ℃
Back pressure: 2.0 Mpa Injection speed: 33 mm / s <Evaluation of mold deposition (MD)>

The pellets of Examples and Comparative Examples were used as raw materials, and the test piece shown in FIG. 2 was continuously molded (500 times) for 4 hours using a molding machine ("ROBOSHOT S2000i30A" manufactured by FANUC Corporation) under the following molding conditions. Before and after continuous molding, the adhesion area of white deposits in the cavity portion was visually observed, and the state of MD reduction was evaluated according to the following criteria.
○ (Good): No white deposit was observed.
△ (normal): White deposits appear within a range of 7 mm from the vent portion.
× (bad): White deposits appeared more than 7 mm from the ventilated portion.
Here, the ventilation portion means a portion of the mold corresponding to the left end of the test piece shown in FIG. 2.
[Molding conditions]
Cylinder temperature: 360 ° C
Mold temperature: 90 ° C
Injection time: 2 seconds Cooling time: 5 seconds <Sliding wear amount>

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 pins (10 mm in diameter and 10 mm in length ) And measurement test pieces (80 mm x 80 mm x 1 mm). As shown in FIG. 3, a load is applied to the stylus on the test piece for measurement, and after the reciprocating sliding test is performed under the following reciprocating conditions, the total mass reduction of the stylus and the test piece for measurement is calculated to obtain the sliding wear amount. The results are shown in Tables 1 and 2.
[Molding conditions]
Cylinder temperature: 350 ℃
Mold temperature: 80 ℃
Injection speed: 33 mm / s
[Reciprocating sliding conditions]
Sliding speed: 5 cm / s Stroke: 20 mm Weight: 9.8 Newton (1 kg)
Number of reciprocations: 3000 times

[Table 1]

[Table 2]
Note) —: Due to the increase in resin temperature and viscosity, it cannot be extruded
[Industrial profitability]

It is clear from the results described in Tables 1 and 2 that the molded articles of the examples have the same adhesiveness and impact resistance as before, while reducing sliding abrasion resistance. In particular, it can be seen that when the content of talc is 25 to 45% by mass, the melt viscosity of the obtained composition hardly increases any more, and when this composition is molded, MD hardly occurs, and The adhesiveness of the obtained molded article can be easily further improved.

no.

[Fig. 1] Fig. 1 (a) is a diagram for explaining a method for manufacturing a sample for evaluating epoxy adhesiveness, and Fig. 1 (b) is a diagram for explaining a method for evaluating epoxy adhesiveness.

[Fig. 2] Fig. 2 is a diagram for explaining a test piece for evaluating mold deposit (MD).

[Fig. 3] Fig. 3 is a diagram for explaining a method for evaluating the amount of sliding wear.

Claims (3)

A liquid crystalline resin composition for a sliding wear-resistant member includes: (A) Liquid crystal resin; (B) talc; and (C) an epoxy-containing copolymer, The median particle diameter of the (B) talc is 50 μm or less, and the content of the (C) epoxy-group-containing copolymer is 2.0 to 6.5% by mass. The composition according to item 1 of the scope of patent application, wherein the content of the (B) talc is 25 to 45% by mass. A sliding abrasion-resistant member is composed of the composition described in item 1 or item 2 of the scope of patent application.