WO2019054187A1 - 耐摺動摩耗部材用液晶性樹脂組成物及びそれを用いた耐摺動摩耗部材 - Google Patents
耐摺動摩耗部材用液晶性樹脂組成物及びそれを用いた耐摺動摩耗部材 Download PDFInfo
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- WO2019054187A1 WO2019054187A1 PCT/JP2018/032095 JP2018032095W WO2019054187A1 WO 2019054187 A1 WO2019054187 A1 WO 2019054187A1 JP 2018032095 W JP2018032095 W JP 2018032095W WO 2019054187 A1 WO2019054187 A1 WO 2019054187A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Definitions
- 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.
- 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.
- the present invention has been made to solve the above-mentioned problems, and its object is to provide a sliding wear resistant member having reduced sliding wear while having the same adhesiveness and impact resistance as conventional ones. It is an object of the present invention to provide a liquid crystalline resin composition for a sliding wear resistant member used for manufacturing and a sliding wear resistant member using the same.
- the present inventors have intensively studied to solve the above problems. As a result, by using a liquid crystalline resin composition which contains a liquid crystalline resin, talc having a specific median diameter and an epoxy group-containing copolymer, and the content of the epoxy group-containing copolymer is within a predetermined range.
- the inventors have found that the above problems can be solved, and have completed the present invention. More specifically, the present invention provides the following.
- a liquid crystalline resin (A), (B) talc, and (C) an epoxy group-containing copolymer are contained, and the median diameter of the (B) talc is 50 ⁇ m or less, and the (C) epoxy group is The content of the contained copolymer is 2.0 to 6.5% by mass, and the liquid crystalline resin composition for a sliding wear resistant member.
- composition according to (1) wherein the content of the (B) talc is 25 to 45% by mass.
- a sliding wear resistant member comprising the composition according to (1) or (2).
- the sliding wear resistant member is manufactured using the liquid crystalline resin composition for sliding wear resistant member of the present invention as a raw material, the sliding wear is reduced while having the same adhesiveness and impact resistance as the conventional one. A sliding-resistant wear member is obtained.
- FIG.1 (a) is a figure for demonstrating the manufacturing method of the sample for epoxy adhesiveness evaluation
- FIG.1 (b) is a figure for demonstrating the method of epoxy adhesiveness evaluation
- FIG. 2 is a figure for demonstrating the test piece for evaluation of mold deposit (MD).
- FIG. 3 is a diagram for explaining a method of sliding wear evaluation.
- the liquid crystalline resin composition for a sliding wear resistant member of the present invention comprises (A) a liquid crystalline resin, (B) talc, and (C) an epoxy group-containing copolymer.
- 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.
- liquid crystalline resin 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.
- 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
- Specific 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-)
- 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, 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.
- 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 about 0.001 to 1% by weight, preferably 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. Generally, 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.
- the preferable content of the (A) liquid crystalline resin is 38.5 to 83% by mass.
- the content of the component (A) is preferably 38.5% by mass or more from the viewpoint of fluidity, and the content of the component (A) is preferably 83% by mass or less from the viewpoint of heat resistance.
- the content of the component (A) is more preferably 44 to 77.5% by mass, still more preferably 50 to 72% by mass, and particularly preferably 55 to 67% by mass.
- (B) talc When (B) talc is used 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.
- (B) Talc can be used singly or in combination of two or more.
- the median diameter of talc is 50 ⁇ m or less. When the median diameter is more than 50 ⁇ m, 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 above-mentioned median diameter is preferably 10 to 25 ⁇ m, more preferably 14 to 23 ⁇ m, and still more preferably 17 to 21 ⁇ m, since adhesion is easily improved and melt viscosity and MD are easily reduced.
- a median diameter means the median value of the volume reference
- a mold deposit means the deposit
- the content of the component (B) is preferably 15 to 55% by mass in the liquid crystal composition of the present invention.
- the above content is more preferably 20 to 50% by mass, still more preferably 25 to 45% by mass, still more preferably 30 or more, because the adhesion is more easily improved and the melt viscosity and MD are more easily reduced. It is ⁇ 40% by mass.
- 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.
- Examples of the (C1) epoxy group-containing olefin copolymer include copolymers composed of a repeating unit derived from an ⁇ -olefin and a repeating unit derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid.
- the ⁇ -olefin is not particularly limited, and examples thereof include ethylene, propylene and butene. Among them, ethylene is preferably used.
- the glycidyl ester of an ⁇ , ⁇ -unsaturated acid is represented by the following general formula (IV). Glycidyl esters of ⁇ , ⁇ -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.
- the content of repeating units derived from ⁇ -olefin is 87 to 98% by mass, and the content of repeating units derived from glycidyl ester of ⁇ , ⁇ -unsaturated acid is 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, ⁇ -methylstyrene, and maleic anhydride as a third component.
- Repeating units derived from one or more of olefinically unsaturated esters such as acids may be contained in an amount of 0 to 48 parts by mass with respect to 100 parts by mass of the above two components.
- the epoxy group-containing olefin 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, generally, 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 and an ⁇ -olefin and a glycidyl ester of an ⁇ , ⁇ -unsaturated acid It can be produced by the method of copolymerization under or without. It can also be produced by mixing an ⁇ -olefin with a glycidyl ester of an ⁇ , ⁇ -unsaturated acid and a radical generator, and melt graft copolymerization 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 ⁇ , ⁇ -unsaturated acid.
- the glycidyl ester of the ⁇ , ⁇ -unsaturated acid is the same as that described for the component (C1), and thus the description thereof is omitted.
- Styrenes include styrene, ⁇ -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-containing styrene-based copolymer containing 40% by mass or less of these repeating units in the copolymer is preferred as the component (C2).
- the content of repeating units derived from glycidyl esters of ⁇ , ⁇ -unsaturated acids is 2 to 20% by mass, and the content of repeating units derived from styrenes Is preferably 80 to 98% by 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, styrenes and glycidyl esters of ⁇ , ⁇ -unsaturated acids are usually added 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 ⁇ , ⁇ -unsaturated acid and a radical generator are mixed and melt graft copolymerized in an extruder.
- the (C) epoxy group-containing copolymer a (C1) epoxy group-containing olefin copolymer is preferable from the viewpoint of heat resistance.
- 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 epoxy group-containing copolymer (C) 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% by mass, and the still more preferable content is 3.0 to 5.0% by mass.
- 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.
- (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 ⁇ m 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.
- the content of particles having a particle size of 50 ⁇ m 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.
- the compounding amount of (D) carbon black is preferably in the range of 0.5 to 5% by mass in the liquid crystalline resin composition.
- 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.
- the amount of carbon black is 5% by mass or less, it is difficult to become uneconomical and it is difficult to generate bumps.
- 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.
- the compounding amount of the (E) mold release agent is preferably in the range of 0.1 to 3% by mass in the liquid crystalline resin composition. While the mold release property at the time of shaping
- 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 are fillers other than (B) talc and (D) carbon black, and examples thereof include particulate fillers such as silica.
- 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.
- the preparation method of the liquid crystalline resin composition for a sliding wear resistant member of the present invention is not particularly limited.
- the components (A) to (C) are blended, and the components are melt-kneaded using a single- or twin-screw extruder to prepare a liquid crystalline resin composition for a sliding wear resistant member. It will be.
- 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.
- the melt viscosity a value obtained by a measurement method in accordance with ISO 11443 is adopted under the conditions of a cylinder temperature higher by 10 to 20 ° C. than the melting point of the liquid crystalline resin and a shear rate of 1000 sec ⁇ 1 .
- a sliding wear resistant member is manufactured using the liquid crystalline resin composition of the present invention.
- the sliding wear-resistant member of the present invention has the same adhesion and impact resistance as conventional ones, but the sliding wear is reduced.
- 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.
- 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.
- 10 Torr ie, 1330 Pa
- 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.
- HBA 4-hydroxybenzoic acid
- HNA 2-hydroxy-6-naphthoic acid
- TA terephthalic acid
- BP 4,4'-dihydroxybiphenyl
- APAP 4-acetoxyaminophenol
- APAP 126 g (5 mol%)
- Metal catalyst potassium acetate catalyst
- 110 mg Acylation agent acetic anhydride
- 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 is in accordance with ISO 11443 using a capillary type 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 Tables 1 and 2.
- ⁇ Evaluation of mold deposit (MD)> The test piece shown in FIG. 2 is continuously molded for 4 hours (500 times) under the following molding conditions using the pellets of the examples and comparative examples as the raw materials and using a molding machine ("ROBOSHOT S2000i 30A" manufactured by FANUC Co., Ltd.) Before and after the continuous molding, the adhesion area of the white deposit on the cavity was visually observed, and the condition of MD reduction was evaluated according to the following criteria. ⁇ (good): no white deposit was observed. ⁇ (normal): White deposits were generated within 7 mm from the vent portion. X (defect): White deposits were generated over 7 mm from the vent portion.
- a vent part means the part on the mold corresponding to the left end of the test piece shown in FIG. ⁇ Molding condition ⁇ Cylinder temperature: 360 ° C Mold temperature: 90 ° C Injection time: 2 sec Cooling time: 5 seconds
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Abstract
Description
本発明の耐摺動摩耗部材用液晶性樹脂組成物は、(A)液晶性樹脂、(B)タルク、及び、(C)エポキシ基含有共重合体を含有する。
本発明で使用する(A)液晶性樹脂とは、光学異方性溶融相を形成し得る性質を有する溶融加工性ポリマーを指す。異方性溶融相の性質は、直交偏光子を利用した慣用の偏光検査法により確認することが出来る。より具体的には、異方性溶融相の確認は、Leitz偏光顕微鏡を使用し、Leitzホットステージに載せた溶融試料を窒素雰囲気下で40倍の倍率で観察することにより実施できる。本発明に適用できる液晶性ポリマーは直交偏光子の間で検査したときに、たとえ溶融静止状態であっても偏光は通常透過し、光学的に異方性を示す。
(1)主として芳香族ヒドロキシカルボン酸及びその誘導体の1種又は2種以上に由来する繰り返し単位からなるポリエステル;
(2)主として(a)芳香族ヒドロキシカルボン酸及びその誘導体の1種又は2種以上に由来する繰り返し単位と、(b)芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の1種又は2種以上に由来する繰り返し単位と、(c)芳香族ジオール、脂環族ジオール、脂肪族ジオール、及びそれらの誘導体の少なくとも1種又は2種以上に由来する繰り返し単位、とからなるポリエステル;
(3)主として(a)芳香族ヒドロキシカルボン酸及びその誘導体の1種又は2種以上に由来する繰り返し単位と、(b)芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体の1種又は2種以上に由来する繰り返し単位と、(c)芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の1種又は2種以上に由来する繰り返し単位、とからなるポリエステルアミド;
(4)主として(a)芳香族ヒドロキシカルボン酸及びその誘導体の1種又は2種以上に由来する繰り返し単位と、(b)芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体の1種又は2種以上に由来する繰り返し単位と、(c)芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の1種又は2種以上に由来する繰り返し単位と、(d)芳香族ジオール、脂環族ジオール、脂肪族ジオール、及びそれらの誘導体の少なくとも1種又は2種以上に由来する繰り返し単位、とからなるポリエステルアミド等が挙げられる。更に上記の構成成分に必要に応じ分子量調整剤を併用してもよい。
(B)タルクは、(C)エポキシ基含有共重合体と組み合わせて用いることにより、本発明の液晶性樹脂組成物から得られる成形体の接着性を向上させ、かつ、同成形体の摺動摩耗性を低減させることに寄与する。(B)タルクは、1種単独で又は2種以上組み合わせて使用することができる。
本発明の液晶性組成物は、(C)エポキシ基含有共重合体を含有する。(C)エポキシ基含有共重合体は、1種単独で又は2種以上組み合わせて使用することができる。(C)エポキシ基含有共重合体としては、特に限定されず、例えば、(C1)エポキシ基含有オレフィン系共重合体及び(C2)エポキシ基含有スチレン系共重合体からなる群より選択される少なくとも1種が挙げられる。2.0~6.5質量%の(C)エポキシ基含有共重合体は、(B)タルクと組み合わせて用いることにより、本発明の液晶性樹脂組成物から得られる成形体の摺動摩耗性を低減させることに寄与する。
本発明に任意成分として用いる(D)カーボンブラックは、樹脂着色に用いられる一般的に入手可能なものであれば、特に限定されるものではない。通常、(D)カーボンブラックには一次粒子が凝集して出来上がる塊状物が含まれているが、50μm以上の大きさの塊状物が著しく多く含まれていない限り、本発明の樹脂組成物を成形してなる成形体の表面に多くのブツ(カーボンブラックが凝集した細かいブツブツ状突起物(細かい凹凸))は発生しにくい。上記塊状物粒子径が50μm以上の粒子の含有率が20ppm以下であると、成形体表面の起毛抑制効果が高くなりやすい。好ましい含有率は5ppm以下である。
本発明に任意成分として用いる(E)離型剤としては、一般的に入手可能なものであれば、特に限定されるものではなく、例えば、脂肪酸エステル類、脂肪酸金属塩類、脂肪酸アミド類、低分子量ポリオレフィン等が挙げられ、ペンタエリスリトールの脂肪酸エステル(例えば、ペンタエリスリトールテトラステアレート)が好ましい。
本発明の液晶性樹脂組成物には、本発明の効果を害さない範囲で、その他の重合体、その他の充填剤、一般に合成樹脂に添加される公知の物質、即ち、酸化防止剤や紫外線吸収剤等の安定剤、帯電防止剤、難燃剤、染料や顔料等の着色剤、潤滑剤、結晶化促進剤、結晶核剤等も要求性能に応じ適宜添加することができる。
本発明の耐摺動摩耗部材用液晶性樹脂組成物の調製方法は特に限定されない。例えば、上記(A)~(C)成分を配合して、これらを1軸又は2軸押出機を用いて溶融混練処理することで、耐摺動摩耗部材用液晶性樹脂組成物の調製が行われる。
本発明の液晶性樹脂組成物を用いて、耐摺動摩耗部材を製造する。本発明の耐摺動摩耗部材は、従来と同等の接着性及び耐衝撃性を有しつつ、摺動摩耗性が低減されている。本発明の耐摺動摩耗部材は、使用時に2つ以上の部材が動的に接触するような部品に用いることができ、具体的には、例えば、FPCコネクター等のコネクター;メモリーカードソケット等のソケット;レンズホルダー等のカメラモジュール用部品;リレー等に用いることができる。
・液晶性ポリエステルアミド樹脂
重合容器に下記の原料を仕込んだ後、反応系の温度を140℃に上げ、140℃で1時間反応させた。その後、更に340℃まで4.5時間かけて昇温し、そこから15分かけて10Torr(即ち1330Pa)まで減圧にして、酢酸、過剰の無水酢酸、及びその他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレットを得た。得られたペレットについて、窒素気流下、300℃で2時間の熱処理を行って、目的のポリマーを得た。得られたポリマーの融点は336℃、350℃における溶融粘度は19.0Pa・sであった。なお、上記ポリマーの溶融粘度は、後述する溶融粘度の測定方法と同様にして測定した。
(I)4-ヒドロキシ安息香酸(HBA);1380g(60モル%)
(II)2-ヒドロキシ-6-ナフトエ酸(HNA);157g(5モル%)
(III)テレフタル酸(TA);484g(17.5モル%)
(IV)4,4’-ジヒドロキシビフェニル(BP);388g(12.5モル%)
(V)4-アセトキシアミノフェノール(APAP);126g(5モル%)
金属触媒(酢酸カリウム触媒);110mg
アシル化剤(無水酢酸);1659g
・タルク1:クラウンタルクPP(松村産業(株)製、タルク、メディアン径14.6μm)
・タルク2:GH50(林化成(株)製、タルク、メディアン径19.5μm)
・タルク3:MS-KY(日本タルク(株)製、タルク、メディアン径22.4μm)
・マイカ:AB-25S((株)ヤマグチマイカ製、マイカ、メディアン径25.0μm)
・エポキシ基含有オレフィン系共重合体:ボンドファースト2C(住友化学(株)製、エチレン-グリシジルメタクリレート共重合体、グリシジルメタクリレートの含有量6質量%)
・カーボンブラック:VULCAN XC305(キャボットジャパン(株)製、平均粒子径20nm、粒子径50μm以上の粒子の割合が20ppm以下)
・離型剤:ペンタエリスリトールテトラステアレート(エメリーオレオケミカルズジャパン(株)製)
上記成分を、表1又は2に示す割合で二軸押出機((株)日本製鋼所製TEX30α型)を用いて、シリンダー温度350℃にて溶融混練し、耐摺動摩耗部材用液晶性樹脂組成物ペレットを得た。
実施例及び比較例の液晶性樹脂組成物の溶融粘度を、上記ペレットを用いて測定した。具体的には、キャピラリー式レオメーター((株)東洋精機製作所製、キャピログラフ1D:ピストン径10mm)により、シリンダー温度350℃、せん断速度1000sec-1の条件での見かけの溶融粘度をISO 11443に準拠して測定した。測定には、内径1mm、長さ20mmのオリフィスを用いた。結果を表1及び2に示す。
実施例及び比較例のペレットを、成形機(住友重機械工業(株)製 「SE100DU」)を用いて、以下の成形条件で成形し、130mm×13mm×0.8mmの曲げ試験片を作製した。この試験片を用いて、ASTM D790に準拠し、曲げ強度、曲げ弾性率、及び破断歪を測定した。このうち、曲げ弾性率の測定結果を表1及び2に示す。
〔成形条件〕
シリンダー温度: 350℃
金型温度: 90℃
射出速度: 33mm/sec
保圧: 50MPa
実施例及び比較例のペレットを、成形機(住友重機械工業(株)製 「SE100DU」)を用いて、以下の成形条件で成形し、試験片(ISO試験片Type1A、厚み4mm)を得た。この試験片を2分割して、図1(a)に示すように、エポキシ系接着剤(ヘンケル社製ロックタイト3128NH)で貼り合わせた(硬化条件:80℃×30分)。その後、図1(b)に示すように、貼り合わされた試験片を設置して、引張試験機を用いて、矢印方向に荷重を加えて、剥がれたときの荷重から、接着強度を評価した。結果を表1及び2に示す。
〔成形条件〕
シリンダー温度: 350℃
金型温度: 80℃
射出速度: 33mm/sec
〔引張試験条件〕
試験機:オリエンテック、テンシロンRTC-1325A
試験速度:10mm/min
実施例及び比較例のペレットを、成形機(住友重機械工業(株)製 「SE100DU」)を用いて、以下の成形条件で測定用試験片(4mm×10mm×80mm)に成形した。この試験片を用いて、ISO 179-1に準拠した方法でシャルピー衝撃値を測定した。結果を表1及び2に示す。
〔成形条件〕
シリンダー温度: 350℃
金型温度: 80℃
背圧: 2.0MPa
射出速度: 33mm/sec
実施例及び比較例のペレットを原料とし、かつ、成形機(ファナック(株)製 「ROBOSHOT S2000i30A」を用いて、以下の成形条件で、図2に示す試験片を4時間連続成形(500回)した。連続成形前後で、キャビティ部の白色付着物の付着面積を目視にて観察し、以下の基準でMD低減の状況を評価した。
○(良好):白色付着物が見られなかった。
△(普通):白色付着物がベント部より7mm以内の範囲に発生していた。
×(不良):白色付着物がベント部より7mmを超えて発生していた。
ここで、ベント部とは、図2に示す試験片の左端に対応する金型上の部分をいう。
〔成形条件〕
シリンダー温度: 360℃
金型温度: 90℃
射出時間: 2sec
冷却時間: 5sec
実施例及び比較例のペレットを、成形機(住友重機械工業(株)製 「SE100DU」)を用いて、以下の成形条件で成形し、測定用ピン(直径10mm、長さ10mm)及び測定用試験片(80mm×80mm×1mm)を得た。図3に示す通り、測定用試験片上で測定用ピンに荷重をかけ、下記の往復摺動条件で往復摺動試験を行った後、測定用ピンと測定用試験片との合計の質量減少量を算出して、摺動摩耗量とした。結果を表1及び2に示す。
〔成形条件〕
シリンダー温度: 350℃
金型温度: 80℃
射出速度: 33mm/sec
〔往復摺動条件〕
すべり速度:5cm/sec
ストローク:20mm
荷重:9.8N(1kg重)
往復回数:3000回
Claims (3)
- (A)液晶性樹脂、
(B)タルク、及び
(C)エポキシ基含有共重合体
を含有し、
前記(B)タルクのメディアン径は、50μm以下であり、
前記(C)エポキシ基含有共重合体の含有量は、2.0~6.5質量%である耐摺動摩耗部材用液晶性樹脂組成物。 - 前記(B)タルクの含有量は、25~45質量%である請求項1に記載の組成物。
- 請求項1又は2に記載の組成物からなる耐摺動摩耗部材。
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