WO2005059035A1 - Composition of liquid-crystalline polymer - Google Patents

Composition of liquid-crystalline polymer Download PDF

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Publication number
WO2005059035A1
WO2005059035A1 PCT/JP2004/018778 JP2004018778W WO2005059035A1 WO 2005059035 A1 WO2005059035 A1 WO 2005059035A1 JP 2004018778 W JP2004018778 W JP 2004018778W WO 2005059035 A1 WO2005059035 A1 WO 2005059035A1
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Prior art keywords
crystalline polymer
liquid crystalline
polymer composition
weight
oxides
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PCT/JP2004/018778
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French (fr)
Japanese (ja)
Inventor
Yuko Yamamoto
Kazufumi Watanabe
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Polyplastics Co., Ltd.
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Publication of WO2005059035A1 publication Critical patent/WO2005059035A1/en

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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

Definitions

  • the present invention relates to a liquid crystalline polymer composition having excellent sliding properties and providing a molded article having good mechanical properties.
  • general-purpose engineering plastics such as polyacetal do not have sufficient heat resistance under high-temperature atmospheres during assembly processes such as component densification and surface mounting. And did not stand use.
  • general-purpose engineering plastics have not been able to satisfy the dimensional accuracy required for small precision mechanical parts due to their large molding shrinkage and linear expansion coefficient.
  • Patent Document 1 proposes the use of glassy carbon as a filler for liquid crystal polyester.In this case, good sliding characteristics are obtained for hard metals such as counterpart stainless steel.
  • Patent Document 2 proposes using a liquid crystal polyester in which a specific metal oxide and a specific fluororesin are blended as a filler, but the effect of reducing the amount of wear is not significant. Not enough.
  • Patent Document 1 Japanese Patent Laid-Open No. 4-4296
  • Patent Document 2 JP-A-10-25402
  • the present invention solves the above problems, and provides a liquid crystalline polymer composition which has excellent sliding characteristics, provides a molded article having a small specific wear and good mechanical properties.
  • the purpose is.
  • a liquid crystal polymer has an oxide, a peroxide, a double oxide, a metal of a metal belonging to Group 1A or 2A of the periodic table.
  • a liquid crystal polymer composition which achieves the above object is obtained by blending at least one compound selected from carbonates and a specific limited fluororesin in a specific amount, respectively.
  • the present inventors have found that a sliding component having excellent sliding characteristics can be provided by using the same, and have reached the present invention.
  • the present invention relates to the liquid crystalline polymer (A), wherein at least one selected from oxides, peroxides, double oxides, and carbonates of metals belonging to Group 1A or 2A of the periodic table is used. More than one kind of compound (B) 3—60% by weight (of the total composition), after polymerization, once undergoing a molding step, and then turned into powder, which does not flow under the following test conditions (C) 0.1— It is a liquid crystal polymer composition containing 30% by weight (of all compositions).
  • the liquid crystalline polymer composition of the present invention exhibits excellent sliding properties and good mechanical properties. , And an excellent sliding part can be provided.
  • the liquid crystalline polymer (A) used in the present invention refers to a melting force polymer having a property capable of forming an optically anisotropic molten phase.
  • the properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, confirmation of the anisotropic molten phase can be performed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times.
  • the liquid crystalline polymer applicable to the present invention is inspected between crossed polarizers, even if it is in a molten stationary state, polarized light is normally transmitted, and exhibits optical anisotropy.
  • the liquid crystal polymer (A) as described above is not particularly limited, but is preferably an aromatic polyester or an aromatic polyesteramide, and the aromatic polyester or the aromatic polyesteramide is partially contained in the same molecular chain. Is included in the range. They are preferably at least about 2. Odl / g, more preferably 2.0-10 Odl / g, when dissolved in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C. ) Are used.
  • the aromatic polyester or aromatic polyesteramide as the liquid crystalline polymer (A) applicable to the present invention is particularly preferably selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines.
  • a polyester mainly comprising one or more aromatic hydroxycarboxylic acids and derivatives thereof;
  • Preferred examples of the specific compound constituting the liquid crystalline polymer (A) applicable to the present invention include aromatic hydroxycanolevonic acid such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; Aromatic diols such as 6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcinol, compounds represented by the following general formula (I) and the following general formula ( ⁇ ); 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-phenyl And aromatic amines such as rangenamine.
  • aromatic hydroxycanolevonic acid such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid
  • an aromatic hydroxycarboxylic acid composed of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid is a main structural unit.
  • Aromatic polyester and aromatic polyester amide as components.
  • the present invention is particularly effective for a liquid crystalline polymer having a relatively low melt viscosity in which the stringing phenomenon is likely to occur, and specifically, at a temperature higher by 10 to 15 ° C than the melting point. It has a remarkable effect on liquid crystalline polymers with a melt viscosity of 550 Pa's at a shear rate of 100 sec- 1 .
  • Oxides and peroxides of metals belonging to Group 1A or 2A of the periodic table used in the present invention are represented by the general formulas M ⁇ , M' ⁇ or M' ⁇ (wherein M is Group 1A, M 'Is a metal element belonging to Group 2A.)
  • M is preferably selected from Na and K.
  • M ' is preferably selected from Mg, Ca and Ba forces. Examples of this include calcium oxide (99.9%), magnesium oxide (heavy, special grade reagent), barium oxide (for Idani Gaku), barium peroxide (wako first grade), available from Wako Pure Chemical Industries, Ltd. Examples include, but are not limited to, Paiguchi Kisuma 3320 and Micromag 3-30 available from Kyowa Chemical Industry Co., Ltd.
  • the double oxide containing a metal belonging to Group 1A or 2A of the periodic table used in the present invention is represented by the general formula M 0 'mM " ⁇ ⁇ ⁇ 0, pM' O -mM ' O ⁇ ⁇ 0, M ⁇ ⁇ ⁇ "'O ⁇ mM" ⁇ -xHO or MO -pM' OmM '"O ⁇ ⁇ " ⁇ ⁇ ⁇ O
  • M is a metal element belonging to group 1A
  • M ' is a metal element belonging to group 2A
  • M' is a trivalent metal element
  • p, m, n are X is a positive number greater than or equal to 0.
  • M is preferably K.
  • M ' is preferably selected from Mg, Ca, and Ba. Examples of the force include, but are not limited to, talc, wollastonite, attapulgite, sericite, my power, potassium titanate, and barium titanate.
  • the carbonate containing a metal belonging to Group 1A or 2A of the periodic table used in the present invention refers to a general formula MCO, M'CO or M'-M "(CO) Medium, 1A group
  • M is preferably K.
  • M' and M" are selected from Mg, Ca, and Ba. Les, which are preferably things. Examples include, but are not limited to, potassium carbonate, calcium carbonate, dolomite, and the like. Of these, Tanolek, wollastonite, dolomite, oxidation Particularly preferred are wollastonite and tanolek, which are preferably magnesium and potassium titanate. These can be used alone or in combination of one or more.
  • the one with a 300 mesh pass or less is preferred. If it is larger than 300 mesh pass, the effect of imparting sliding properties to the liquid crystal polyester is not much different from that of 300 mesh pass or less, but aspects such as appearance of the molded product and uniform dispersibility in the molded product. From the preferred ,.
  • the fluororesin (C) used in the present invention is a polymer comprising an olefin containing a fluorine atom in a molecule, and specific examples thereof include polytetrafluoroethylene (hereinafter abbreviated as PTFE), A power such as a fluoroethylene-hexafluoropropylene copolymer, a polytrichloroethylene fluoroethylene, or a tetrafluoroethylene-perfluoroalkylbutyl ether copolymer. Particularly preferred is PTFE.
  • the fluororesin used in the present invention is characterized in that it undergoes a molding step such as baking after polymerization, and then is powdered and does not flow. And does not cause flow, specifically, the inner diameter lmm, length ranges Kiyabirari set rheometer with Nozunore shear rate conditions of Yore ,, 360 ° C from LOsec- 1 of LOOOOsec- 1 of 20mm It does not flow under the flow test conditions of changing within. Fluororesins flowing under such conditions are not preferred in terms of improving slidability.
  • the average particle size of the fluororesin is preferably 100 ⁇ m or less, more preferably 30 / m or less for improving the slidability.
  • a fluororesin examples include KT600M (trade name) available from Kitamura Corporation.
  • the method of pulverizing the fluororesin include mechanical pulverization and pulverization by radiation, but mechanical pulverization is preferable in terms of gas generation.
  • the blending ratio of (B) is 360% by weight (of the total composition), preferably 1050% by weight, and more preferably 20-40% by weight.
  • Component (B) is more than 60% by weight In such a case, the fluidity at the time of molding is deteriorated, and it is difficult to obtain a good molded product, which is not preferable.
  • the blending ratio of the component (B) is less than 3% by weight, sufficient mechanical properties cannot be obtained, so that it is not preferable.
  • the mixing ratio of the specific fluororesin (C) is 0.1 to 30% by weight (of the whole composition), preferably 1 to 15% by weight, and more preferably 3 to 15% by weight. — 10% by weight. If the blending ratio of the fluororesin is more than 30% by weight, the mechanical strength and the heat resistance are undesirably reduced. On the other hand, when the blending ratio of the fluororesin is less than 0.1% by weight, the slidability, which is the object of the present invention, is not sufficient, which is not preferable.
  • the composition of the present invention does not impair the effects of the present invention. You may mix
  • the resin that does not form such an anisotropic molten phase may be compatible with the liquid crystalline polymer (A) or may be incompatible.
  • thermoplastic resin that does not form an anisotropic molten phase examples include polyethylene, polypropylene, polybutylene, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl chloride, polyvinylidene, polystyrene, acrylic resin, ABS resin, AS resin, BS resin, polyurethane resin, silicone resin, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, aromatic polyester, polyamide, polyacrylonitrile, polybutyl alcohol, polybutyl ether, polyetherimide, polyamideimide, Polyetheretherimide, polyetherketone, polyethersulfone, polysulfone, polyphenylenesulfide, polyphenyleneoxide, etc.
  • thermosetting resin that does not form a melt phase examples include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin and the like.
  • composition of the present invention may contain, if necessary, for example, a plasticizer, a stabilizer such as an antioxidant or an ultraviolet absorber, a flame retardant, a coloring agent such as a dye or a pigment, a foaming agent, or a divinyl-based compound.
  • the raw material components are contained in the above composition ratio. Normally, kneading is performed by an extruder, extruded into pellets, and used in injection molding. Kneading by such an extruder is not limited.
  • melt viscosity was measured at a shear rate of 100 sec- 1 at a temperature of 360 ° C.
  • the bending strength was measured according to ISO 178.
  • PTFE-1 KT600M (manufactured by Kitamura Co .; does not flow in the above flow test)
  • PTFE-2 KT400M (manufactured by Kitamura; not flowable in the above flow test)
  • PTFE-3 Sefralnorebe I (manufactured by Central Glass; flowable in the flow test described above)
  • PTFE-4 KTL610 (manufactured by Kitamura Corporation; flow in the flow test described above)
  • 'Glass fiber CS03JA419 (made by Asahi Fiberglass)
  • the numerical value of the compounding amount is% by weight.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

A liquid-crystalline-polymer composition which gives a molding having excellent sliding properties and satisfactory mechanical properties. The liquid-crystalline-polymer composition comprises a liquid-crystalline polymer (A) and, compounded therewith, 3 to 60% by weight (based on the whole composition) at least one compound (B) selected among oxides, peroxides, composite oxides, and carbonates of metals belonging to Groups 1A and 2A of the Periodic Table and 0.1 to 30% by weight (based on the whole composition) fluororesin (C) which has been powdered after polymerization and subsequent temporary molding and which does not flow under certain conditions.

Description

明 細 書  Specification
液晶性ポリマー組成物  Liquid crystalline polymer composition
技術分野  Technical field
[0001] 本発明は、優れた摺動特性を有し、かつ良好な機械物性を有する成形体を与える 液晶性ポリマー組成物に関する。  The present invention relates to a liquid crystalline polymer composition having excellent sliding properties and providing a molded article having good mechanical properties.
背景技術  Background art
[0002] 近年の軽薄短小化の進展に伴い、種々の機構部品用途においても、軽量化、コス トダウンの要求が強まり、合成樹脂が使われることが多くなつてきた。こうした、機構部 品用途においては、良好な摺動特性が要求される場合も多ぐ従来から、ポリアセタ ール等の樹脂、あるいは、それらに固体潤滑剤、潤滑油等を摺動性改良材として添 カロした組成物等が使用されてきた。これらは、通常の機械使用温度雰囲気、たとえば 、一 40°C— 70°Cの温度範囲においては良好な摺動特性を示すものの、高温多湿の 条件下では、摩耗量の増大、寸法変化、変形などを起こし使用することができなくな る。また、 OA機器や、電子部品などにおいて、部品の高密度化や表面実装等の組 立工程における高温雰囲気下では、ポリアセタール等の汎用エンジニアリングプラス チックは、耐熱性が不足し、変形はおろか、溶融を起こして使用に耐えなかった。ま た、このような汎用エンジニアリングプラスチックでは、成形収縮率や線膨張係数が大 きいため、小型精密機構部品などで要求される寸法精度を満足することができなか つた。  [0002] In recent years, with the progress of lightening and miniaturization, demands for weight reduction and cost reduction have been increasing in various mechanical parts applications, and synthetic resins have been increasingly used. In such mechanical component applications, good sliding characteristics are often required, and resins such as polyacetal and solid lubricants and lubricating oils have been used as sliding property improving materials. Additive compositions have been used. They exhibit good sliding properties in normal machine operating temperature atmospheres, for example, in the temperature range of 140 ° C to 70 ° C, but increase in wear, dimensional change, and deformation under high temperature and high humidity conditions. Will not work. In OA equipment, electronic components, etc., general-purpose engineering plastics such as polyacetal do not have sufficient heat resistance under high-temperature atmospheres during assembly processes such as component densification and surface mounting. And did not stand use. In addition, such general-purpose engineering plastics have not been able to satisfy the dimensional accuracy required for small precision mechanical parts due to their large molding shrinkage and linear expansion coefficient.
[0003] 一方、液晶性ポリマーは、耐熱性、機械的物性に優れた熱可塑性樹脂に近年需要 を伸ばしている。このような液晶性ポリマーにガラス繊維等の充填材を配合し、上記 摺動部品に適用することが試みられている。かかる摺動部品に要求される性能の一 つとして、相手材が硬質部材であっても軟質部材であっても優れた摺動性 (低摩擦 係数）を示すと共に、 自身および相手材を傷つけにくい（低磨耗量）という点が挙げら れる。従来、特許文献 1には、液晶ポリエステルに充填材としてガラス状炭素を用いる ことが提案されている力 この場合、相手材カ Sステンレス鋼などの硬質の金属に対し ては良好な摺動特性を示すものの、アルミニウムのような軟質金属に対しては、相手 材を磨耗させてしまうため好ましくない。また、特許文献 2には、液晶ポリエステルに 充填剤として特定の金属酸化物、及び特定のフッ素樹脂を配合したものを用いること が提案されてレ、るが、磨耗量の低減に関してはその効果は十分とは言えなかった。 特許文献 1：特開平 4 - 4296号公報 [0003] On the other hand, the demand for liquid crystalline polymers for thermoplastic resins having excellent heat resistance and mechanical properties has been increasing in recent years. Attempts have been made to mix a filler such as glass fiber with such a liquid crystalline polymer and apply it to the above sliding parts. One of the performances required for such a sliding component is that it exhibits excellent sliding properties (low friction coefficient) regardless of whether the mating member is a hard member or a soft member, and does not easily damage itself and the mating member. (Low wear). Conventionally, Patent Document 1 proposes the use of glassy carbon as a filler for liquid crystal polyester.In this case, good sliding characteristics are obtained for hard metals such as counterpart stainless steel. Although shown, for soft metals such as aluminum It is not preferable because the material is worn. Patent Document 2 proposes using a liquid crystal polyester in which a specific metal oxide and a specific fluororesin are blended as a filler, but the effect of reducing the amount of wear is not significant. Not enough. Patent Document 1: Japanese Patent Laid-Open No. 4-4296
特許文献 2：特開平 10 - 25402号公報  Patent Document 2: JP-A-10-25402
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0004] 本発明は、以上の問題点を解決して、優れた摺動特性を有すると共に比摩耗量が 少なぐかつ良好な機械物性を有する成形体を与える液晶性ポリマー組成物を提供 することを目的とするものである。 [0004] The present invention solves the above problems, and provides a liquid crystalline polymer composition which has excellent sliding characteristics, provides a molded article having a small specific wear and good mechanical properties. The purpose is.
課題を解決するための手段  Means for solving the problem
[0005] 本発明者らは、上記問題点を解決するために鋭意検討した結果、液晶性ポリマー に周期律表の 1 Aまたは 2A族に属する金属の酸化物、過酸化物、複酸化物、及び 炭酸化物から選ばれた少なくとも 1種以上の化合物と、特定の限定されたフッ素樹脂 とをそれぞれ特定量配合することにより上記目的が達成される液晶性ポリマー組成 物が得られ、該組成物を用いることにより摺動特性に優れた摺動部品を提供し得るこ とを見出し本発明に至った。  [0005] The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a liquid crystal polymer has an oxide, a peroxide, a double oxide, a metal of a metal belonging to Group 1A or 2A of the periodic table. A liquid crystal polymer composition which achieves the above object is obtained by blending at least one compound selected from carbonates and a specific limited fluororesin in a specific amount, respectively. The present inventors have found that a sliding component having excellent sliding characteristics can be provided by using the same, and have reached the present invention.
[0006] 即ち本発明は、液晶性ポリマー (A)に対して、周期律表の 1Aまたは 2A族に属する 金属の酸化物、過酸化物、複酸化物、及び炭酸化物から選ばれた少なくとも 1種以 上の化合物 (B) 3— 60重量％ (全組成物中）、重合後、一旦成形工程を経た後に粉 末化され、下記の試験条件で流動を起こさないフッ素樹脂 (C) 0.1— 30重量％ (全組 成物中）を配合してなる液晶性ポリマー組成物である。  [0006] That is, the present invention relates to the liquid crystalline polymer (A), wherein at least one selected from oxides, peroxides, double oxides, and carbonates of metals belonging to Group 1A or 2A of the periodic table is used. More than one kind of compound (B) 3—60% by weight (of the total composition), after polymerization, once undergoing a molding step, and then turned into powder, which does not flow under the following test conditions (C) 0.1— It is a liquid crystal polymer composition containing 30% by weight (of all compositions).
(フッ素樹脂の流動試験条件）  (Fluid resin flow test conditions)
内径 lmm、長さ 20mmのノズノレを持つキヤビラリ一式レオメーターを用レ、、 360°Cの条 件で剪断速度を lOsec— 1から lOOOOsec— 1の範囲内で変化させる。 Use a complete set of rheometers with a diameter of lmm and a length of 20mm. Change the shear rate within the range of lOsec- 1 to lOOOOsec- 1 at 360 ° C.
発明の効果  The invention's effect
[0007] 本発明の液晶性ポリマー組成物は、優れた摺動特性を示し、且つ良好な機械物性 を有する成形品を与えることができ、優れた摺動部品を提供し得る。 [0007] The liquid crystalline polymer composition of the present invention exhibits excellent sliding properties and good mechanical properties. , And an excellent sliding part can be provided.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0008] 以下、本発明を詳細に説明する。本発明で使用する液晶性ポリマー (A)とは、光学 異方性溶融相を形成し得る性質を有する溶融力卩ェ性ポリマーを指す。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。  Hereinafter, the present invention will be described in detail. The liquid crystalline polymer (A) used in the present invention refers to a melting force polymer having a property capable of forming an optically anisotropic molten phase. The properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, confirmation of the anisotropic molten phase can be performed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. When the liquid crystalline polymer applicable to the present invention is inspected between crossed polarizers, even if it is in a molten stationary state, polarized light is normally transmitted, and exhibits optical anisotropy.
[0009] 前記のような液晶性ポリマー (A)としては特に限定されないが、芳香族ポリエステル 又は芳香族ポリエステルアミドであることが好ましく、芳香族ポリエステル又は芳香族 ポリエステルアミドを同一分子鎖中に部分的に含むポリエステルもその範囲にある。 これらは 60°Cでペンタフルオロフェノールに濃度 0. 1重量％で溶解したときに、好ま しくは少なくとも約 2. Odl/g、さらに好ましくは 2. 0- 10. Odl/gの対数粘度（I. V. )を有するものが使用される。  [0009] The liquid crystal polymer (A) as described above is not particularly limited, but is preferably an aromatic polyester or an aromatic polyesteramide, and the aromatic polyester or the aromatic polyesteramide is partially contained in the same molecular chain. Is included in the range. They are preferably at least about 2. Odl / g, more preferably 2.0-10 Odl / g, when dissolved in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C. ) Are used.
[0010] 本発明に適用できる液晶性ポリマー (A)としての芳香族ポリエステル又は芳香族ポ リエステルアミドとして特に好ましくは、芳香族ヒドロキシカルボン酸、芳香族ヒドロキシ ァミン、芳香族ジァミンの群から選ばれた少なくとも 1種以上の化合物を構成成分とし て有する芳香族ポリエステル、芳香族ポリエステルアミドである。 [0010] The aromatic polyester or aromatic polyesteramide as the liquid crystalline polymer (A) applicable to the present invention is particularly preferably selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines. An aromatic polyester and an aromatic polyesteramide having at least one compound as a constituent component.
[0011] より具体的には、 [0011] More specifically,
(1)主として芳香族ヒドロキシカルボン酸およびその誘導体の 1種又は 2種以上から なるポリエステル；  (1) A polyester mainly comprising one or more aromatic hydroxycarboxylic acids and derivatives thereof;
(2)主として（a)芳香族ヒドロキシカルボン酸およびその誘導体の 1種又は 2種以上と 、（b)芳香族ジカルボン酸、脂環族ジカルボン酸およびその誘導体の 1種又は 2種以 上と、（c)芳香族ジオール、脂環族ジオール、脂肪族ジオールおよびその誘導体の 少なくとも 1種又は 2種以上、とからなるポリエステル；  (2) mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, (C) a polyester comprising at least one or two or more aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof;
(3)主として（a)芳香族ヒドロキシカルボン酸およびその誘導体の 1種又は 2種以上と 、（b)芳香族ヒドロキシァミン、芳香族ジァミンおよびその誘導体の 1種又は 2種以上 と、（c)芳香族ジカルボン酸、脂環族ジカルボン酸およびその誘導体の 1種又は 2種 以上、とからなるポリエステルアミド； (3) Mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof And (c) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, polyester amides;
(4)主として（a)芳香族ヒドロキシカルボン酸およびその誘導体の 1種又は 2種以上と 、（b)芳香族ヒドロキシァミン、芳香族ジァミンおよびその誘導体の 1種又は 2種以上 と、（c)芳香族ジカルボン酸、脂環族ジカルボン酸およびその誘導体の 1種又は 2種 以上と、（d)芳香族ジオール、脂環族ジオール、脂肪族ジオールおよびその誘導体 の少なくとも 1種又は 2種以上、とからなるポリエステルアミドなどが挙げられる。さらに 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。  (4) Mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof, (c ) One or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, and (d) at least one or two or more aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof, And polyester amides consisting of Further, a molecular weight modifier may be used in combination with the above constituents as necessary.
[0012] 本発明に適用できる前記液晶性ポリマー (A)を構成する具体的化合物の好ましい 例としては、 p—ヒドロキシ安息香酸、 6—ヒドロキシー 2_ナフトェ酸等の芳香族ヒドロキ シカノレボン酸、 2, 6—ジヒドロキシナフタレン、 1 , 4—ジヒドロキシナフタレン、 4, 4 '—ジ ヒドロキシビフエニル、ハイドロキノン、レゾルシン、下記一般式（I)および下記一般式 (Π)で表される化合物等の芳香族ジオール;テレフタル酸、イソフタル酸、 4, 4'ージフ 工ニルジカルボン酸、 2, 6—ナフタレンジカルボン酸および下記一般式（III)で表され る化合物等の芳香族ジカルボン酸； p—アミノフヱノール、 p—フエ二レンジァミン等の芳 香族ァミン類が挙げられる。  Preferred examples of the specific compound constituting the liquid crystalline polymer (A) applicable to the present invention include aromatic hydroxycanolevonic acid such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; Aromatic diols such as 6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcinol, compounds represented by the following general formula (I) and the following general formula (Π); 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-phenyl And aromatic amines such as rangenamine.
[0013] [化 1]  [0013] [Chemical 1]
HO X - <T oH ( I )
Figure imgf000005_0001
HO X-<T oH (I)
Figure imgf000005_0001
HOOC -i Y -( COOH ( I ) HOOC -i Y-(COOH (I)
[0014] (但し、 X ：アルキレン（CI一 C4)、アルキリデン、 -0-、 -SO-、 -SO -(Where X is alkylene (CI-C4), alkylidene, -0-, -SO-, -SO-
2 、 _S -、 -CO-よ り選ばれる基、 Y： -(CH ) -(n = l 4)、 -0(CH ) 0- (n = 1一 4)より選ばれる基) 2, a group selected from _S-, -CO-, Y: a group selected from-(CH)-(n = l4), -0 (CH) 0- (n = 1 to 4))
2 n 2 n  2 n 2 n
本発明が適用される特に好ましい液晶性ポリマー (A)としては、 p—ヒドロキシ安息香 酸、 6—ヒドロキシー 2—ナフトェ酸からなる芳香族ヒドロキシカルボン酸を主構成単位 成分とする芳香族ポリエステルおよび芳香族ポリエステルアミドである。 As a particularly preferred liquid crystalline polymer (A) to which the present invention is applied, an aromatic hydroxycarboxylic acid composed of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid is a main structural unit. Aromatic polyester and aromatic polyester amide as components.
[0015] 尚、本発明は、糸引き現象が発生しやすい、比較的溶融粘度の低い液晶性ポリマ 一に対して特に有効であり、具体的には、融点より 10— 15°C高い温度での剪断速度 lOOOsec— 1の溶融粘度が 5 50Pa' sの液晶性ポリマーに著しい効果を発揮するもの である。 [0015] The present invention is particularly effective for a liquid crystalline polymer having a relatively low melt viscosity in which the stringing phenomenon is likely to occur, and specifically, at a temperature higher by 10 to 15 ° C than the melting point. It has a remarkable effect on liquid crystalline polymers with a melt viscosity of 550 Pa's at a shear rate of 100 sec- 1 .
[0016] 次に、本発明で用いられる (B)成分について説明する。本発明で用いられる周期律 表の 1Aまたは 2A族に属する金属の酸化物、過酸化物は、一般式 M〇、 M'〇また は M'〇（これらの式中、 Mは 1A族、 M'は 2A族に属する金属元素である。）で表さ れるものである。特に Mは Na、 Kから選ばれたものが好ましぐ M'は Mg, Ca， Ba力、 ら選ばれたものであることが好ましい。この例としては、和光純薬工業 (株）より入手で きる酸化カルシウム (99.9%)、酸化マグネシウム（重質、試薬特級）、酸化バリウム (ィ匕 学用）、過酸化バリウム (和光一級)、協和化学工業 (株)より入手できる商品名パイ口 キスマ 3320、ミクロマグ 3-30などが挙げられるがこれに限定されるものではない。  Next, the component (B) used in the present invention will be described. Oxides and peroxides of metals belonging to Group 1A or 2A of the periodic table used in the present invention are represented by the general formulas M〇, M'〇 or M'〇 (wherein M is Group 1A, M 'Is a metal element belonging to Group 2A.) In particular, M is preferably selected from Na and K. M 'is preferably selected from Mg, Ca and Ba forces. Examples of this include calcium oxide (99.9%), magnesium oxide (heavy, special grade reagent), barium oxide (for Idani Gaku), barium peroxide (wako first grade), available from Wako Pure Chemical Industries, Ltd. Examples include, but are not limited to, Paiguchi Kisuma 3320 and Micromag 3-30 available from Kyowa Chemical Industry Co., Ltd.
[0017] また、本発明で用いられる、周期律表の 1Aまたは 2A族に属する金属を含む複酸 ィ匕物とは、一般式 M 0 'mM"〇 ·χΗ 0、 pM' O -mM'O ·χΗ 0、 M〇·ρΜ"' O · mM"〇 -xH Oまたは M O -pM' OmM'" O ·ηΜ"〇 ·χΗ O [0017] Further, the double oxide containing a metal belonging to Group 1A or 2A of the periodic table used in the present invention is represented by the general formula M 0 'mM "〇 · χΗ0, pM' O -mM ' O · χΗ 0, M〇 · ρΜ "'O · mM" 〇 -xHO or MO -pM' OmM '"O · ηΜ" 〇 · χΗ O
(これらの式中、 Mは 1A族に属する金属元素、 M'は 2A族に属する金属元素、 M" は 4価の金属元素、 M' "は 3価の金属元素、 p, m, nは 1以上の正数、 xは 0以上の 正数）で表されるものである。特に、 Mは Kであることが好ましぐ M'は Mg, Ca, Ba 力 選ばれたものであることが好ましい。この例としては、タルク、ウォラストナイト、ァタ パルジャイト、セリサイト、マイ力、チタン酸カリウム、チタン酸バリウムなどが挙げられる 力 Sこれらに限定されるものではない。  (Where M is a metal element belonging to group 1A, M 'is a metal element belonging to group 2A, M "is a tetravalent metal element, M'" is a trivalent metal element, and p, m, n are X is a positive number greater than or equal to 0). In particular, M is preferably K. M 'is preferably selected from Mg, Ca, and Ba. Examples of the force include, but are not limited to, talc, wollastonite, attapulgite, sericite, my power, potassium titanate, and barium titanate.
[0018] また、本発明で用いられる、周期律表の 1Aまたは 2A族に属する金属を含む炭酸 化物とは、一般式 M CO、 M' COまたは M' -M" (CO ) (これらの式中、 Mは 1A族[0018] The carbonate containing a metal belonging to Group 1A or 2A of the periodic table used in the present invention refers to a general formula MCO, M'CO or M'-M "(CO) Medium, 1A group
、 M'および M"は 2A族に属する金属元素）で表されるものである。特に、 Mは Kであ ることが好ましぐ M'および M"は Mg， Ca, Baから選ばれたものであることが好まし レ、。この例としては、炭酸カリウム、炭酸カルシウム、ドロマイトなどが挙げられるがこれ らに限定されるものではなレ、。これらのうち、タノレク、ウォラストナイト、ドロマイト、酸化 マグネシウム、チタン酸カリウムであることが好ましぐウォラストナイト、タノレクであるこ とが特に好ましい。これらは、単独で、または 1種以上を同時に用いることができる。ま た、本発明で用いられる周期律表の 1A、または 2A族に属する金属の酸化物、過酸 化物、複酸化物、及び炭酸化物から選ばれた少なくとも 1種以上の化合物の粒子の 大きさは、 300メッシュパス以下のものが好ましレ、。 300メッシュパスよりも大きい場合 、液晶ポリエステルに摺動特性を付与する効果は、 300メッシュパス以下のものとさほ ど変わらないが、成形品の外観、成形品中での均一分散性などの面から好ましくな レ、。 , M 'and M "are groups 2A). In particular, M is preferably K. M' and M" are selected from Mg, Ca, and Ba. Les, which are preferably things. Examples include, but are not limited to, potassium carbonate, calcium carbonate, dolomite, and the like. Of these, Tanolek, wollastonite, dolomite, oxidation Particularly preferred are wollastonite and tanolek, which are preferably magnesium and potassium titanate. These can be used alone or in combination of one or more. The particle size of at least one compound selected from the group consisting of oxides, peroxides, double oxides, and carbonates of metals belonging to Group 1A or 2A of the periodic table used in the present invention. The one with a 300 mesh pass or less is preferred. If it is larger than 300 mesh pass, the effect of imparting sliding properties to the liquid crystal polyester is not much different from that of 300 mesh pass or less, but aspects such as appearance of the molded product and uniform dispersibility in the molded product. From the preferred ,.
[0019] 本発明で用いられるフッ素樹脂 (C)とは、分子中にフッ素原子を含むォレフィンから なる重合体で、具体的な例としてはポリテトラフルォロエチレン（以下 PTFEと略す）、 テトラフルォロエチレン一へキサフルォロプロピレン共重合体、ポリトリクロ口フルォロェ チレン、テトラフルォロエチレン一パーフルォロアルキルビュルエーテル共重合体な どである力 特に PTFEが好ましい。  [0019] The fluororesin (C) used in the present invention is a polymer comprising an olefin containing a fluorine atom in a molecule, and specific examples thereof include polytetrafluoroethylene (hereinafter abbreviated as PTFE), A power such as a fluoroethylene-hexafluoropropylene copolymer, a polytrichloroethylene fluoroethylene, or a tetrafluoroethylene-perfluoroalkylbutyl ether copolymer. Particularly preferred is PTFE.
[0020] 本発明で用いられるフッ素樹脂は、重合後、一旦焼成等の成形工程を経た後に粉 末化され流動を起こさないことを特徴としている。流動を起こさないとは、具体的には 、内径 lmm、長さ 20mmのノズノレを持つキヤビラリ一式レオメーターを用レ、、 360°Cの条 件で剪断速度を lOsec— 1から lOOOOsec— 1の範囲内で変化させるという流動試験条件の 下で流動を起こさないものを意味する。該条件下で流動するフッ素樹脂は、摺動性 改善の点で好ましくない。 [0020] The fluororesin used in the present invention is characterized in that it undergoes a molding step such as baking after polymerization, and then is powdered and does not flow. And does not cause flow, specifically, the inner diameter lmm, length ranges Kiyabirari set rheometer with Nozunore shear rate conditions of Yore ,, 360 ° C from LOsec- 1 of LOOOOsec- 1 of 20mm It does not flow under the flow test conditions of changing within. Fluororesins flowing under such conditions are not preferred in terms of improving slidability.
[0021] また、フッ素樹脂の平均粒径は 100 μ m以下であることが摺動性改善のために望ま しぐ更に望ましくは 30 / m以下のものである。このようなフッ素樹脂の例としては、 ( 株）喜多村より入手できる商品名 KT600M等が挙げられる。また、フッ素樹脂の粉末 化の手法としては、機械的粉砕、放射線による粉砕等があるが、ガス発生の点で、機 械的粉砕によるものが好ましい。  The average particle size of the fluororesin is preferably 100 μm or less, more preferably 30 / m or less for improving the slidability. Examples of such a fluororesin include KT600M (trade name) available from Kitamura Corporation. Examples of the method of pulverizing the fluororesin include mechanical pulverization and pulverization by radiation, but mechanical pulverization is preferable in terms of gas generation.
[0022] 本発明の液晶性ポリマー組成物において、周期律表の 1Aまたは 2A族に属する金 属の酸化物、過酸化物、複酸化物、及び炭酸化物から選ばれた少なくとも 1種以上 の化合物 (B)の配合割合は 3 60重量％ (全組成物中）であり、好ましくは 10 50重 量％、更に好ましくは 20— 40重量％である。 (B)成分の配合割合が 60重量％よりも多 い場合は、成形加工時の流動性が悪くなり、良好な成形品を得ることが難しくなるた め好ましくない。また、 (B)成分の配合割合が 3重量％未満の場合は、十分な機械特 性が得られなレ、ため好ましくなレ、。 In the liquid crystalline polymer composition of the present invention, at least one compound selected from the group consisting of metal oxides, peroxides, double oxides, and carbonates belonging to Group 1A or 2A of the periodic table The blending ratio of (B) is 360% by weight (of the total composition), preferably 1050% by weight, and more preferably 20-40% by weight. Component (B) is more than 60% by weight In such a case, the fluidity at the time of molding is deteriorated, and it is difficult to obtain a good molded product, which is not preferable. In addition, when the blending ratio of the component (B) is less than 3% by weight, sufficient mechanical properties cannot be obtained, so that it is not preferable.
[0023] 本発明の液晶性ポリマー組成物において、特定のフッ素樹脂 (C)の配合割合は 0.1 一 30重量％ (全組成物中）であり、好ましくは 1一 15重量％、更に好ましくは 3— 10重 量％である。フッ素樹脂の配合割合が 30重量％より多い場合は、機械強度の低下や 耐熱性の低下を招く好ましくない。また、フッ素樹脂の配合割合が 0.1重量％未満の 場合は、本発明の目的である摺動性の発現が十分ではないため好ましくない。  [0023] In the liquid crystalline polymer composition of the present invention, the mixing ratio of the specific fluororesin (C) is 0.1 to 30% by weight (of the whole composition), preferably 1 to 15% by weight, and more preferably 3 to 15% by weight. — 10% by weight. If the blending ratio of the fluororesin is more than 30% by weight, the mechanical strength and the heat resistance are undesirably reduced. On the other hand, when the blending ratio of the fluororesin is less than 0.1% by weight, the slidability, which is the object of the present invention, is not sufficient, which is not preferable.
[0024] また、本発明の組成物には、液晶性ポリマー (A)に加え、本発明の効果を損なわな レ、範囲で補助的に少量の異方性溶融相を形成しなレ、熱可塑性樹脂、熱硬化性樹脂 を配合してもよい。このような異方性溶融相を形成しない樹脂は、液晶性ポリマー (A) と相溶であってもよいし、非相溶であってもよい。  [0024] In addition to the liquid crystalline polymer (A), the composition of the present invention does not impair the effects of the present invention. You may mix | blend a plastic resin and a thermosetting resin. The resin that does not form such an anisotropic molten phase may be compatible with the liquid crystalline polymer (A) or may be incompatible.
[0025] 異方性溶融相を形成しない熱可塑性樹脂としては、例えばポリエチレン、ポリプロピ レン、ポリブチレン、ポリブタジエン、ポリイソプレン、ポリ酢酸ビュル、ポリ塩化ビニル 、ポリビニリデン、ポリスチレン、アクリル系樹脂、 ABS樹脂、 AS樹脂、 BS樹脂、ポリ ウレタン、シリコーン樹脂、ポリアセタール、ポリカーボネート、ポリエチレンテレフタレ ート、ポリブチレンテレフタレート、芳香族ポリエステル、ポリアミド、ポリアクリロニトリル 、ポリビュルアルコール、ポリビュルエーテル、ポリエーテルイミド、ポリアミドイミド、ポ リエ一テルエーテルイミド、ポリエーテルエーテルケトン、ポリエーテルサルホン、ポリ サルホン、ポリフエ二レンサルファイド、ポリフエ二レンォキシド等を挙げることができ、 異方性溶融相を形成しない熱硬化性樹脂としては、例えばフエノール樹脂、ェポキ シ樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル樹脂、アルキド樹脂等を挙げ ること力 Sできる。  [0025] Examples of the thermoplastic resin that does not form an anisotropic molten phase include polyethylene, polypropylene, polybutylene, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl chloride, polyvinylidene, polystyrene, acrylic resin, ABS resin, AS resin, BS resin, polyurethane resin, silicone resin, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, aromatic polyester, polyamide, polyacrylonitrile, polybutyl alcohol, polybutyl ether, polyetherimide, polyamideimide, Polyetheretherimide, polyetheretherketone, polyethersulfone, polysulfone, polyphenylenesulfide, polyphenyleneoxide, etc. Examples of the thermosetting resin that does not form a melt phase include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin and the like.
[0026] また、本発明の組成物には、必要に応じて、例えば可塑剤、酸化防止剤や紫外線 吸収剤等の安定剤、難燃剤、染料や顔料等の着色剤、発泡剤、ジビニル系化合物、 過酸化物や加硫剤等の架橋剤、流動性や離型性改善のための滑剤としての低分子 有機化合物等を適宜配合することができる。  [0026] The composition of the present invention may contain, if necessary, for example, a plasticizer, a stabilizer such as an antioxidant or an ultraviolet absorber, a flame retardant, a coloring agent such as a dye or a pigment, a foaming agent, or a divinyl-based compound. Compounds, crosslinking agents such as peroxides and vulcanizing agents, and low molecular weight organic compounds as lubricants for improving fluidity and releasability can be appropriately compounded.
[0027] 本発明の液晶性ポリマー組成物を製造するには、原料成分を前記組成割合で含 有させ、混練すればよぐ通常、押出機で混練し、ペレット状に押出し、射出成形等 に用いる力 このような押出機による混練に限定されるものではない。 [0027] In order to produce the liquid crystalline polymer composition of the present invention, the raw material components are contained in the above composition ratio. Normally, kneading is performed by an extruder, extruded into pellets, and used in injection molding. Kneading by such an extruder is not limited.
実施例  Example
[0028] 以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるも のではない。尚、実施例中の物性の測定および試験は次の方法で行った。  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In addition, the measurement and the test of the physical property in an Example were performed by the following method.
(1)摺動性試験  (1) Slidability test
鈴木式摺動試験機を用い、内径 20mm、外径 25.6mm、高さ 15mmの円筒状試験片 を使用し、 S55C製 φ 10mmのピンを相手材として、圧力 3.92MPa、速度 30cm/secの 条件下で 24時間摺動させた後の比磨耗量を測定した。  Using a Suzuki-type sliding tester, a cylindrical test piece with an inner diameter of 20 mm, an outer diameter of 25.6 mm, and a height of 15 mm, using a S55C φ10 mm pin as a mating material, a pressure of 3.92 MPa and a speed of 30 cm / sec. The specific abrasion after sliding for 24 hours under was measured.
(2)溶融粘度  (2) Melt viscosity
φ lmm、 L = 20mmのオリフィスを使用し、温度 360°Cにて剪断速度 lOOOsec— 1の時の 溶融粘度を測定した。 Using an orifice with φ lmm and L = 20 mm, the melt viscosity was measured at a shear rate of 100 sec- 1 at a temperature of 360 ° C.
(3)曲げ試験  (3) Bending test
ISO 178に準拠し、曲げ強度の測定を行った。  The bending strength was measured according to ISO 178.
実施例 1一 6  Example 11
液晶性ポリエステル (LCP ;ポリプラスチックス（株)製、ベクトラ E950i)と表 1に示す 成分を表 1に示す割合でドライブレンドした後、二軸押出機（(株）日本製鋼所製、 TE X—30ひ型）にて溶融混練し、ペレット化した。このペレットから射出成形機により上記 試験片を作成し、評価した。結果を表 1に示す。  After dry blending a liquid crystalline polyester (LCP; Vectra E950i, manufactured by Polyplastics Co., Ltd.) with the components shown in Table 1, in a ratio shown in Table 1, a twin-screw extruder (manufactured by Nippon Steel Works, TE X -30 molds) to form a pellet. The test pieces were prepared from the pellets using an injection molding machine and evaluated. The results are shown in Table 1.
[0029] 実施例で使用した各成分は以下のものである。 [0029] Each component used in the examples is as follows.
(B)成分  (B) component
'ウォラストナイト一 1 : Nyglos8 (NYC〇社製）  'Wollast Knight 1: Nyglos8 (NYC〇)
•ウォラストナイト一 2： Nyglos5 (NYC〇社製）  • Wollast Night 1 2: Nyglos5 (NYCNY)
•チタン酸カリウム: TISMO N (大塚化学社製）  • Potassium titanate: TISMO N (Otsuka Chemical Co., Ltd.)
•マイ力： A— 41 (山口雲母社製）  • My power: A—41 (Miyako Yamaguchi)
'タルク：クラウンタルク PP (松村産業社製）  'Talc: Crown Talc PP (Matsumura Sangyo)
(C)成分  (C) component
• PTFE-1： KT600M (喜多村社製；前記流動試験で流動せず） • PTFE-2： KT400M (喜多村社製；前記流動試験で流動せず） • PTFE-1: KT600M (manufactured by Kitamura Co .; does not flow in the above flow test) • PTFE-2: KT400M (manufactured by Kitamura; not flowable in the above flow test)
比較例 1一 9  Comparative Example 11
比較例として、 (C)成分を配合しない場合 (比較例 1一 4)、（B)成分に代えてガラス 繊維を用いた場合（比較例 5)、本発明の要件を満たさなレ、 PTFE— 3— 4を用いた場 合 (比較例 6— 7)、成分 (C)、成分 ）の配合量が過大の場合 (比較例 6— 7)につい て、実施例と上記試験片を作成し、評価した。結果を表 1に示す。  As a comparative example, when the component (C) was not blended (Comparative Examples 14 to 14), and when glass fiber was used instead of the component (B) (Comparative Example 5), PTFE which did not satisfy the requirements of the present invention was used. In the case where 3-4 was used (Comparative Example 6-7) and the amount of component (C), the component) was too large (Comparative Example 6-7), the example and the above test piece were prepared. evaluated. The results are shown in Table 1.
[0030] 比較例で使用した各成分は以下のものである。 [0030] The components used in the comparative examples are as follows.
配合した量  Incorporated amount
(C)成分 (比較品）  (C) component (comparative product)
. PTFE-3：セフラルノレーブ I (セントラル硝子製；前記流動試験で流動）  PTFE-3: Sefralnorebe I (manufactured by Central Glass; flowable in the flow test described above)
• PTFE-4： KTL610 (喜多村社製；前記流動試験で流動）  • PTFE-4: KTL610 (manufactured by Kitamura Corporation; flow in the flow test described above)
その他  Other
'ガラス繊維： CS03JA419 (旭ファイバーグラス社製）  'Glass fiber: CS03JA419 (made by Asahi Fiberglass)
[0031] [表 1] [0031] [Table 1]
Figure imgf000011_0001
Figure imgf000011_0001
配合量の数値は重量％である The numerical value of the compounding amount is% by weight.

Claims

請求の範囲 The scope of the claims
[1] 液晶性ポリマー (A)に対して、周期律表の 1Aまたは 2A族に属する金属の酸化物、 過酸化物、複酸化物、及び炭酸化物から選ばれた少なくとも 1種以上の化合物 (B) 3 一 60重量％ (全組成物中）、重合後、一旦成形工程を経た後に粉末化され、下記の 試験条件で流動を起こさないフッ素樹脂 (C) 0.1 30重量％ (全組成物中）を配合し てなる液晶性ポリマー組成物。  [1] At least one compound selected from oxides, peroxides, double oxides, and carbonates of metals belonging to Group 1A or 2A of the periodic table with respect to the liquid crystalline polymer (A) ( B) 3 60% by weight (of all compositions), fluoropolymer (C) 0.130% by weight (in the total composition), which is powdered after undergoing a molding step once after polymerization and does not flow under the following test conditions ), A liquid crystalline polymer composition comprising:
(フッ素樹脂の流動試験条件）  (Fluid resin flow test conditions)
内径 lmm、長さ 20mmのノズノレを持つキヤビラリ一式レオメーターを用レ、、 360°Cの条 件で剪断速度を lOsec— 1から lOOOOsec— 1の範囲内で変化させる。 Use a complete set of rheometers with a diameter of lmm and a length of 20mm. Change the shear rate within the range of lOsec- 1 to lOOOOsec- 1 at 360 ° C.
[2] 周期律表の 1 Aまたは 2A族に属する金属の酸化物、過酸化物、複酸化物、及び炭 酸化物から選ばれた少なくとも 1種以上の化合物 (B)力 タルク、ウォラストナイト、ドロ マイト、酸化マグネシウム、チタン酸カリウム、マイ力から選ばれる少なくとも 1種以上 の化合物である請求項 1記載の液晶性ポリマー組成物。  [2] At least one compound selected from oxides, peroxides, double oxides, and carbonates of metals belonging to Group 1A or 2A of the Periodic Table (B) Force talc, wollastonite 2. The liquid crystalline polymer composition according to claim 1, wherein the composition is at least one compound selected from the group consisting of dolomite, magnesium oxide, potassium titanate, and mycium.
[3] フッ素樹脂 (C)が、機械的粉砕により粉末化されたものである請求項 1又は 2記載の 液晶性ポリマー組成物。  3. The liquid crystalline polymer composition according to claim 1, wherein the fluororesin (C) is powdered by mechanical pulverization.
[4] 請求項 1一 3の何れ力 4項記載の液晶性ポリマー組成物からなる成形品。  [4] A molded article comprising the liquid crystalline polymer composition according to item 4, wherein the liquid crystalline polymer composition is described in item 4.
[5] 請求項 1一 3の何れ力 4項記載の液晶性ポリマー組成物からなる摺動部品。  [5] A sliding component comprising the liquid crystalline polymer composition according to any one of [1] to [3].
PCT/JP2004/018778 2003-12-17 2004-12-16 Composition of liquid-crystalline polymer WO2005059035A1 (en)

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JP2006182877A (en) * 2004-12-27 2006-07-13 Nippon Petrochemicals Co Ltd Slide member
CN114096613B (en) * 2019-08-27 2023-05-02 东丽株式会社 Liquid crystal polyester resin composition, laminate, liquid crystal polyester resin film, and method for producing same

Citations (3)

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Publication number Priority date Publication date Assignee Title
JPH05320675A (en) * 1992-05-15 1993-12-03 Nippon Petrochem Co Ltd Sliding resin composition for soft metal
JPH1025402A (en) * 1996-07-09 1998-01-27 Sumitomo Chem Co Ltd Liquid-crystal polyester resin composition
JP2003171538A (en) * 2001-12-07 2003-06-20 Dainippon Ink & Chem Inc Liquid crystal polyester resin composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05320675A (en) * 1992-05-15 1993-12-03 Nippon Petrochem Co Ltd Sliding resin composition for soft metal
JPH1025402A (en) * 1996-07-09 1998-01-27 Sumitomo Chem Co Ltd Liquid-crystal polyester resin composition
JP2003171538A (en) * 2001-12-07 2003-06-20 Dainippon Ink & Chem Inc Liquid crystal polyester resin composition

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