WO2024143334A1 - Liquid crystalline resin composition and connector using same - Google Patents

Liquid crystalline resin composition and connector using same Download PDF

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Publication number
WO2024143334A1
WO2024143334A1 PCT/JP2023/046579 JP2023046579W WO2024143334A1 WO 2024143334 A1 WO2024143334 A1 WO 2024143334A1 JP 2023046579 W JP2023046579 W JP 2023046579W WO 2024143334 A1 WO2024143334 A1 WO 2024143334A1
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resin composition
liquid crystal
crystal resin
mass
liquid crystalline
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PCT/JP2023/046579
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French (fr)
Japanese (ja)
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真奈 中村
昭宏 長永
峰生 大竹
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ポリプラスチックス株式会社
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Publication of WO2024143334A1 publication Critical patent/WO2024143334A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention has been made to solve the above problems, and its purpose is to provide a liquid crystalline resin composition with good flowability and releasability that gives a molded article with excellent mechanical strength and suppressed blistering, and a connector using the same.
  • the liquid crystalline resin composition has a content of the plate-like filler (E) of 5 to 15% by mass based on the entire liquid crystalline resin composition.
  • a molded article comprising a liquid crystal resin composition according to any one of (1) to (5).
  • FIG. 1(a) is a perspective view showing a U-shaped liquid crystalline resin molding used in the evaluation of releasability carried out in the examples
  • FIG. 1(b) is a side view showing the U-shaped liquid crystalline resin molding.
  • the liquid crystal resin composition of the present invention contains (A) a liquid crystal resin, (B) whiskers, (C) an epoxy group-containing olefin polymer, and (D) a polyhydric alcohol fatty acid ester.
  • the liquid crystal resin (A) used in the present invention refers to a melt-processable polymer having the property of being capable of forming an optically anisotropic molten phase.
  • the property of the anisotropic molten phase can be confirmed by a conventional polarized light inspection method using crossed polarizers. More specifically, the anisotropic molten phase can be confirmed by observing a molten sample placed on a Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarizing microscope.
  • the liquid crystal polymer applicable to the present invention is inspected between crossed polarizers, it usually transmits polarized light even in a molten stationary state, and is optically anisotropic.
  • the type of liquid crystal resin (A) as described above is not particularly limited, but is preferably an aromatic polyester and/or an aromatic polyester amide. Polyesters that partially contain aromatic polyesters and/or aromatic polyester amides in the same molecular chain are also included in this range.
  • the liquid crystal resin (A) one that has an inherent viscosity (I.V.) of preferably at least about 2.0 dl/g, and more preferably 2.0 to 10.0 dl/g when dissolved in pentafluorophenol at a concentration of 0.1% by mass at 60°C is preferably used.
  • the aromatic polyester or aromatic polyesteramide as the liquid crystal resin (A) applicable to the present invention is particularly preferably an aromatic polyester or aromatic polyesteramide having as a constituent component a constituent unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof.
  • the content of the constituent units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and their derivatives is preferably 45 mol% or more, more preferably 50 mol% or more, even more preferably 55 mol% or more, even more preferably 60 mol% or more, and particularly preferably 62 mol% or more, based on all the constituent units, from the viewpoint of suppressing fluctuations in the molecular structure of (A) liquid crystal resin.
  • the upper limit of the content is not particularly limited, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, 75 mol% or less, or 70 mol% or less, based on all the constituent units.
  • aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid
  • aromatic diols such as 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcin, compounds represented by the following general formula (I) and compounds represented by the following general formula (II)
  • aromatic dicarboxylic acids such as 1,4-phenylenedicarboxylic acid, 1,3-phenylenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid and compounds represented by the following general formula (III); aromatic amines such as p-aminophenol, p-phenylenediamine and N-acetyl-p-aminophenol.
  • aromatic hydroxycarboxylic acid and its derivatives 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, or a combination thereof are preferred from the viewpoints of reactivity and stability of the molecular structure of the liquid crystal resin (A).
  • X is a group selected from alkylene (C 1 to C 4 ), alkylidene, —O—, —SO—, —SO 2 —, —S—, and —CO—.
  • the liquid crystal resin (A) used in the present invention can be prepared by a known method using direct polymerization or transesterification from the above monomer compound (or mixture of monomers). Usually, melt polymerization, solution polymerization, slurry polymerization, solid-phase polymerization, or a combination of two or more of these methods is used, and melt polymerization or a combination of melt polymerization and solid-phase polymerization is preferably used.
  • melt polymerization, solution polymerization, slurry polymerization, solid-phase polymerization, or a combination of two or more of these methods is used, and melt polymerization or a combination of melt polymerization and solid-phase polymerization is preferably used.
  • the above compounds capable of forming esters may be used in the polymerization as they are, or may be modified from a precursor to a derivative capable of forming the ester at a stage prior to polymerization.
  • catalysts can be used in these polymerizations, and representative examples include metal salt catalysts such as potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris(2,4-pentanedionato)cobalt(III), and organic compound catalysts such as 1-methylimidazole and 4-dimethylaminopyridine.
  • the amount of catalyst used is generally about 0.001 to 1% by mass, and preferably about 0.01 to 0.2% by mass, based on the total mass of the monomers. If necessary, the molecular weight of the polymer produced by these polymerization methods can be further increased by solid-phase polymerization, in which the polymer is heated under reduced pressure or in an inert gas.
  • the melt viscosity of the liquid crystal resin (A) obtained by the above method is not particularly limited.
  • a resin having a melt viscosity at the molding temperature of 3 Pa ⁇ s to 500 Pa ⁇ s at a shear rate of 1000 sec -1 can be used.
  • a resin having a viscosity that is too high is not preferred because it significantly deteriorates the flowability.
  • the liquid crystal resin (A) may be a mixture of two or more kinds of liquid crystal resins.
  • the fiber diameter of the (B) whiskers is preferably 0.2 to 15 ⁇ m or less, and more preferably 0.25 to 10 ⁇ m. When the fiber diameter is within the above range, the mechanical strength of the molded body is more likely to be improved.
  • the fiber diameter of the (B) whiskers is determined by observing the whiskers with a scanning electron microscope and measuring the fiber diameter of 30 whiskers, and the average of these values is used. The fiber diameter of the (B) whiskers in the liquid crystalline resin composition is measured by applying the above method to the whiskers remaining after the liquid crystalline resin composition is heated at 600°C for 2 hours to incinerate the composition.
  • the aspect ratio of the whiskers i.e., the value of the average fiber length/fiber diameter, is preferably 8 or more, more preferably 10 to 100, and even more preferably 15 to 75, from the viewpoint of the mechanical strength of a molded article such as a connector that contains the liquid crystalline resin composition according to the present invention.
  • the liquid crystal resin composition of the present invention contains an epoxy group-containing olefin polymer (C).
  • the liquid crystal resin composition of the present invention tends to have a well-balanced and excellent mechanical strength and blister resistance while maintaining the excellent mold releasability of the liquid crystal resin composition of the present invention.
  • epoxy group-containing olefin polymers include copolymers composed of repeating units derived from ⁇ -olefins and repeating units derived from glycidyl esters of ⁇ , ⁇ -unsaturated acids.
  • the epoxy group-containing olefin polymers may be used alone or in combination of two or more types.
  • the ⁇ -olefin is not particularly limited, and examples thereof include ethylene, propylene, butene, among which ethylene is preferably used.
  • the glycidyl ester of an ⁇ , ⁇ -unsaturated acid is represented by the following general formula (IV).
  • R' represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a group represented by -R 1 -COOH, and R 1 represents an alkylene group having 1 to 5 carbon atoms.
  • the content of repeating units derived from ⁇ -olefin is preferably 87 to 98% by mass, and the content of repeating units derived from glycidyl ester of ⁇ , ⁇ -unsaturated acid is preferably 13 to 2% by mass.
  • the epoxy group-containing olefin polymer may contain, in addition to the above two components, a third component of repeating units derived from one or more olefin-based unsaturated monomers such as acrylonitrile, acrylic acid esters, methacrylic acid esters, ⁇ -methylstyrene, maleic anhydride, etc., in an amount of 0 to 48 parts by mass per 100 parts by mass of the above two components, as long as it does not impair the present invention.
  • a third component of repeating units derived from one or more olefin-based unsaturated monomers such as acrylonitrile, acrylic acid esters, methacrylic acid esters, ⁇ -methylstyrene, maleic anhydride, etc.
  • Epoxy group-containing olefin polymers can be easily prepared by a normal radical polymerization method using monomers corresponding to each component and a radical polymerization catalyst. More specifically, they can usually be produced by a method in which an ⁇ -olefin and a glycidyl ester of an ⁇ , ⁇ -unsaturated acid are copolymerized in the presence of a radical generator at 500 to 4000 atmospheres and 100 to 300°C in the presence or absence of a suitable solvent or chain transfer agent.
  • the liquid crystal resin composition according to the present invention contains (D) a polyhydric alcohol fatty acid ester.
  • the mold releasability of the liquid crystal resin composition is likely to be improved, and the molded article is likely to have excellent mechanical strength and blister resistance.
  • the (D) polyhydric alcohol fatty acid ester may be used alone or in combination of two or more.
  • a polyhydric alcohol is a compound having two or more alcoholic hydroxyl groups in the molecule.
  • the polyhydric alcohol is preferably a polyhydric alcohol having 3 to 32 carbon atoms.
  • Examples of the polyhydric alcohol include polyglycerols such as glycerin, diglycerin, and decaglycerin; pentaerythritol; dipentaerythritol; diethylene glycol; and propylene glycol.
  • the polyhydric alcohol may be used alone or in combination of two or more. In terms of the heat resistance of the resulting polyhydric alcohol fatty acid ester, pentaerythritol and dipentaerythritol are particularly preferred as polyhydric alcohols.
  • the content of the plate-like filler (E) is preferably 5 to 15 mass% relative to the entire liquid crystal resin composition of the present invention. When the content of the plate-like filler (E) is within the above range, it is easier to obtain a molded article with suppressed anisotropy from the resulting composition while maintaining excellent mechanical strength.
  • the content of the plate-like filler (E) is more preferably 6 to 13 mass%, and even more preferably 8 to 12 mass%.
  • the talc usable in the present invention preferably has a total content of Fe2O3 , Al2O3 and CaO of 2.5 % by mass or less, a total content of Fe2O3 and Al2O3 of more than 1.0% by mass and 2.0 % by mass or less, and a CaO content of less than 0.5% by mass , relative to the total solid content of the talc. That is, the talc usable in the present invention may contain at least one of Fe2O3 , Al2O3 and CaO in addition to SiO2 and MgO as the main components, and each component may be contained within the above content range.
  • Mica is a pulverized silicate mineral containing aluminum, potassium, magnesium, sodium, iron, etc.
  • Examples of mica that can be used in the present invention include muscovite, phlogopite, biotite, and artificial mica, among which muscovite is preferred because of its good hue and low cost.
  • wet grinding and dry grinding are known as methods for grinding minerals.
  • mica raw ore is coarsely ground in a dry grinder, water is added to the slurry, and the resulting material is then wet-ground and dehydrated.
  • the dry grinding method is a common method with low cost, but the wet grinding method makes it easier to grind minerals thinly and finely.
  • it is preferable to use thin and finely ground material because it can obtain mica having the above-mentioned median diameter and the preferred thickness described below. Therefore, in the present invention, it is preferable to use mica produced by the wet grinding method.
  • a step of dispersing the ground material in water is necessary, so that in order to increase the dispersion efficiency of the ground material, it is common to add a flocculating sedimentation agent and/or a sedimentation aid to the ground material.
  • flocculating sedimentation agents and sedimentation aids examples include polyaluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, copper chloride, polyferric sulfate, polyferric chloride, iron-silica inorganic polymer flocculant, ferric chloride-silica inorganic polymer flocculant, hydrated lime (Ca(OH) 2 ), caustic soda (NaOH), soda ash (Na 2 CO 3 ), etc.
  • These flocculating sedimentation agents and sedimentation aids have an alkaline or acidic pH.
  • the mica used in the present invention is preferably one that does not use a flocculating sedimentation agent and/or a sedimentation aid when wet grinding.
  • a flocculating sedimentation agent and/or a sedimentation aid when used, decomposition of the polymer in the liquid crystalline resin composition is unlikely to occur, and large amounts of gas are unlikely to be generated, or a decrease in the molecular weight of the polymer is unlikely to occur, making it easier to maintain the performance of the resulting molded article better.
  • the thickness of the mica that can be used in the present invention is preferably 0.01 to 1 ⁇ m, and particularly preferably 0.03 to 0.3 ⁇ m, as measured by observation under an electron microscope. If the thickness of the mica is 0.01 ⁇ m or more, the mica is less likely to crack during melt processing of the liquid crystalline resin composition, which is preferable since it may be easier to improve the rigidity of the molded article. If the thickness of the mica is 1 ⁇ m or less, the effect of improving the rigidity of the molded article is likely to be sufficient, which is preferable.
  • the mica that can be used in the present invention may be surface-treated with a silane coupling agent or the like, and/or may be granulated with a binder to form granules.
  • liquid crystal resin composition of the present invention other polymers, other fillers, other release agents, and known substances generally added to synthetic resins, i.e., stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, crystallization accelerators, crystal nucleating agents, etc., may be appropriately added depending on the required performance, within a range that does not impair the effects of the present invention.
  • Epoxy group-containing styrene polymers include known epoxy group-containing styrene polymers, including copolymers composed of repeating units derived from styrenes and repeating units derived from glycidyl esters of ⁇ , ⁇ -unsaturated acids.
  • Epoxy group-free olefin polymers include, for example, polyethylene, polypropylene, polybutene, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-octene copolymers, polybutadiene, polyisoprene, polychloroprene, ethylene-propylene-butadiene copolymers, ethylene-propylene-isoprene copolymers, ethylene-propylene-chloroprene copolymers, ethylene-ethyl acrylate copolymers, ethylene-vinyl acetate copolymers, etc.
  • the other fillers refer to fillers other than (B) whiskers and (E) plate-like fillers, and examples thereof include (C) granular fillers such as silica; fibrous fillers other than (B) whiskers, such as glass fiber; and carbon black. Since the effect of suppressing nap formation on the surface of the molded product is likely to be high, it is preferable that the liquid crystalline resin composition of the present invention does not contain fibrous fillers other than (B) whiskers, such as glass fiber.
  • the other release agent refers to a release agent other than the polyhydric alcohol fatty acid ester (D), and examples thereof include fatty acid metal salts such as calcium stearate, fatty acid amides, low molecular weight polyolefins, and the like. Since a molded article having improved blister resistance while maintaining superior mechanical strength and superior release properties can be easily obtained from the liquid crystal resin composition of the present invention, it is preferable that the liquid crystal resin composition of the present invention does not contain a release agent other than the polyhydric alcohol fatty acid ester (D), for example, a fatty acid metal salt such as calcium stearate.
  • a release agent other than the polyhydric alcohol fatty acid ester (D) for example, a fatty acid metal salt such as calcium stearate.
  • the preparation of the resin composition of the present invention is not particularly limited.
  • the above-mentioned (A) component, (B) component, (C) component, (D) component, optionally (E) component, and optionally other components are mixed, and melt-kneaded using a single-screw or twin-screw extruder to prepare a liquid crystal resin composition.
  • Aromatic polyester amide The following raw materials were charged into a polymerization vessel, and the temperature of the reaction system was raised to 140°C and reacted at 140°C for 1 hour. Thereafter, the temperature was further raised to 340°C over 4.5 hours, and the pressure was reduced to 10 Torr (i.e., 1330 Pa) over 15 minutes, and melt polymerization was carried out while distilling out acetic acid, excess acetic anhydride, and other low boiling points.

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Abstract

Provided are a liquid crystalline resin composition with good flowability and mold release properties, having excellent mechanical strength and providing a molded body with suppressed blistering, and a connector using the same.　A liquid crystalline resin composition according to the present invention contains (A) a liquid crystalline resin, (B) whiskers, (C) an epoxy group-containing olefinic polymer, and (D) a polyhydric alcohol fatty acid ester, wherein, relative to the total liquid crystalline resin composition, the content of (B) the whiskers is 20-40 mass%, the content of (C) the epoxy group-containing olefinic polymer is 0.5-6 mass%, and the content of (D) the polyhydric alcohol fatty acid ester is 0.1-2.0 mass%. The liquid crystalline resin composition according to the present invention further contains (E) a plate-like filler, and the content of (E) the plate-like filler is 5-15 mass% relative to the total liquid crystalline resin composition. A molded body according to the present invention contains the liquid crystalline resin composition. A connector according to the present invention is formed of the molded body.

Description

液晶性樹脂組成物及びそれを用いたコネクターLiquid crystal resin composition and connector using same
　本発明は、液晶性樹脂組成物及びそれを用いたコネクターに関する。 The present invention relates to a liquid crystalline resin composition and a connector using the same.
　液晶性ポリエステル樹脂に代表される液晶性樹脂は、優れた機械的強度、耐熱性、耐薬品性、電気的性質等をバランス良く有し、優れた寸法安定性も有するため高機能エンジニアリングプラスチックとして広く利用されている。 Liquid crystal resins, such as liquid crystal polyester resins, have a good balance of excellent mechanical strength, heat resistance, chemical resistance, electrical properties, etc., and also have excellent dimensional stability, so they are widely used as high-performance engineering plastics.
　特に、近年のエレクトロニクス機器の小型化及び薄型化に伴い、エレクトロニクス機器を構成する電子部品（コネクター等）の低背化及び狭ピッチ化に対するニーズがある。例えば、特許文献１には、マイカ及びガラス繊維で強化された液晶性樹脂組成物から成形されたコネクターが開示されている。このようなコネクターは、耐熱性、そり変形の抑制、寸法安定性等が要求される、基板対基板（Ｂ　ｔｏ　Ｂ）コネクターや、フレキシブルプリント基板（ＦＰＣ）とフレキシブルフラットケーブル（ＦＦＣ）とを接続するために使用されるＦＰＣコネクター等として採用されている。 In particular, with the recent trend toward smaller and thinner electronic devices, there is a need for lower heights and narrower pitches in the electronic components (connectors, etc.) that make up the electronic devices. For example, Patent Document 1 discloses a connector molded from a liquid crystalline resin composition reinforced with mica and glass fibers. Such connectors are used as board-to-board (B to B) connectors, which require heat resistance, suppression of warpage deformation, dimensional stability, etc., and FPC connectors used to connect flexible printed circuit boards (FPCs) and flexible flat cables (FFCs).
　また、液晶性樹脂組成物には、ブリスター発生の問題が生じ得る。即ち、液晶性ポリエステル、液晶性ポリエステルアミド等の液晶性ポリマーは、高温熱安定性が良いため、高温での熱処理を要する材料に使用される場合が多い。しかし、成形品を高温の空気中及び液体中に長時間放置すると、表面にブリスターと呼ばれる細かい膨れが生じるという問題が起こる。 In addition, liquid crystal resin compositions can have the problem of blister formation. That is, liquid crystal polymers such as liquid crystal polyesters and liquid crystal polyesteramides have good thermal stability at high temperatures, so they are often used in materials that require heat treatment at high temperatures. However, if a molded product is left in high-temperature air or liquid for a long period of time, a problem occurs in which fine swellings called blisters form on the surface.
　この現象の一原因は、液晶性ポリマーが溶融状態にある時に発生する分解ガス等が成形品内部に持ち込まれ、その後、高温の熱処理を行う際にそのガスが膨張し、加熱で軟化した成形品表面を押し上げ、押し上げられた部分がブリスターとして現れることである。このような原因で発生するブリスターの発生が低減された液晶性樹脂組成物としては、例えば、特許文献２には、液晶性ポリエステルと特定の脂肪酸エステルと充填材と脂肪酸金属塩とを含有する液晶性樹脂組成物が開示されている。 One cause of this phenomenon is that decomposition gases and the like generated when the liquid crystalline polymer is in a molten state are carried into the molded product, and then when the product is subjected to high-temperature heat treatment, the gases expand and push up the surface of the molded product that has been softened by heating, causing the pushed-up parts to appear as blisters. For example, Patent Document 2 discloses a liquid crystalline resin composition that contains a liquid crystalline polyester, a specific fatty acid ester, a filler, and a fatty acid metal salt, as an example of a liquid crystalline resin composition that reduces the occurrence of blisters caused by such causes.
特開２００６－３７０６１号公報JP 2006-37061 A 特開２００９－１７９６９３号公報JP 2009-179693 A
　本発明者らの検討によれば、従来の液晶性樹脂組成物からコネクターを成形しようとすると、当該液晶性樹脂組成物の流動性及び離型性が十分ではなく加工性に劣るため、低背化及び狭ピッチ化に対するニーズに対応したコネクターの製造が困難であった。また、機械的強度及び耐ブリスター性にバランスよく優れる成形体を従来の液晶性樹脂組成物から得ることは容易ではない。 According to the inventors' investigations, when attempting to mold a connector from a conventional liquid crystalline resin composition, the liquid crystalline resin composition has insufficient fluidity and releasability, making it poor in processability, and therefore it has been difficult to manufacture a connector that meets the needs for a low height and narrow pitch. In addition, it is not easy to obtain a molded product that has a good balance between mechanical strength and blister resistance from a conventional liquid crystalline resin composition.
　本発明は、上記課題を解決するためになされたものであり、その目的は、機械的強度に優れ、ブリスター発生が抑制された成形体を与える、流動性及び離型性が良好な液晶性樹脂組成物及びそれを用いたコネクターを提供することにある。 The present invention has been made to solve the above problems, and its purpose is to provide a liquid crystalline resin composition with good flowability and releasability that gives a molded article with excellent mechanical strength and suppressed blistering, and a connector using the same.
　本発明者らは、上記課題を解決するために鋭意研究を重ねた。その結果、液晶性樹脂とウィスカーとエポキシ基含有オレフィン系重合体と多価アルコール脂肪酸エステルとを、特定の割合で含有する液晶性樹脂組成物を用いることで、上記課題を解決できることを見出し、本発明を完成するに至った。より具体的には本発明は以下のものを提供する。 The present inventors have conducted extensive research to solve the above problems. As a result, they have found that the above problems can be solved by using a liquid crystalline resin composition that contains a liquid crystalline resin, whiskers, an epoxy group-containing olefin polymer, and a polyhydric alcohol fatty acid ester in specific ratios, and have completed the present invention. More specifically, the present invention provides the following:
　（１）　（Ａ）液晶性樹脂、
　（Ｂ）ウィスカー、
　（Ｃ）エポキシ基含有オレフィン系重合体、及び
　（Ｄ）多価アルコール脂肪酸エステル
を含有する液晶性樹脂組成物であって、
　前記液晶性樹脂組成物全体に対して、
　前記（Ｂ）ウィスカーの含有量は、２０～４０質量％、
　前記（Ｃ）エポキシ基含有オレフィン系重合体の含有量は、０．５～６質量％、
　前記（Ｄ）多価アルコール脂肪酸エステルの含有量は、０．１～２．０質量％
である液晶性樹脂組成物。 (1) (A) a liquid crystalline resin,
(B) whiskers,
A liquid crystalline resin composition comprising: (C) an epoxy group-containing olefin polymer; and (D) a polyhydric alcohol fatty acid ester,
With respect to the entire liquid crystal resin composition,
The content of the whiskers (B) is 20 to 40 mass %,
The content of the epoxy group-containing olefin polymer (C) is 0.5 to 6 mass %,
The content of the polyhydric alcohol fatty acid ester (D) is 0.1 to 2.0% by mass.
The liquid crystal resin composition according to the present invention is
　（２）　前記（Ａ）液晶性樹脂は、芳香族ヒドロキシカルボン酸及びその誘導体からなる群より選ばれる少なくとも１種に由来する構成単位を構成成分として有する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（１）に記載の液晶性樹脂組成物。 (2) The liquid crystal resin composition according to (1), wherein the (A) liquid crystal resin is an aromatic polyester or aromatic polyester amide having as a constituent a structural unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof.
　（３）　前記（Ｄ）多価アルコール脂肪酸エステルは、ペンタエリスリトールの脂肪酸エステル及びジペンタエリスリトールの脂肪酸エステルからなる群より選ばれる少なくとも１種である（１）又は（２）に記載の液晶性樹脂組成物。 (3) The liquid crystal resin composition according to (1) or (2), wherein the (D) polyhydric alcohol fatty acid ester is at least one selected from the group consisting of pentaerythritol fatty acid esters and dipentaerythritol fatty acid esters.
　（４）　前記液晶性樹脂組成物全体に対して、前記（Ｂ）ウィスカーの含有量は、２５～４０質量％である（１）から（３）のいずれかに記載の液晶性樹脂組成物。 (4) A liquid crystal resin composition according to any one of (1) to (3), in which the content of the whiskers (B) is 25 to 40 mass% relative to the entire liquid crystal resin composition.
　（５）　更に（Ｅ）板状充填剤を含有する（１）から（４）のいずれかに記載の液晶性樹脂組成物であって、
　前記液晶性樹脂組成物全体に対して、前記（Ｅ）板状充填剤の含有量は、５～１５質量％である液晶性樹脂組成物。 (5) The liquid crystalline resin composition according to any one of (1) to (4), further comprising (E) a plate-like filler,
The liquid crystalline resin composition has a content of the plate-like filler (E) of 5 to 15% by mass based on the entire liquid crystalline resin composition.
　（６）　コネクター用である（１）から（５）のいずれかに記載の液晶性樹脂組成物。 (6) A liquid crystal resin composition according to any one of (1) to (5) for use in a connector.
　（７）　コネクターを製造するための、（１）から（５）のいずれかに記載の液晶性樹脂組成物の使用。 (7) Use of the liquid crystal resin composition according to any one of (1) to (5) for producing a connector.
　（８）　（１）から（５）のいずれかに記載の液晶性樹脂組成物を含む成形体。 (8) A molded article comprising a liquid crystal resin composition according to any one of (1) to (5).
　（９）　（８）に記載の成形体からなるコネクター。 (9) A connector made of the molded article described in (8).
　本発明の液晶性樹脂組成物を含む成形体は、機械的強度及び離型性に優れ、ブリスター発生が抑制されている。 　Molded articles containing the liquid crystal resin composition of the present invention have excellent mechanical strength and releasability, and the occurrence of blisters is suppressed.
図１（ａ）は、実施例で行った離型性評価に用いたコの字型液晶性樹脂成形体を示す斜視図であり、図１（ｂ）は、上記コの字型液晶性樹脂成形体を示す側面図である。FIG. 1(a) is a perspective view showing a U-shaped liquid crystalline resin molding used in the evaluation of releasability carried out in the examples, and FIG. 1(b) is a side view showing the U-shaped liquid crystalline resin molding.
　以下、本発明の実施形態について説明する。なお、本発明は以下の実施形態に限定されない。 The following describes an embodiment of the present invention. Note that the present invention is not limited to the following embodiment.
＜液晶性樹脂組成物＞
　本発明の液晶性樹脂組成物は、（Ａ）液晶性樹脂、（Ｂ）ウィスカー、（Ｃ）エポキシ基含有オレフィン系重合体、及び（Ｄ）多価アルコール脂肪酸エステルを含有する。 <Liquid Crystalline Resin Composition>
The liquid crystal resin composition of the present invention contains (A) a liquid crystal resin, (B) whiskers, (C) an epoxy group-containing olefin polymer, and (D) a polyhydric alcohol fatty acid ester.
［（Ａ）液晶性樹脂］
　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。 [(A) Liquid Crystalline Resin]
The liquid crystal resin (A) used in the present invention refers to a melt-processable polymer having the property of being capable of forming an optically anisotropic molten phase. The property of the anisotropic molten phase can be confirmed by a conventional polarized light inspection method using crossed polarizers. More specifically, the anisotropic molten phase can be confirmed by observing a molten sample placed on a Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarizing microscope. When the liquid crystal polymer applicable to the present invention is inspected between crossed polarizers, it usually transmits polarized light even in a molten stationary state, and is optically anisotropic.
　上記のような（Ａ）液晶性樹脂の種類としては特に限定されず、芳香族ポリエステル及び／又は芳香族ポリエステルアミドであることが好ましい。また、芳香族ポリエステル及び／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。（Ａ）液晶性樹脂としては、６０℃でペンタフルオロフェノールに濃度０．１質量％で溶解したときに、好ましくは少なくとも約２．０ｄｌ／ｇ、更に好ましくは２．０～１０．０ｄｌ／ｇの対数粘度（Ｉ．Ｖ．）を有するものが好ましく使用される。 The type of liquid crystal resin (A) as described above is not particularly limited, but is preferably an aromatic polyester and/or an aromatic polyester amide. Polyesters that partially contain aromatic polyesters and/or aromatic polyester amides in the same molecular chain are also included in this range. As the liquid crystal resin (A), one that has an inherent viscosity (I.V.) of preferably at least about 2.0 dl/g, and more preferably 2.0 to 10.0 dl/g when dissolved in pentafluorophenol at a concentration of 0.1% by mass at 60°C is preferably used.
　本発明に適用できる（Ａ）液晶性樹脂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は、特に好ましくは、芳香族ヒドロキシカルボン酸及びその誘導体からなる群より選ばれる少なくとも１種に由来する構成単位を構成成分として有する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。 The aromatic polyester or aromatic polyesteramide as the liquid crystal resin (A) applicable to the present invention is particularly preferably an aromatic polyester or aromatic polyesteramide having as a constituent component a constituent unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof.
　より具体的には、
（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からなる群より選ばれる少なくとも１種に由来する構成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からなる群より選ばれる少なくとも１種に由来する構成単位と、（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からなる群より選ばれる少なくとも１種に由来する構成単位と、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からなる群より選ばれる少なくとも１種に由来する構成単位と、（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からなる群より選ばれる少なくとも１種に由来する構成単位と、（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からなる群より選ばれる少なくとも１種に由来する構成単位と、からなるポリエステル；
（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からなる群より選ばれる少なくとも１種に由来する構成単位と、（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からなる群より選ばれる少なくとも１種に由来する構成単位と、（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からなる群より選ばれる少なくとも１種に由来する構成単位と、からなるポリエステルアミド；
（５）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からなる群より選ばれる少なくとも１種に由来する構成単位と、（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からなる群より選ばれる少なくとも１種に由来する構成単位と、（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からなる群より選ばれる少なくとも１種に由来する構成単位と、（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からなる群より選ばれる少なくとも１種に由来する構成単位と、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。 More specifically,
(1) A polyester mainly composed of structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof;
(2) A polyester mainly composed of (a) a structural unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) a structural unit derived from at least one selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof;
(3) A polyester mainly composed of (a) a structural unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, (b) a structural unit derived from at least one selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof, and (c) a structural unit derived from at least one selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof;
(4) A polyesteramide mainly composed of (a) a structural unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, (b) a structural unit derived from at least one selected from the group consisting of aromatic hydroxyamines, aromatic diamines, and derivatives thereof, and (c) a structural unit derived from at least one selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof;
(5) Polyesteramides mainly consisting of (a) at least one constituent unit selected from the group consisting of aromatic hydroxycarboxylic acids and their derivatives, (b) at least one constituent unit selected from the group consisting of aromatic hydroxyamines, aromatic diamines and their derivatives, (c) at least one constituent unit selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids and their derivatives, and (d) at least one constituent unit selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols and their derivatives. If necessary, a molecular weight modifier may be used in combination with the above constituents.
　（Ａ）液晶性樹脂において、芳香族ヒドロキシカルボン酸及びその誘導体からなる群より選ばれる少なくとも１種に由来する構成単位の含有量は、（Ａ）液晶性樹脂の分子構造が変動するのを低く抑える観点から、全構成単位に対し、好ましくは４５モル％以上であり、より好ましくは５０モル％以上であり、更により好ましくは５５モル％以上であり、一層更により好ましくは６０モル％以上であり、特に好ましくは６２モル％以上である。上記含有量の上限は、特に限定されず、全構成単位に対し、１００モル％以下でよく、９０モル％以下、８０モル％以下、７５モル％以下、又は７０モル％以下でもよい。 In (A) liquid crystal resin, the content of the constituent units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and their derivatives is preferably 45 mol% or more, more preferably 50 mol% or more, even more preferably 55 mol% or more, even more preferably 60 mol% or more, and particularly preferably 62 mol% or more, based on all the constituent units, from the viewpoint of suppressing fluctuations in the molecular structure of (A) liquid crystal resin. The upper limit of the content is not particularly limited, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, 75 mol% or less, or 70 mol% or less, based on all the constituent units.
　本発明に適用できる（Ａ）液晶性樹脂を構成する具体的化合物の好ましい例としては、４－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸等の芳香族ヒドロキシカルボン酸；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’－ジヒドロキシビフェニル、ハイドロキノン、レゾルシン、下記一般式（Ｉ）で表される化合物、及び下記一般式（ＩＩ）で表される化合物等の芳香族ジオール；１，４－フェニレンジカルボン酸、１，３－フェニレンジカルボン酸、４，４’－ジフェニルジカルボン酸、２，６－ナフタレンジカルボン酸、及び下記一般式（ＩＩＩ）で表される化合物等の芳香族ジカルボン酸；ｐ－アミノフェノール、ｐ－フェニレンジアミン、Ｎ－アセチル－ｐ－アミノフェノール等の芳香族アミン類が挙げられる。前述の芳香族ヒドロキシカルボン酸及びその誘導体としては、反応性や（Ａ）液晶性樹脂の分子構造の安定性等の観点から、４－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸、又はこれらの組み合わせが好ましい。
Figure JPOXMLDOC01-appb-C000001
 （Ｘ：アルキレン（Ｃ１～Ｃ４）、アルキリデン、－Ｏ－、－ＳＯ－、－ＳＯ２－、－Ｓ－、及び－ＣＯ－より選ばれる基である。）
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
 （Ｙ：－（ＣＨ２）ｎ－（ｎ＝１～４）及び－Ｏ（ＣＨ２）ｎＯ－（ｎ＝１～４）より選ばれる基である。） Preferable examples of specific compounds constituting the liquid crystal resin (A) applicable to the present invention include aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; aromatic diols such as 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcin, compounds represented by the following general formula (I) and compounds represented by the following general formula (II); aromatic dicarboxylic acids such as 1,4-phenylenedicarboxylic acid, 1,3-phenylenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid and compounds represented by the following general formula (III); aromatic amines such as p-aminophenol, p-phenylenediamine and N-acetyl-p-aminophenol. As the aromatic hydroxycarboxylic acid and its derivatives, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, or a combination thereof are preferred from the viewpoints of reactivity and stability of the molecular structure of the liquid crystal resin (A).
Figure JPOXMLDOC01-appb-C000001
 (X is a group selected from alkylene (C 1 to C 4 ), alkylidene, —O—, —SO—, —SO 2 —, —S—, and —CO—.)
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
 (Y is a group selected from -( CH2 ) n- (n = 1 to 4) and -O( CH2 ) nO- (n = 1 to 4).)
　本発明に用いられる（Ａ）液晶性樹脂の調製は、上記のモノマー化合物（又はモノマーの混合物）から直接重合法やエステル交換法を用いて公知の方法で行うことができ、通常は溶融重合法、溶液重合法、スラリー重合法、固相重合法等、又はこれらの２種以上の組み合わせが用いられ、溶融重合法、又は溶融重合法と固相重合法との組み合わせが好ましく用いられる。エステル形成能を有する上記化合物類はそのままの形で重合に用いてもよく、また、重合の前段階で前駆体から該エステル形成能を有する誘導体に変性されたものでもよい。これらの重合に際しては種々の触媒の使用が可能であり、代表的なものとしては、酢酸カリウム、酢酸マグネシウム、酢酸第一錫、テトラブチルチタネート、酢酸鉛、酢酸ナトリウム、三酸化アンチモン、トリス（２，４－ペンタンジオナト）コバルト（ＩＩＩ）等の金属塩系触媒、１－メチルイミダゾール、４－ジメチルアミノピリジン等の有機化合物系触媒が挙げられる。触媒の使用量は一般にはモノマーの全質量に対して約０．００１～１質量％、特に約０．０１～０．２質量％が好ましい。これらの重合方法により製造されたポリマーは更に必要があれば、減圧又は不活性ガス中で加熱する固相重合法により分子量の増加を図ることができる。 The liquid crystal resin (A) used in the present invention can be prepared by a known method using direct polymerization or transesterification from the above monomer compound (or mixture of monomers). Usually, melt polymerization, solution polymerization, slurry polymerization, solid-phase polymerization, or a combination of two or more of these methods is used, and melt polymerization or a combination of melt polymerization and solid-phase polymerization is preferably used. The above compounds capable of forming esters may be used in the polymerization as they are, or may be modified from a precursor to a derivative capable of forming the ester at a stage prior to polymerization. Various catalysts can be used in these polymerizations, and representative examples include metal salt catalysts such as potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris(2,4-pentanedionato)cobalt(III), and organic compound catalysts such as 1-methylimidazole and 4-dimethylaminopyridine. The amount of catalyst used is generally about 0.001 to 1% by mass, and preferably about 0.01 to 0.2% by mass, based on the total mass of the monomers. If necessary, the molecular weight of the polymer produced by these polymerization methods can be further increased by solid-phase polymerization, in which the polymer is heated under reduced pressure or in an inert gas.
　上記のような方法で得られた（Ａ）液晶性樹脂の溶融粘度は特に限定されない。一般には成形温度での溶融粘度が剪断速度１０００ｓｅｃ－１で３Ｐａ・ｓ以上５００Ｐａ・ｓ以下のものが使用可能である。しかし、それ自体あまり高粘度のものは流動性が非常に悪化するため好ましくない。なお、上記（Ａ）液晶性樹脂は２種以上の液晶性樹脂の混合物であってもよい。 The melt viscosity of the liquid crystal resin (A) obtained by the above method is not particularly limited. In general, a resin having a melt viscosity at the molding temperature of 3 Pa·s to 500 Pa·s at a shear rate of 1000 sec -1 can be used. However, a resin having a viscosity that is too high is not preferred because it significantly deteriorates the flowability. The liquid crystal resin (A) may be a mixture of two or more kinds of liquid crystal resins.
　本発明の液晶性樹脂組成物全体に対して、（Ａ）液晶性樹脂の含有量は、好ましくは５２～７９．４質量％又は３７～７４．４質量％であり、より好ましくは５３．５～７４．０５質量％又は４０．５～６８．０５質量％であり、更により好ましくは６２～７３．７５質量％又は５０～６５．７５質量％である。（Ａ）成分の含有量が上記範囲内であると、流動性、耐熱性等の点で好ましい。 The content of the liquid crystal resin (A) relative to the entire liquid crystal resin composition of the present invention is preferably 52 to 79.4% by mass or 37 to 74.4% by mass, more preferably 53.5 to 74.05% by mass or 40.5 to 68.05% by mass, and even more preferably 62 to 73.75% by mass or 50 to 65.75% by mass. If the content of the (A) component is within the above range, it is preferable in terms of fluidity, heat resistance, etc.
［（Ｂ）ウィスカー］
　本発明に係る液晶性樹脂組成物には、ウィスカーが含まれる。本発明に係る液晶性樹脂組成物にウィスカーが含まれることにより、液晶性樹脂組成物の流動性を維持しつつ、成形体の機械的強度が向上しやすい。本明細書において、ウィスカーとは、鉱物繊維を指し、より具体的には、針状単結晶を指す。ウィスカーは、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。 [(B) Whiskers]
The liquid crystal resin composition according to the present invention contains whiskers. By containing whiskers in the liquid crystal resin composition according to the present invention, the mechanical strength of the molded article is likely to be improved while maintaining the fluidity of the liquid crystal resin composition. In this specification, whiskers refer to mineral fibers, more specifically, needle-like single crystals. The whiskers can be used alone or in combination of two or more types.
　（Ｂ）ウィスカーの平均繊維長は、好ましくは５～２００μｍであり、より好ましくは７～１７０μｍであり、更により好ましくは９～１５０μｍである。上記平均繊維長が上記範囲内であると、成形体の機械的強度がより向上しやすい。なお、本明細書において、（Ｂ）ウィスカーの平均繊維長としては、ウィスカーの実体顕微鏡画像１０枚をＣＣＤカメラからＰＣに取り込み、画像測定機によって画像処理手法により、実体顕微鏡画像１枚ごとに１００本のウィスカー、即ち、合計１０００本のウィスカーについて繊維長を測定した値の平均を採用する。液晶性樹脂組成物中の（Ｂ）ウィスカーの平均繊維長は、液晶性樹脂組成物を６００℃で２時間の加熱により灰化して残存したウィスカーについて、上記方法を適用することで測定される。 The average fiber length of the (B) whiskers is preferably 5 to 200 μm, more preferably 7 to 170 μm, and even more preferably 9 to 150 μm. When the average fiber length is within the above range, the mechanical strength of the molded body is more likely to be improved. In this specification, the average fiber length of the (B) whiskers is determined by importing 10 stereomicroscope images of the whiskers from a CCD camera into a PC, and measuring the fiber length of 100 whiskers per stereomicroscope image, i.e., a total of 1,000 whiskers, using an image processing method with an image measuring device. The average fiber length of the (B) whiskers in the liquid crystal resin composition is measured by applying the above method to the whiskers remaining after heating the liquid crystal resin composition at 600° C. for 2 hours to incinerate it.
　（Ｂ）ウィスカーの繊維径は、好ましくは０．２～１５μｍ以下であり、より好ましくは０．２５～１０μｍである。上記繊維径が上記範囲内であると、成形体の機械的強度がより向上しやすい。なお、本明細書において、（Ｂ）ウィスカーの繊維径としては、ウィスカーを走査型電子顕微鏡で観察し、３０本のウィスカーについて繊維径を測定した値の平均を採用する。液晶性樹脂組成物中の（Ｂ）ウィスカーの繊維径は、液晶性樹脂組成物を６００℃で２時間の加熱により灰化して残存したウィスカーについて、上記方法を適用することで測定される。 The fiber diameter of the (B) whiskers is preferably 0.2 to 15 μm or less, and more preferably 0.25 to 10 μm. When the fiber diameter is within the above range, the mechanical strength of the molded body is more likely to be improved. In this specification, the fiber diameter of the (B) whiskers is determined by observing the whiskers with a scanning electron microscope and measuring the fiber diameter of 30 whiskers, and the average of these values is used. The fiber diameter of the (B) whiskers in the liquid crystalline resin composition is measured by applying the above method to the whiskers remaining after the liquid crystalline resin composition is heated at 600°C for 2 hours to incinerate the composition.
　（Ｂ）ウィスカーのアスペクト比、即ち、平均繊維長／繊維径の値は、本発明に係る液晶性樹脂組成物を含む、コネクター等の成形体の機械的強度等の観点から、好ましくは８以上であり、より好ましくは１０～１００であり、更により好ましくは１５～７５である。 (B) The aspect ratio of the whiskers, i.e., the value of the average fiber length/fiber diameter, is preferably 8 or more, more preferably 10 to 100, and even more preferably 15 to 75, from the viewpoint of the mechanical strength of a molded article such as a connector that contains the liquid crystalline resin composition according to the present invention.
　（Ｂ）ウィスカーとしては、特に限定されず、例えば、チタン酸カリウムウィスカー、ケイ酸カルシウムウィスカー（ウォラストナイト）、炭酸カルシウムウィスカー、酸化亜鉛ウィスカー、ホウ酸アルミニウムウィスカー、窒化珪素ウィスカー、三窒化珪素ウィスカー、塩基性硫酸マグネシウムウィスカー、チタン酸バリウムウィスカー、炭化珪素ウィスカー、ボロンウィスカーが挙げられ、入手性等の点で、チタン酸カリウムウィスカー、ケイ酸カルシウムウィスカー（ウォラストナイト）、炭酸カルシウムウィスカー、酸化亜鉛ウィスカー、ホウ酸アルミニウムウィスカー等が好ましく、チタン酸カリウムウィスカー、ケイ酸カルシウムウィスカー（ウォラストナイト）等がより好ましい。 (B) Whiskers are not particularly limited, and examples include potassium titanate whiskers, calcium silicate whiskers (wollastonite), calcium carbonate whiskers, zinc oxide whiskers, aluminum borate whiskers, silicon nitride whiskers, silicon trinitride whiskers, basic magnesium sulfate whiskers, barium titanate whiskers, silicon carbide whiskers, and boron whiskers. In terms of availability, potassium titanate whiskers, calcium silicate whiskers (wollastonite), calcium carbonate whiskers, zinc oxide whiskers, aluminum borate whiskers, and the like are preferred, with potassium titanate whiskers, calcium silicate whiskers (wollastonite), and the like being more preferred.
　（Ｂ）成分の含有量は、本発明の液晶性樹脂組成物全体に対して、２０～４０質量％である。（Ｂ）成分の含有量が上記範囲内であると、液晶性樹脂組成物の流動性を維持しつつ、成形体の機械的強度が向上しやすい。（Ｂ）成分の含有量は、好ましくは２２．５～４０質量％であり、より好ましくは２５～３５質量％であり、更により好ましくは２５～３２．５質量％である。 The content of component (B) is 20 to 40% by mass based on the total liquid crystal resin composition of the present invention. When the content of component (B) is within the above range, the mechanical strength of the molded product is likely to be improved while maintaining the fluidity of the liquid crystal resin composition. The content of component (B) is preferably 22.5 to 40% by mass, more preferably 25 to 35% by mass, and even more preferably 25 to 32.5% by mass.
［（Ｃ）エポキシ基含有オレフィン系重合体］
　本発明の液晶性樹脂組成物は、（Ｃ）エポキシ基含有オレフィン系重合体を含有する。本発明の液晶性樹脂組成物が（Ｃ）エポキシ基含有オレフィン系重合体を含有すると、本発明の液晶性樹脂組成物の優れた離型性を維持しつつ、成形体の機械的強度及び耐ブリスター性がバランスよく優れるものとなりやすい。 [(C) Epoxy group-containing olefin polymer]
The liquid crystal resin composition of the present invention contains an epoxy group-containing olefin polymer (C). When the liquid crystal resin composition of the present invention contains an epoxy group-containing olefin polymer (C), the liquid crystal resin composition of the present invention tends to have a well-balanced and excellent mechanical strength and blister resistance while maintaining the excellent mold releasability of the liquid crystal resin composition of the present invention.
　エポキシ基含有オレフィン系重合体としては、例えば、α－オレフィンに由来する繰り返し単位とα，β－不飽和酸のグリシジルエステルに由来する繰り返し単位とから構成される共重合体が挙げられる。エポキシ基含有オレフィン系重合体は、１種単独で用いても２種以上を組み合わせて用いてもよい。 Examples of epoxy group-containing olefin polymers include copolymers composed of repeating units derived from α-olefins and repeating units derived from glycidyl esters of α,β-unsaturated acids. The epoxy group-containing olefin polymers may be used alone or in combination of two or more types.
　α－オレフィンは特に限定されず、例えば、エチレン、プロピレン、ブテン等が挙げられるが、中でもエチレンが好ましく用いられる。α，β－不飽和酸のグリシジルエステルは下記一般式（ＩＶ）で示されるものである。下記一般式（ＩＶ）中、Ｒ’は、水素原子、炭素原子数１～５のアルキル基、又は－Ｒ１－ＣＯＯＨで示される基を表し、Ｒ１は、炭素原子数１～５のアルキレン基を表す。α，β－不飽和酸のグリシジルエステルは、例えばアクリル酸グリシジルエステル、メタクリル酸グリシジルエステル、エタクリル酸グリシジルエステル、イタコン酸グリシジルエステル等であるが、特にメタクリル酸グリシジルエステルが好ましい。
Figure JPOXMLDOC01-appb-C000004
 The α-olefin is not particularly limited, and examples thereof include ethylene, propylene, butene, among which ethylene is preferably used. The glycidyl ester of an α,β-unsaturated acid is represented by the following general formula (IV). In the following general formula (IV), R' represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a group represented by -R 1 -COOH, and R 1 represents an alkylene group having 1 to 5 carbon atoms. The glycidyl ester of an α,β-unsaturated acid is, for example, acrylic acid glycidyl ester, methacrylic acid glycidyl ester, ethacrylic acid glycidyl ester, itaconic acid glycidyl ester, etc., with methacrylic acid glycidyl ester being particularly preferred.
Figure JPOXMLDOC01-appb-C000004
　エポキシ基含有オレフィン系重合体において、α－オレフィンに由来する繰り返し単位の含有量は８７～９８質量％であり、α，β－不飽和酸のグリシジルエステルに由来する繰り返し単位の含有量は１３～２質量％であることが好ましい。 In the epoxy group-containing olefin polymer, the content of repeating units derived from α-olefin is preferably 87 to 98% by mass, and the content of repeating units derived from glycidyl ester of α,β-unsaturated acid is preferably 13 to 2% by mass.
　エポキシ基含有オレフィン系重合体は、本発明を損なわない範囲で上記２成分以外に第３成分としてアクリロニトリル、アクリル酸エステル、メタクリル酸エステル、α－メチルスチレン、無水マレイン酸等のオレフィン系不飽和モノマーの１種又は２種以上に由来する繰り返し単位を、上記２成分１００質量部に対し０～４８質量部含有してもよい。 The epoxy group-containing olefin polymer may contain, in addition to the above two components, a third component of repeating units derived from one or more olefin-based unsaturated monomers such as acrylonitrile, acrylic acid esters, methacrylic acid esters, α-methylstyrene, maleic anhydride, etc., in an amount of 0 to 48 parts by mass per 100 parts by mass of the above two components, as long as it does not impair the present invention.
　エポキシ基含有オレフィン系重合体は、各成分に対応するモノマー及びラジカル重合触媒を用いて通常のラジカル重合法により容易に調製することができる。より具体的には、通常、α－オレフィンとα，β－不飽和酸のグリシジルエステルとをラジカル発生剤の存在下、５００～４０００気圧、１００～３００℃で適当な溶媒や連鎖移動剤の存在下又は不存在下に共重合させる方法により製造できる。また、α－オレフィンとα，β－不飽和酸のグリシジルエステル及びラジカル発生剤とを混合し、押出機の中で溶融グラフト共重合させる方法によっても製造できる。 Epoxy group-containing olefin polymers can be easily prepared by a normal radical polymerization method using monomers corresponding to each component and a radical polymerization catalyst. More specifically, they can usually be produced by a method in which an α-olefin and a glycidyl ester of an α,β-unsaturated acid are copolymerized in the presence of a radical generator at 500 to 4000 atmospheres and 100 to 300°C in the presence or absence of a suitable solvent or chain transfer agent. They can also be produced by a method in which an α-olefin, a glycidyl ester of an α,β-unsaturated acid, and a radical generator are mixed and melt-graft-copolymerized in an extruder.
　（Ｃ）エポキシ基含有オレフィン系重合体の含有量は、本発明の液晶性樹脂組成物全体に対して、０．５～６質量％であり、好ましくは０．７５～５．５質量％であり、より好ましくは１～５質量％である。（Ｃ）成分の含有量が上記範囲内であると、液晶性樹脂組成物の優れた離型性を維持しつつ、成形体の機械的強度及び耐ブリスター性がバランスよく優れるものとなりやすい。 The content of the epoxy group-containing olefin polymer (C) is 0.5 to 6 mass % relative to the total liquid crystal resin composition of the present invention, preferably 0.75 to 5.5 mass %, and more preferably 1 to 5 mass %. When the content of the component (C) is within the above range, the molded article tends to have a good balance of excellent mechanical strength and blister resistance while maintaining the excellent mold releasability of the liquid crystal resin composition.
［（Ｄ）多価アルコール脂肪酸エステル］
　本発明に係る液晶性樹脂組成物は、（Ｄ）多価アルコール脂肪酸エステルを含む。本発明に係る液晶性樹脂組成物が（Ｄ）多価アルコール脂肪酸エステルを含むと、液晶性樹脂組成物の離型性が向上しやすく、成形体は、機械的強度及び耐ブリスター性に優れるものとなりやすい。（Ｄ）多価アルコール脂肪酸エステルは、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。 [(D) Polyhydric alcohol fatty acid ester]
The liquid crystal resin composition according to the present invention contains (D) a polyhydric alcohol fatty acid ester. When the liquid crystal resin composition according to the present invention contains (D) a polyhydric alcohol fatty acid ester, the mold releasability of the liquid crystal resin composition is likely to be improved, and the molded article is likely to have excellent mechanical strength and blister resistance. The (D) polyhydric alcohol fatty acid ester may be used alone or in combination of two or more.
　（Ｄ）多価アルコール脂肪酸エステルは、脂肪酸と多価アルコールとが縮合してなる部分エステル又はフルエステルである。なお、部分エステルは、多価アルコールの一部のヒドロキシ基が脂肪酸でアシル化されてなるものであり、フルエステルは、多価アルコールの全てのヒドロキシ基が脂肪酸でアシル化されてなるものである。 (D) Polyhydric alcohol fatty acid esters are partial esters or full esters formed by condensation of fatty acids and polyhydric alcohols. A partial ester is formed when some of the hydroxyl groups of a polyhydric alcohol are acylated with fatty acids, and a full ester is formed when all of the hydroxyl groups of a polyhydric alcohol are acylated with fatty acids.
　脂肪酸としては、炭素原子数１０～３２の高級脂肪酸が好ましい。脂肪酸としては、例えば、デカン酸、ウンデカン酸、ドデカン酸、トリデカン酸、テトラデカン酸、ペンタデカン酸、ヘキサデカン酸（パルミチン酸）、ヘプタデカン酸、オクタデカン酸（ステアリン酸）、ノナデカン酸、イコサン酸、ドコサン酸、ヘキサコサン酸等の飽和脂肪酸；パルミトレイン酸、オレイン酸、リノール酸、リノレン酸、エイコセン酸、エイコサペンタエン酸、セトレイン酸等の不飽和脂肪酸が挙げられる。脂肪酸は、１種単独で又は２種以上組み合わせて用いてもよい。脂肪酸としては、炭素原子数１０～２２の脂肪酸が好ましく、炭素原子数１４～２０の脂肪酸がより好ましい。 As the fatty acid, a higher fatty acid having 10 to 32 carbon atoms is preferable. As the fatty acid, for example, saturated fatty acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, docosanoic acid, and hexacosanoic acid; and unsaturated fatty acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid can be used alone or in combination of two or more kinds. As the fatty acid, a fatty acid having 10 to 22 carbon atoms is preferable, and a fatty acid having 14 to 20 carbon atoms is more preferable.
　多価アルコールは、分子内にアルコール性ヒドロキシ基を２個以上有する化合物である。多価アルコールとしては、炭素原子数が３～３２の多価アルコールが好ましい。多価アルコールとしては、例えば、グリセリン、ジグリセリン、デカグリセリン等のポリグリセリン；ペンタエリスリトール；ジペンタエリスリトール；ジエチレングリコール；プロピレングリコールが挙げられる。多価アルコールは、１種単独で又は２種以上組み合わせて用いてもよい。得られる多価アルコール脂肪酸エステルの耐熱性の点で、多価アルコールとしては、中でも、ペンタエリスリトール及びジペンタエリスリトールが好ましい。 A polyhydric alcohol is a compound having two or more alcoholic hydroxyl groups in the molecule. The polyhydric alcohol is preferably a polyhydric alcohol having 3 to 32 carbon atoms. Examples of the polyhydric alcohol include polyglycerols such as glycerin, diglycerin, and decaglycerin; pentaerythritol; dipentaerythritol; diethylene glycol; and propylene glycol. The polyhydric alcohol may be used alone or in combination of two or more. In terms of the heat resistance of the resulting polyhydric alcohol fatty acid ester, pentaerythritol and dipentaerythritol are particularly preferred as polyhydric alcohols.
　（Ｄ）多価アルコール脂肪酸エステルとしては、例えば、ペンタエリスリトールの脂肪酸エステル、ジペンタエリスリトールの脂肪酸エステルが挙げられ、液晶性樹脂組成物を含む成形体が機械的強度、耐ブリスター性、及び離型性にバランスよく優れるものとなりやすい点で、ペンタエリスリトールテトラパルミテート、ジペンタエリスリトールテトラパルミテート、ペンタエリスリトールテトラステアレート、及びジペンタエリスリトールテトラステアレートが好ましく、ペンタエリスリトールテトラステアレート及びジペンタエリスリトールテトラステアレートがより好ましい。 (D) Examples of polyhydric alcohol fatty acid esters include fatty acid esters of pentaerythritol and fatty acid esters of dipentaerythritol. Pentaerythritol tetrapalmitate, dipentaerythritol tetrapalmitate, pentaerythritol tetrastearate, and dipentaerythritol tetrastearate are preferred, with pentaerythritol tetrastearate and dipentaerythritol tetrastearate being more preferred, in that molded articles containing the liquid crystal resin composition tend to have a good balance of mechanical strength, blister resistance, and releasability.
　（Ｄ）多価アルコール脂肪酸エステルは、多価アルコールと脂肪酸とを、脱水重縮合によりエステル化させることにより得ることができる。なお、エステル化の際、多価アルコールのヒドロキシ基の量と、脂肪酸の量とを適宜調整することにより、部分エステル又はフルエステルを作り分けることができる。 (D) Polyhydric alcohol fatty acid esters can be obtained by esterifying polyhydric alcohols and fatty acids through dehydration polycondensation. During esterification, partial or full esters can be produced by appropriately adjusting the amount of hydroxyl groups in the polyhydric alcohol and the amount of fatty acid.
　（Ｄ）多価アルコール脂肪酸エステルは、熱重量分析（ＴＧＡ）で求められる５％重量減少温度（ＴＢ）が２５０℃以上であることが好ましく、２８０℃以上であることがより好ましい。上記５％重量減少温度が２５０℃以上であると、組成物の成形の際、多価アルコール脂肪酸エステルが熱分解しにくい。 (D) The polyhydric alcohol fatty acid ester preferably has a 5% weight loss temperature (TB) determined by thermogravimetric analysis (TGA) of 250°C or higher, and more preferably 280°C or higher. If the 5% weight loss temperature is 250°C or higher, the polyhydric alcohol fatty acid ester is less susceptible to thermal decomposition when the composition is molded.
　（Ｄ）多価アルコール脂肪酸エステルの含有量は、液晶性樹脂組成物全体に対して、０．１～２．０質量％である。（Ｄ）多価アルコール脂肪酸エステルの含有量が上記範囲内であると、液晶性樹脂組成物の離型性が向上しやすく、成形体は、機械的強度及び耐ブリスター性に優れるものとなりやすい。（Ｄ）多価アルコール脂肪酸エステルの含有量は、液晶性樹脂組成物全体に対して、好ましくは０．１５～１．５質量％であり、より好ましくは０．２～１．０質量％であり、更により好ましくは０．２５～０．５質量％である。 The content of (D) polyhydric alcohol fatty acid ester is 0.1 to 2.0% by mass with respect to the entire liquid crystal resin composition. When the content of (D) polyhydric alcohol fatty acid ester is within the above range, the mold releasability of the liquid crystal resin composition is likely to be improved, and the molded article is likely to have excellent mechanical strength and blister resistance. The content of (D) polyhydric alcohol fatty acid ester is preferably 0.15 to 1.5% by mass with respect to the entire liquid crystal resin composition, more preferably 0.2 to 1.0% by mass, and even more preferably 0.25 to 0.5% by mass.
［（Ｅ）板状充填剤］
　本発明に係る液晶性樹脂組成物は、板状充填剤が含んでもよい。本発明に係る液晶性樹脂組成物が板状充填剤を含むことにより、優れた機械的強度を維持しつつ、異方性が抑制された成形体を得やすい。板状充填剤は、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。 [(E) Plate-like filler]
The liquid crystal resin composition according to the present invention may contain a plate-like filler. By containing the plate-like filler in the liquid crystal resin composition according to the present invention, it is easy to obtain a molded product with suppressed anisotropy while maintaining excellent mechanical strength. The plate-like filler can be used alone or in combination of two or more.
　（Ｅ）成分のメディアン径は、好ましくは１０～５０μｍである。上記メディアン径が上記範囲内であると、得られる組成物からは、優れた機械的強度を維持しつつ、異方性が抑制された成形体を更に得やすい。上記メディアン径は、好ましくは１５～４０μｍであり、より好ましくは２０～３０μｍである。なお、本明細書において、（Ｅ）成分のメディアン径とは、レーザー回折／散乱式粒度分布測定法で測定した体積基準の中央値をいう。液晶性樹脂組成物中の（Ｅ）成分のメディアン径は、液晶性樹脂組成物を６００℃で２時間の加熱により灰化して残存した（Ｅ）成分について、上記方法を適用することで測定される。 The median diameter of component (E) is preferably 10 to 50 μm. When the median diameter is within the above range, it is easier to obtain a molded body with suppressed anisotropy from the obtained composition while maintaining excellent mechanical strength. The median diameter is preferably 15 to 40 μm, and more preferably 20 to 30 μm. In this specification, the median diameter of component (E) refers to the volume-based median value measured by a laser diffraction/scattering particle size distribution measurement method. The median diameter of component (E) in the liquid crystal resin composition is measured by applying the above method to the component (E) remaining after heating the liquid crystal resin composition at 600° C. for 2 hours to incinerate it.
　本発明の液晶性樹脂組成物全体に対して、（Ｅ）板状充填剤の含有量は、好ましくは５～１５質量％である。（Ｅ）板状充填剤の含有量が上記範囲内であると、得られる組成物からは、優れた機械的強度を維持しつつ、異方性が抑制された成形体を更に得やすい。（Ｅ）板状充填剤の含有量は、より好ましくは６～１３質量％であり、更により好ましくは８～１２質量％である。 The content of the plate-like filler (E) is preferably 5 to 15 mass% relative to the entire liquid crystal resin composition of the present invention. When the content of the plate-like filler (E) is within the above range, it is easier to obtain a molded article with suppressed anisotropy from the resulting composition while maintaining excellent mechanical strength. The content of the plate-like filler (E) is more preferably 6 to 13 mass%, and even more preferably 8 to 12 mass%.
　本発明における板状充填剤としては、タルク、マイカ、ガラスフレーク、各種の金属箔等が挙げられる。液晶性樹脂組成物の流動性を悪化させることなく、液晶性樹脂組成物から得られる成形体の異方性を抑制させるという点で、タルク及びマイカからなる群より選択される１種以上が好ましく、マイカがより好ましい。 The plate-like filler in the present invention may be talc, mica, glass flakes, various metal foils, etc. From the viewpoint of suppressing the anisotropy of the molded article obtained from the liquid crystalline resin composition without deteriorating the fluidity of the liquid crystalline resin composition, one or more selected from the group consisting of talc and mica are preferred, and mica is more preferred.
　〔タルク〕
　本発明において使用できるタルクとしては、当該タルクの全固形分量に対して、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量が２．５質量％以下であり、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１．０質量％超２．０質量％以下であり、かつＣａＯの含有量が０．５質量％未満であるものが好ましい。即ち、本発明において使用できるタルクは、その主成分たるＳｉＯ２及びＭｇＯの他、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯのうちの少なくとも１種を含有し、各成分が上記の含有量範囲で含有するものであってもよい。 〔talc〕
The talc usable in the present invention preferably has a total content of Fe2O3 , Al2O3 and CaO of 2.5 % by mass or less, a total content of Fe2O3 and Al2O3 of more than 1.0% by mass and 2.0 % by mass or less, and a CaO content of less than 0.5% by mass , relative to the total solid content of the talc. That is, the talc usable in the present invention may contain at least one of Fe2O3 , Al2O3 and CaO in addition to SiO2 and MgO as the main components, and each component may be contained within the above content range.
　上記タルクにおいて、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量が２．５質量％以下であると、液晶性樹脂組成物の成形加工性及び当該液晶性樹脂組成物から成形された成形体の耐熱性が悪化しにくい。そのため、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量は、１．０質量％以上２．０質量％以下が好ましい。 In the talc, when the total content of Fe2O3 , Al2O3 and CaO is 2.5 mass % or less, the moldability of the liquid crystal resin composition and the heat resistance of the molded article molded from the liquid crystal resin composition are unlikely to deteriorate. Therefore, the total content of Fe2O3 , Al2O3 and CaO is preferably 1.0 mass% or more and 2.0 mass% or less .
　また、上記タルクのうち、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１．０質量％超のタルクは入手しやすい。また、上記タルクにおいて、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が２．０質量％以下であると、液晶性樹脂組成物の成形加工性及び当該液晶性樹脂組成物から成形された成形体の耐熱性が悪化しにくい。そのため、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量は、１．０質量％超１．７質量％以下が好ましい。 Among the above talcs, talc having a total content of Fe2O3 and Al2O3 of more than 1.0% by mass is easily available. In addition, in the above talc, when the total content of Fe2O3 and Al2O3 is 2.0% by mass or less, the moldability of the liquid crystal resin composition and the heat resistance of the molded body molded from the liquid crystal resin composition are not easily deteriorated. Therefore, the total content of Fe2O3 and Al2O3 is preferably more than 1.0% by mass and 1.7% by mass or less.
　また、上記タルクにおいて、ＣａＯの含有量が０．５質量％未満であると、液晶性樹脂組成物の成形加工性及び当該液晶性樹脂組成物から成形された成形体の耐熱性が悪化しにくい。そのため、ＣａＯの含有量は、０．０１質量％以上０．４質量％以下が好ましい。 In addition, if the CaO content in the talc is less than 0.5% by mass, the moldability of the liquid crystal resin composition and the heat resistance of the molded body formed from the liquid crystal resin composition are unlikely to deteriorate. Therefore, the CaO content is preferably 0.01% by mass or more and 0.4% by mass or less.
　〔マイカ〕
　マイカとは、アルミニウム、カリウム、マグネシウム、ナトリウム、鉄等を含んだケイ酸塩鉱物の粉砕物である。本発明において使用できるマイカとしては、白雲母、金雲母、黒雲母、人造雲母等が挙げられるが、これらのうち色相が良好であり、低価格であるという点で白雲母が好ましい。 [Mica]
Mica is a pulverized silicate mineral containing aluminum, potassium, magnesium, sodium, iron, etc. Examples of mica that can be used in the present invention include muscovite, phlogopite, biotite, and artificial mica, among which muscovite is preferred because of its good hue and low cost.
　また、マイカの製造において、鉱物を粉砕する方法としては、湿式粉砕法及び乾式粉砕法が知られている。湿式粉砕法とは、マイカ原石を乾式粉砕機にて粗粉砕した後、水を加えてスラリー状態にて湿式粉砕で本粉砕し、その後、脱水、乾燥を行う方法である。湿式粉砕法と比較して、乾式粉砕法は低コストで一般的な方法であるが、湿式粉砕法を用いると、鉱物を薄く細かく粉砕することがより容易である。上記のメディアン径と後述する好ましい厚みとを有するマイカが得られるという理由で、本発明においては薄く細かい粉砕物を使用することが好ましい。したがって、本発明においては、湿式粉砕法により製造されたマイカを使用するのが好ましい。 In addition, in the production of mica, wet grinding and dry grinding are known as methods for grinding minerals. In the wet grinding method, mica raw ore is coarsely ground in a dry grinder, water is added to the slurry, and the resulting material is then wet-ground and dehydrated. Compared to the wet grinding method, the dry grinding method is a common method with low cost, but the wet grinding method makes it easier to grind minerals thinly and finely. In the present invention, it is preferable to use thin and finely ground material because it can obtain mica having the above-mentioned median diameter and the preferred thickness described below. Therefore, in the present invention, it is preferable to use mica produced by the wet grinding method.
　また、湿式粉砕法においては、被粉砕物を水に分散させる工程が必要であるため、被粉砕物の分散効率を高めるために、被粉砕物に凝集沈降剤及び／又は沈降助剤を加えることが一般的である。本発明において使用できる凝集沈降剤及び沈降助剤としては、ポリ塩化アルミニウム、硫酸アルミニウム、硫酸第一鉄、硫酸第二鉄、塩化コッパラス、ポリ硫酸鉄、ポリ塩化第二鉄、鉄－シリカ無機高分子凝集剤、塩化第二鉄－シリカ無機高分子凝集剤、消石灰（Ｃａ（ＯＨ）２）、苛性ソーダ（ＮａＯＨ）、ソーダ灰（Ｎａ２ＣＯ３）等が挙げられる。これらの凝集沈降剤及び沈降助剤は、ｐＨがアルカリ性又は酸性である。本発明で使用するマイカは、湿式粉砕する際に凝集沈降剤及び／又は沈降助剤を使用していないものが好ましい。凝集沈降剤及び／又は沈降助剤で処理されていないマイカを使用すると、液晶性樹脂組成物中のポリマーの分解が生じにくく、多量のガス発生やポリマーの分子量低下等が起きにくいため、得られる成形体の性能をより良好に維持するのが容易である。 In addition, in the wet grinding method, a step of dispersing the ground material in water is necessary, so that in order to increase the dispersion efficiency of the ground material, it is common to add a flocculating sedimentation agent and/or a sedimentation aid to the ground material. Examples of flocculating sedimentation agents and sedimentation aids that can be used in the present invention include polyaluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, copper chloride, polyferric sulfate, polyferric chloride, iron-silica inorganic polymer flocculant, ferric chloride-silica inorganic polymer flocculant, hydrated lime (Ca(OH) 2 ), caustic soda (NaOH), soda ash (Na 2 CO 3 ), etc. These flocculating sedimentation agents and sedimentation aids have an alkaline or acidic pH. The mica used in the present invention is preferably one that does not use a flocculating sedimentation agent and/or a sedimentation aid when wet grinding. When mica that has not been treated with a flocculating sedimentation agent and/or a sedimentation aid is used, decomposition of the polymer in the liquid crystalline resin composition is unlikely to occur, and large amounts of gas are unlikely to be generated, or a decrease in the molecular weight of the polymer is unlikely to occur, making it easier to maintain the performance of the resulting molded article better.
　本発明において使用できるマイカの厚みは、電子顕微鏡の観察により実測した厚みが０．０１～１μｍであることが好ましく、０．０３～０．３μｍであることが特に好ましい。マイカの厚みが０．０１μｍ以上であると、液晶性樹脂組成物の溶融加工の際にマイカが割れにくくなるため、成形体の剛性が向上しやすい可能性があるため好ましい。マイカの厚みが１μｍ以下であると、成形体の剛性に対する改良効果が十分となりやすいため好ましい。 The thickness of the mica that can be used in the present invention is preferably 0.01 to 1 μm, and particularly preferably 0.03 to 0.3 μm, as measured by observation under an electron microscope. If the thickness of the mica is 0.01 μm or more, the mica is less likely to crack during melt processing of the liquid crystalline resin composition, which is preferable since it may be easier to improve the rigidity of the molded article. If the thickness of the mica is 1 μm or less, the effect of improving the rigidity of the molded article is likely to be sufficient, which is preferable.
　本発明において使用できるマイカは、シランカップリング剤等で表面処理されていてもよく、かつ／又は、結合剤で造粒し顆粒状とされていてもよい。 The mica that can be used in the present invention may be surface-treated with a silane coupling agent or the like, and/or may be granulated with a binder to form granules.
［その他の成分］
　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、その他の離型剤、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。 [Other ingredients]
To the liquid crystal resin composition of the present invention, other polymers, other fillers, other release agents, and known substances generally added to synthetic resins, i.e., stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, crystallization accelerators, crystal nucleating agents, etc., may be appropriately added depending on the required performance, within a range that does not impair the effects of the present invention.
　その他の重合体としては、例えば、エポキシ基含有スチレン系重合体、エポキシ基非含有オレフィン系重合体等が挙げられる。エポキシ基含有スチレン系重合体としては、例えば、スチレン類に由来する繰り返し単位とα，β－不飽和酸のグリシジルエステルに由来する繰り返し単位とから構成される共重合体を含め、公知のエポキシ基含有スチレン系重合体が挙げられる。エポキシ基非含有オレフィン系重合体としては、例えば、ポリエチレン、ポリプロピレン、ポリブテン、エチレン－プロピレン共重合体、エチレン－ブテン共重合体、エチレン－オクテン共重合体、ポリブタジエン、ポリイソプレン、ポリクロロプレン、エチレン－プロピレン－ブタジエン共重合体、エチレン－プロピレン－イソプレン共重合体、エチレン－プロピレン－クロロプレン共重合体、エチレン－エチルアクリレート共重合体、エチレン－酢酸ビニル共重合体等が挙げられる。 Other polymers include, for example, epoxy group-containing styrene polymers and non-epoxy group-containing olefin polymers. Epoxy group-containing styrene polymers include known epoxy group-containing styrene polymers, including copolymers composed of repeating units derived from styrenes and repeating units derived from glycidyl esters of α,β-unsaturated acids. Epoxy group-free olefin polymers include, for example, polyethylene, polypropylene, polybutene, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-octene copolymers, polybutadiene, polyisoprene, polychloroprene, ethylene-propylene-butadiene copolymers, ethylene-propylene-isoprene copolymers, ethylene-propylene-chloroprene copolymers, ethylene-ethyl acrylate copolymers, ethylene-vinyl acetate copolymers, etc.
　その他の充填剤とは、（Ｂ）ウィスカー及び（Ｅ）板状充填剤以外の充填剤をいい、例えば、シリカ等の（Ｃ）粒状充填剤；ガラス繊維等の、（Ｂ）ウィスカー以外の繊維状充填剤；カーボンブラック等が挙げられる。成形体表面の起毛抑制効果が高くなりやすいことから、本発明の液晶性樹脂組成物は、（Ｂ）ウィスカー以外の繊維状充填剤、例えば、ガラス繊維を含有しないことが好ましい。 The other fillers refer to fillers other than (B) whiskers and (E) plate-like fillers, and examples thereof include (C) granular fillers such as silica; fibrous fillers other than (B) whiskers, such as glass fiber; and carbon black. Since the effect of suppressing nap formation on the surface of the molded product is likely to be high, it is preferable that the liquid crystalline resin composition of the present invention does not contain fibrous fillers other than (B) whiskers, such as glass fiber.
　その他の離型剤とは、（Ｄ）多価アルコール脂肪酸エステル以外の離型剤をいい、例えば、ステアリン酸カルシウム等の脂肪酸金属塩；脂肪酸アミド類；低分子量ポリオレフィン等が挙げられる。より優れた機械的強度及びより優れた離型性を維持しつつ、耐ブリスター性がより向上した成形体を本発明の液晶性樹脂組成物から得やすいことから、本発明の液晶性樹脂組成物は、（Ｄ）多価アルコール脂肪酸エステル以外の離型剤、例えば、ステアリン酸カルシウム等の脂肪酸金属塩を含有しないことが好ましい。 The other release agent refers to a release agent other than the polyhydric alcohol fatty acid ester (D), and examples thereof include fatty acid metal salts such as calcium stearate, fatty acid amides, low molecular weight polyolefins, and the like. Since a molded article having improved blister resistance while maintaining superior mechanical strength and superior release properties can be easily obtained from the liquid crystal resin composition of the present invention, it is preferable that the liquid crystal resin composition of the present invention does not contain a release agent other than the polyhydric alcohol fatty acid ester (D), for example, a fatty acid metal salt such as calcium stearate.
［液晶性樹脂組成物の調製］
　本発明の樹脂組成物の調製は特に限定されない。例えば、上記（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分、任意に（Ｅ）成分、及び任意にその他の成分を配合して、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、液晶性樹脂組成物の調製が行われる。 [Preparation of Liquid Crystalline Resin Composition]
The preparation of the resin composition of the present invention is not particularly limited. For example, the above-mentioned (A) component, (B) component, (C) component, (D) component, optionally (E) component, and optionally other components are mixed, and melt-kneaded using a single-screw or twin-screw extruder to prepare a liquid crystal resin composition.
［液晶性樹脂組成物］
　上記のようにして得られた本発明の液晶性樹脂組成物の溶融粘度は、流動性の観点から、好ましくは１００Ｐａ・ｓｅｃ以下であり、より好ましくは９０Ｐａ・ｓｅｃ以下であり、更により好ましくは８５Ｐａ・ｓｅｃ以下である。上記溶融粘度の下限は、特に限定されず、５Ｐａ・ｓｅｃ以上でよく、１０Ｐａ・ｓｅｃ以上でも２０Ｐａ・ｓｅｃ以上でもよい。溶融時の流動性が高く、成形性に優れる点も本発明の液晶性樹脂組成物の特徴の一つである。本明細書において、溶融粘度としては、液晶性樹脂の融点よりも１０～３０℃高いシリンダー温度、剪断速度１０００ｓｅｃ－１の条件で、ＩＳＯ　１１４４３に準拠した測定方法で得られた値を採用する。 [Liquid Crystalline Resin Composition]
The melt viscosity of the liquid crystal resin composition of the present invention obtained as described above is preferably 100 Pa·sec or less, more preferably 90 Pa·sec or less, and even more preferably 85 Pa·sec or less, from the viewpoint of fluidity. The lower limit of the melt viscosity is not particularly limited, and may be 5 Pa·sec or more, 10 Pa·sec or more, or 20 Pa·sec or more. One of the features of the liquid crystal resin composition of the present invention is that it has high fluidity when melted and excellent moldability. In this specification, the melt viscosity is a value obtained by a measurement method in accordance with ISO 11443 under the conditions of a cylinder temperature 10 to 30° C. higher than the melting point of the liquid crystal resin and a shear rate of 1000 sec −1 .
＜コネクター＞
　上記液晶性樹脂組成物は、コネクター用とすることができる。より具体的にいうと、上記液晶性樹脂組成物は、コネクターを製造するために使用することができる。即ち、上記液晶性樹脂組成物を用いて、コネクターを製造することができる。本発明のコネクターは、本発明の液晶性樹脂組成物を含む成形体からなる。本発明の液晶性樹脂組成物を含む成形体は、機械的強度及び離型性に優れ、ブリスター発生が抑制されているので、耐ブリスター性に優れた高性能のコネクターとして好適に用いることができる。なお、上記成形体は、本発明の液晶性樹脂組成物を成形することにより得ることができる。成形方法としては、特に限定されず、例えば、射出成形が挙げられる。 <Connector>
The liquid crystal resin composition can be used for a connector. More specifically, the liquid crystal resin composition can be used to manufacture a connector. That is, the connector can be manufactured using the liquid crystal resin composition. The connector of the present invention is made of a molded article containing the liquid crystal resin composition of the present invention. The molded article containing the liquid crystal resin composition of the present invention has excellent mechanical strength and releasability, and blister generation is suppressed, so that it can be suitably used as a high-performance connector with excellent blister resistance. The molded article can be obtained by molding the liquid crystal resin composition of the present invention. The molding method is not particularly limited, and for example, injection molding can be mentioned.
　上記コネクターとしては、例えば、平面状コネクター（ＣＰＵソケット、ＬＧＡソケット）、ＦＰＣコネクター、長尺コネクター、基板対基板（Ｂ　ｔｏ　Ｂ）コネクター、メモリーカード用コネクター、メモリーモジュール用コネクター等が挙げられる。 Examples of the above connectors include planar connectors (CPU sockets, LGA sockets), FPC connectors, long connectors, board-to-board (B to B) connectors, memory card connectors, memory module connectors, etc.
　平面状コネクターは、ＣＰＵソケット等の外枠内部に格子構造を有する平面状コネクターである。電子部品の小型化が進んでおり、それに合わせて平面状コネクターも薄肉化、狭ピッチ化が進んでいる。格子部が非常に薄肉の平面状コネクターにおいては、格子部へ樹脂を充填しようとすると、流動性が十分でないために充填圧が高くなり、結果として得られる平面状コネクターのそり変形量が多くなる等という問題がある。本発明のコネクターであれば、低そり性が向上し、その他曲げ特性等も改善され、用いる樹脂組成物の流動性も高いため、端子を保持する樹脂部分の最小肉厚が０．３ｍｍ以下、格子部のピッチ間隔が１．５ｍｍ以下の平面状コネクターであってもそりが生じにくく、靭性の高いコネクターを得ることができる。また、本発明の樹脂組成物は流動性も高いため、薄肉、狭ピッチの平面状コネクターであっても、容易に成形することができる。 The planar connector is a planar connector that has a lattice structure inside the outer frame of a CPU socket or the like. As electronic components become smaller, planar connectors are also becoming thinner and narrower in pitch. In planar connectors with very thin lattice sections, when resin is filled into the lattice section, the filling pressure is high due to insufficient fluidity, resulting in a problem of a large amount of warping deformation of the planar connector. The connector of the present invention has improved low warping properties and other improved bending properties, and the fluidity of the resin composition used is also high, so that even planar connectors with a minimum thickness of 0.3 mm or less for the resin part that holds the terminal and a pitch interval of the lattice section of 1.5 mm or less are less likely to warp, and a connector with high toughness can be obtained. In addition, the resin composition of the present invention has high fluidity, so that even thin, narrow-pitch planar connectors can be easily molded.
　ＦＰＣ基板と接続するＦＰＣコネクターは、通常一定ピッチで配列されており、近年の機器の小型化の要求に伴い、この接続部の配列ピッチはさらなる狭ピッチ化が要求されている。しかし、狭ピッチを持つコネクターを成形するためには、樹脂組成物の流動性が必要になり、また、コネクターとして実際に使用するためにコネクターには、そりが少なく、一定水準以上の靭性、機械的強度を持つことが求められる。本発明のコネクターは用いる樹脂組成物の性質により、靭性等の曲げ特性が充分高く、低そりであり、更に樹脂組成物の流動性も高いことから、狭ピッチ化の進んだＦＰＣコネクターにも適用できる。ここで、「狭ピッチ」とは、接続部の間のピッチが１ｍｍ以下である。本発明のコネクターは、ピッチ間隔１ｍｍ以下、端子間肉厚０．２ｍｍ以下の小型のコネクターであっても好ましく適用することができる。 FPC connectors that connect to FPC boards are usually arranged at a fixed pitch, but with the recent demand for miniaturization of devices, there is a demand for the arrangement pitch of these connections to be even narrower. However, in order to mold a connector with a narrow pitch, the resin composition needs to have fluidity, and in order to actually use it as a connector, the connector needs to have little warping and a certain level of toughness and mechanical strength or higher. Due to the properties of the resin composition used, the connector of the present invention has sufficiently high bending properties such as toughness, low warping, and the resin composition also has high fluidity, so it can be used in FPC connectors with narrower pitches. Here, "narrow pitch" means that the pitch between the connection parts is 1 mm or less. The connector of the present invention can be preferably used even in small connectors with a pitch of 1 mm or less and a terminal-to-terminal thickness of 0.2 mm or less.
　長尺コネクターとは、長さ方向に沿って接続部を多く設けてあるコネクターである。このようなコネクターにおいても狭ピッチ化、薄肉化が進んでいる。本発明のコネクターは、端子間ピッチ１．５ｍｍ以下、端子間肉厚０．３ｍｍ以下であっても充分に適用することができる。 A long connector is a connector that has many connections along its length. Even in such connectors, the pitch is becoming narrower and the wall thickness is becoming thinner. The connector of the present invention can be fully applied even when the terminal pitch is 1.5 mm or less and the terminal wall thickness is 0.3 mm or less.
　基板対基板（Ｂ　ｔｏ　Ｂ）コネクターとは、印刷配線基板同士を接合するのに使用されるコネクターである。印刷配線基板を用いる電子機器の小型化に伴って、コネクターの実装面積の狭小化が要求され、また両印刷配線基板の間の距離を小さくするために低背化が要求されている。本発明のコネクターは、最小肉厚０．３ｍｍ以下、コネクターの端子のピッチが１．５ｍｍ以下のコネクターであっても好ましく適用することができる。 A board-to-board (B to B) connector is a connector used to join printed wiring boards together. As electronic devices that use printed wiring boards become more compact, there is a demand for smaller mounting areas for connectors, and also for lower heights to reduce the distance between the two printed wiring boards. The connector of the present invention can be preferably applied even to connectors with a minimum wall thickness of 0.3 mm or less and a terminal pitch of 1.5 mm or less.
　コネクターを得る方法としては、特に限定されず、従来公知の方法を用いることができ、射出成形法が好ましい。 The method for obtaining the connector is not particularly limited, and any conventionally known method can be used, with injection molding being preferred.
　以下に実施例を挙げて、本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.
＜液晶性樹脂＞
・芳香族ポリエステルアミド
　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。
　４－ヒドロキシ安息香酸（ＨＢＡ）；１３８０ｇ（６０モル％）
　６－ヒドロキシ－２－ナフトエ酸（ＨＮＡ）；１５７ｇ（５モル％）
　１，４－フェニレンジカルボン酸（ＴＡ）；４８４ｇ（１７．５モル％）
　４，４’－ジヒドロキシビフェニル（ＢＰ）；３８８ｇ（１２．５モル％）
　Ｎ－アセチル－ｐ－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 <Liquid Crystalline Resin>
Aromatic polyester amide The following raw materials were charged into a polymerization vessel, and the temperature of the reaction system was raised to 140°C and reacted at 140°C for 1 hour. Thereafter, the temperature was further raised to 340°C over 4.5 hours, and the pressure was reduced to 10 Torr (i.e., 1330 Pa) over 15 minutes, and melt polymerization was carried out while distilling out acetic acid, excess acetic anhydride, and other low boiling points. After the stirring torque reached a predetermined value, nitrogen was introduced to change from a reduced pressure state to a normal pressure state and then to a pressurized state, and the polymer was discharged from the bottom of the polymerization vessel, and the strands were pelletized to obtain pellets. The obtained pellets were subjected to heat treatment at 300°C for 2 hours under a nitrogen stream to obtain the 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 polymer was measured in the same manner as the melt viscosity measurement method described below.
4-Hydroxybenzoic acid (HBA): 1380 g (60 mol%)
6-Hydroxy-2-naphthoic acid (HNA): 157 g (5 mol%)
1,4-phenylenedicarboxylic acid (TA): 484 g (17.5 mol%)
4,4'-dihydroxybiphenyl (BP): 388 g (12.5 mol%)
N-acetyl-p-aminophenol (APAP): 126 g (5 mol%)
Metal catalyst (potassium acetate catalyst): 110 mg
Acylating agent (acetic anhydride): 1659 g
・芳香族ポリエステル
　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３６０℃まで５．５時間かけて昇温し、そこから２０分かけて５Ｔｏｒｒ（即ち、６６７Ｐａ）まで減圧して、酢酸、過剰の無水酢酸、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、ペレットとして目的のポリマーを得た。得られたポリマーの融点は３５５℃、溶融粘度は１０Ｐａ・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。
　４－ヒドロキシ安息香酸（ＨＢＡ）；１０４０ｇ（４８モル％）
　６－ヒドロキシ－２－ナフトエ酸（ＨＮＡ）；８９ｇ（３モル％）
　１，４－フェニレンジカルボン酸（ＴＡ）；５４７ｇ（２１モル％）
　１，３－フェニレンジカルボン酸（ＩＡ）；９１ｇ（３．５モル％）
　４，４’－ジヒドロキシビフェニル（ＢＰ）；７１６ｇ（２４．５モル％）
　酢酸カリウム触媒：１１０ｍｇ
　無水酢酸：１６４４ｇ Aromatic polyester After the following raw materials were charged into a polymerization vessel, the temperature of the reaction system was raised to 140°C and reacted at 140°C for 1 hour. Thereafter, the temperature was further raised to 360°C over 5.5 hours, and the pressure was reduced to 5 Torr (i.e., 667 Pa) over 20 minutes, and melt polymerization was carried out while distilling off acetic acid, excess acetic anhydride, and other low boiling points. After the stirring torque reached a predetermined value, nitrogen was introduced to change the reduced pressure state to normal pressure and then to a pressurized state, and the polymer was discharged from the bottom of the polymerization vessel, and the strands were pelletized to obtain the target polymer as pellets. The melting point of the obtained polymer was 355°C and the melt viscosity was 10 Pa·s. The melt viscosity of the above polymer was measured in the same manner as in the melt viscosity measurement method described below.
4-Hydroxybenzoic acid (HBA): 1040 g (48 mol%)
6-Hydroxy-2-naphthoic acid (HNA): 89 g (3 mol %)
1,4-phenylenedicarboxylic acid (TA): 547 g (21 mol%)
1,3-Phenylenedicarboxylic acid (IA): 91 g (3.5 mol%)
4,4'-dihydroxybiphenyl (BP): 716 g (24.5 mol%)
Potassium acetate catalyst: 110 mg
Acetic anhydride: 1644g
［融点の測定方法］
　ＴＡインスツルメント社製ＤＳＣにて、液晶性樹脂を室温から２０℃／分の昇温条件で加熱した際に観測される吸熱ピーク温度（Ｔｍ１）の測定後、（Ｔｍ１＋４０）℃の温度で２分間保持した後、２０℃／分の降温条件で室温まで一旦冷却した後、再度、２０℃／分の昇温条件で加熱した際に観測される吸熱ピークの温度（Ｔｍ２）を測定し、ポリマーの融点とした。 [Method of measuring melting point]
Using a DSC manufactured by TA Instruments, the liquid crystalline resin was heated from room temperature at a temperature increase rate of 20°C/min to measure the endothermic peak temperature (Tm1), and then held at a temperature of (Tm1+40)°C for 2 minutes. The resin was then cooled to room temperature at a temperature decrease rate of 20°C/min, and then heated again at a temperature increase rate of 20°C/min to measure the endothermic peak temperature (Tm2), which was determined as the melting point of the polymer.
＜液晶性樹脂以外の材料＞
・ウォラストナイト：ＷＯＬＬＡＳＴＯＮＩＴＥ　ＳＨ－１２５０ＢＪ（キンセイマテック（株）製、ケイ酸カルシウムウィスカー（ウォラストナイト）、平均繊維長１３０μｍ、繊維径８μｍ）
・チタン酸カリウム：ティスモＮ－１０２（大塚化学（株）製、チタン酸カリウムウィスカー（チタン酸カリウム繊維）、繊維径０．３～０．６μｍ、平均繊維長１０～２０μｍ）
・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）
・エチレン－グリシジルメタクリレート共重合体：ボンドファーストＢＦ－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％）
・ペンタエリスリトールテトラステアレート：ユニスターＨ－４７６（日油（株）製、ペンタエリスリトールテトラステアレート）
・ステアリン酸カルシウム：カルシウムステアレートＧＦ－２００（日油（株）製、ステアリン酸カルシウム） <Materials other than liquid crystal resin>
Wollastonite: WOLLASTONITE SH-1250BJ (Kinsei Matec Co., Ltd., calcium silicate whisker (wollastonite), average fiber length 130 μm, fiber diameter 8 μm)
Potassium titanate: TISMO N-102 (manufactured by Otsuka Chemical Co., Ltd., potassium titanate whisker (potassium titanate fiber), fiber diameter 0.3 to 0.6 μm, average fiber length 10 to 20 μm)
Mica: AB-25S (manufactured by Yamaguchi Mica Co., Ltd., mica, median diameter 25.0 μm)
Ethylene-glycidyl methacrylate copolymer: Bondfast BF-2C (manufactured by Sumitomo Chemical Co., Ltd., ethylene-glycidyl methacrylate copolymer, glycidyl methacrylate content: 6% by mass)
Pentaerythritol tetrastearate: Unistar H-476 (manufactured by NOF Corporation, pentaerythritol tetrastearate)
Calcium stearate: Calcium stearate GF-200 (calcium stearate, manufactured by NOF Corporation)
＜液晶性樹脂組成物の製造＞
　上記成分を、表１又は表２に示す割合（質量％）で二軸押出機（（株）日本製鋼所製ＴＥＸ３０α型）を用いて、下記のシリンダー温度で溶融混練し、液晶性樹脂組成物ペレットを得た。
〔製造条件〕
シリンダー温度：
　３５０℃：上記芳香族ポリエステルアミドを含有する液晶性樹脂組成物の場合
　３７０℃：上記芳香族ポリエステルを含有する液晶性樹脂組成物の場合 <Production of Liquid Crystalline Resin Composition>
The above components were melt-kneaded in the ratios (mass%) shown in Table 1 or Table 2 using a twin-screw extruder (TEX30α type, manufactured by The Japan Steel Works, Ltd.) at the cylinder temperatures shown below to obtain liquid crystal resin composition pellets.
[Production conditions]
Cylinder Temperature:
350° C.: In the case of a liquid crystal resin composition containing the aromatic polyester amide 370° C.: In the case of a liquid crystal resin composition containing the aromatic polyester
＜溶融粘度＞
　（株）東洋精機製作所製キャピログラフ１Ｂ型を使用し、液晶性樹脂の融点よりも１０～３０℃高い温度で、内径１ｍｍ、長さ２０ｍｍのオリフィスを用いて、剪断速度１０００／秒で、ＩＳＯ１１４４３に準拠して、液晶性樹脂組成物の溶融粘度を測定した。なお、具体的な測定温度は、上記芳香族ポリエステルアミドを含有する液晶性樹脂組成物については３５０℃、上記芳香族ポリエステルを含有する液晶性樹脂組成物については３７０℃であった。結果を表１及び表２に示す。 <Melt Viscosity>
The melt viscosity of the liquid crystal resin composition was measured in accordance with ISO11443 using a Capillograph 1B model manufactured by Toyo Seiki Seisakusho Co., Ltd. at a temperature 10 to 30°C higher than the melting point of the liquid crystal resin, using an orifice with an inner diameter of 1 mm and a length of 20 mm, at a shear rate of 1000/sec. The specific measurement temperatures were 350°C for the liquid crystal resin composition containing the aromatic polyester amide, and 370°C for the liquid crystal resin composition containing the aromatic polyester. The results are shown in Tables 1 and 2.
＜曲げ試験＞
　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、ＩＳＯ試験片Ａ形を得た。この試験片を切り出し、測定用試験片（８０ｍｍ×１０ｍｍ×４ｍｍ）を得た。この測定用試験片を用いて、ＩＳＯ　１７８に準拠し、曲げ強度、曲げ弾性率、及び曲げ歪を測定した。結果を表１及び表２に示す。
〔成形条件〕
　シリンダー温度：
　　　　　３５０℃（実施例１～３及び７～１０並びに比較例１及び３～９）
　　　　　３７０℃（実施例４～６及び比較例２）
　金型温度：９０℃
　射出速度：３３ｍｍ／ｓｅｃ <Bending test>
The pellets of the examples and comparative examples were molded under the following molding conditions using a molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries, Ltd.) to obtain ISO test pieces A type. These test pieces were cut out to obtain test pieces for measurement (80 mm x 10 mm x 4 mm). Using these test pieces for measurement, the bending strength, bending modulus, and bending strain were measured in accordance with ISO 178. The results are shown in Tables 1 and 2.
〔Molding condition〕
Cylinder Temperature:
350°C (Examples 1 to 3 and 7 to 10 and Comparative Examples 1 and 3 to 9)
370°C (Examples 4 to 6 and Comparative Example 2)
Mold temperature: 90°C
Injection speed: 33 mm/sec
＜荷重たわみ温度＞
　下記成形条件で、液晶性樹脂組成物を射出成形し、ＩＳＯ試験片Ａ形を得た。この試験片を８０ｍｍ×１０ｍｍ×４ｍｍに切り出し、試験片を作製した。この試験片を用いて、ＩＳＯ７５－１及び２に準拠して荷重たわみ温度を測定した。荷重たわみ温度を成形体の耐熱性を表す指標として用いた。結果を表１及び表２に示す。
［成形条件］
　成形機：住友重機械工業（株）製、ＳＥ１００ＤＵ
　シリンダー温度：
　　　　　３５０℃（実施例１～３及び７～１０並びに比較例１及び３～９）
　　　　　３７０℃（実施例４～６及び比較例２）
　金型温度：９０℃
　射出速度：３３ｍｍ／ｓｅｃ <Deflection temperature under load>
The liquid crystal resin composition was injection molded under the following molding conditions to obtain an ISO test piece A type. This test piece was cut into 80 mm x 10 mm x 4 mm to prepare a test piece. Using this test piece, the deflection temperature under load was measured in accordance with ISO 75-1 and 2. The deflection temperature under load was used as an index of the heat resistance of the molded product. The results are shown in Tables 1 and 2.
[Molding condition]
Molding machine: SE100DU, manufactured by Sumitomo Heavy Industries, Ltd.
Cylinder Temperature:
350°C (Examples 1 to 3 and 7 to 10 and Comparative Examples 1 and 3 to 9)
370°C (Examples 4 to 6 and Comparative Example 2)
Mold temperature: 90°C
Injection speed: 33 mm/sec
＜ブリスター温度＞
　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、ウェルド部を有する１２．５ｍｍ×１２０ｍｍ×０．８ｍｍの成形品を得た。この成形品を上記ウェルド部で二分割して得た断片を１検体とし、所定温度のホットプレスに５分間挟んだ。その後、目視にて上記検体の表面にブリスターが発生しているかどうかを調べた。ブリスター温度は、ブリスターの発生個数がゼロとなる最高温度とした。なお、上記所定温度は２００～３００℃の範囲において１０℃刻みで設定した。結果を表１及び表２に示す。
〔成形条件〕
　シリンダー温度：
　　　　　３５０℃（実施例１～３及び７～１０並びに比較例１及び３～９）
　　　　　３７０℃（実施例４～６及び比較例２）
　金型温度：９０℃
　射出速度：３３ｍｍ／ｓｅｃ <Blister temperature>
The pellets of the examples and comparative examples were molded under the following molding conditions using a molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries, Ltd.) to obtain a molded product having a weld section and dimensions of 12.5 mm x 120 mm x 0.8 mm. This molded product was divided into two at the weld section, and each of the obtained pieces was used as a specimen, which was then clamped in a hot press at a specified temperature for 5 minutes. The surface of the specimen was then visually inspected for the presence of blisters. The blister temperature was the maximum temperature at which the number of blisters generated was zero. The specified temperature was set in 10°C increments in the range of 200 to 300°C. The results are shown in Tables 1 and 2.
〔Molding condition〕
Cylinder Temperature:
350°C (Examples 1 to 3 and 7 to 10 and Comparative Examples 1 and 3 to 9)
370°C (Examples 4 to 6 and Comparative Example 2)
Mold temperature: 90°C
Injection speed: 33 mm/sec
＜離型性評価＞
　下記成形条件で、液晶性樹脂組成物を射出成形して、図１（ａ）及び図１（ｂ）に示すコの字型液晶性樹脂成形体（厚み：０．５ｍｍ）を作製した。以下の基準に従って、上記成形体の離型性を評価した。結果を表１及び表２に示す。
　○（良好）：上記成形体が金型に張り付いて離型できない不良が発生しなかった。
　×（不良）：上記成形体が金型に張り付いて離型できない不良が１回以上発生した。
［成形条件］
　成形機：住友重機械工業（株）製、ＳＥ３０ＤＵＺ
　シリンダー温度：
　　　　　３５０℃（実施例１～３及び７～１０並びに比較例１及び３～９）
　　　　　３７０℃（実施例４～６及び比較例２）
　金型温度：９０℃
　射出速度：１００ｍｍ／ｓｅｃ
　ショット数：１００ショット <Evaluation of releasability>
The liquid crystal resin composition was injection molded under the following molding conditions to produce a U-shaped liquid crystal resin molded product (thickness: 0.5 mm) as shown in Figure 1 (a) and Figure 1 (b). The mold releasability of the molded product was evaluated according to the following criteria. The results are shown in Tables 1 and 2.
◯ (Good): The molded article did not stick to the mold and could not be released from the mold.
× (bad): The molded product stuck to the mold and could not be released from the mold at least once.
[Molding condition]
Molding machine: SE30DUZ, manufactured by Sumitomo Heavy Industries, Ltd.
Cylinder Temperature:
350°C (Examples 1 to 3 and 7 to 10 and Comparative Examples 1 and 3 to 9)
370°C (Examples 4 to 6 and Comparative Example 2)
Mold temperature: 90°C
Injection speed: 100 mm/sec
Number of shots: 100
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表１及び表２に記載の結果から明らかなように、実施例の液晶性樹脂組成物を含む成形体は、機械的強度及び離型性に優れ、ブリスター発生が抑制されていることが確認された。 As is clear from the results shown in Tables 1 and 2, it was confirmed that the molded articles containing the liquid crystal resin compositions of the examples had excellent mechanical strength and releasability, and the occurrence of blisters was suppressed.

Claims (9)

  1. 　（Ａ）液晶性樹脂、
    　（Ｂ）ウィスカー、
    　（Ｃ）エポキシ基含有オレフィン系重合体、及び
    　（Ｄ）多価アルコール脂肪酸エステル
    を含有する液晶性樹脂組成物であって、
    　前記液晶性樹脂組成物全体に対して、
    　前記（Ｂ）ウィスカーの含有量は、２０～４０質量％、
    　前記（Ｃ）エポキシ基含有オレフィン系重合体の含有量は、０．５～６質量％、
    　前記（Ｄ）多価アルコール脂肪酸エステルの含有量は、０．１～２．０質量％
    である液晶性樹脂組成物。     (A) a liquid crystalline resin,
    (B) whiskers,
    A liquid crystalline resin composition comprising: (C) an epoxy group-containing olefin polymer; and (D) a polyhydric alcohol fatty acid ester,
    With respect to the entire liquid crystal resin composition,
    The content of the whiskers (B) is 20 to 40 mass %,
    The content of the epoxy group-containing olefin polymer (C) is 0.5 to 6 mass %,
    The content of the polyhydric alcohol fatty acid ester (D) is 0.1 to 2.0% by mass.
    The liquid crystal resin composition according to the present invention is
  2. 　前記（Ａ）液晶性樹脂は、芳香族ヒドロキシカルボン酸及びその誘導体からなる群より選ばれる少なくとも１種に由来する構成単位を構成成分として有する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請求項１に記載の液晶性樹脂組成物。 The liquid crystal resin composition according to claim 1, wherein the (A) liquid crystal resin is an aromatic polyester or aromatic polyester amide having as a constituent a structural unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof.
  3. 　前記（Ｄ）多価アルコール脂肪酸エステルは、ペンタエリスリトールの脂肪酸エステル及びジペンタエリスリトールの脂肪酸エステルからなる群より選ばれる少なくとも１種である請求項１又は２に記載の液晶性樹脂組成物。 The liquid crystal resin composition according to claim 1 or 2, wherein the (D) polyhydric alcohol fatty acid ester is at least one selected from the group consisting of fatty acid esters of pentaerythritol and fatty acid esters of dipentaerythritol.
  4. 　前記液晶性樹脂組成物全体に対して、前記（Ｂ）ウィスカーの含有量は、２５～４０質量％である請求項１又は２に記載の液晶性樹脂組成物。 The liquid crystal resin composition according to claim 1 or 2, wherein the content of the whiskers (B) is 25 to 40 mass % relative to the entire liquid crystal resin composition.
  5. 　更に（Ｅ）板状充填剤を含有する請求項１又は２に記載の液晶性樹脂組成物であって、
    　前記液晶性樹脂組成物全体に対して、前記（Ｅ）板状充填剤の含有量は、５～１５質量％である液晶性樹脂組成物。     The liquid crystal resin composition according to claim 1 or 2, further comprising (E) a plate-like filler,
    The liquid crystalline resin composition has a content of the plate-like filler (E) of 5 to 15% by mass based on the entire liquid crystalline resin composition.
  6. 　コネクター用である請求項１又は２に記載の液晶性樹脂組成物。 The liquid crystal resin composition according to claim 1 or 2, which is for use in connectors.
  7. 　コネクターを製造するための、請求項１又は２に記載の液晶性樹脂組成物の使用。 Use of the liquid crystal resin composition according to claim 1 or 2 for producing a connector.
  8. 　請求項１又は２に記載の液晶性樹脂組成物を含む成形体。 A molded article comprising the liquid crystal resin composition according to claim 1 or 2.
  9. 　請求項８に記載の成形体からなるコネクター。 A connector made of the molded article according to claim 8.
PCT/JP2023/046579 2022-12-26 2023-12-26 Liquid crystalline resin composition and connector using same WO2024143334A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017193704A (en) * 2016-04-15 2017-10-26 東レ株式会社 Liquid crystal polyester resin composition and molding comprising the same
WO2019124256A1 (en) * 2017-12-18 2019-06-27 住友化学株式会社 Liquid crystalline polyester composition and molded article
JP2020007394A (en) * 2018-07-03 2020-01-16 ポリプラスチックス株式会社 Liquid crystalline resin composition for sliding wear-resistant members, and sliding wear-resistant member including the same
JP2021055059A (en) * 2019-09-30 2021-04-08 ポリプラスチックス株式会社 Resin composition and connector part using the same
JP2021167408A (en) * 2020-04-08 2021-10-21 ポリプラスチックス株式会社 Resin composition and molding thereof
WO2022004553A1 (en) * 2020-06-30 2022-01-06 ポリプラスチックス株式会社 Liquid crystalline resin composition for ball bearing anti-sliding wear member, and ball bearing anti-sliding wear member using same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017193704A (en) * 2016-04-15 2017-10-26 東レ株式会社 Liquid crystal polyester resin composition and molding comprising the same
WO2019124256A1 (en) * 2017-12-18 2019-06-27 住友化学株式会社 Liquid crystalline polyester composition and molded article
JP2020007394A (en) * 2018-07-03 2020-01-16 ポリプラスチックス株式会社 Liquid crystalline resin composition for sliding wear-resistant members, and sliding wear-resistant member including the same
JP2021055059A (en) * 2019-09-30 2021-04-08 ポリプラスチックス株式会社 Resin composition and connector part using the same
JP2021167408A (en) * 2020-04-08 2021-10-21 ポリプラスチックス株式会社 Resin composition and molding thereof
WO2022004553A1 (en) * 2020-06-30 2022-01-06 ポリプラスチックス株式会社 Liquid crystalline resin composition for ball bearing anti-sliding wear member, and ball bearing anti-sliding wear member using same

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