WO2022191099A1 - Composition de résine de cristaux liquides et article moulé la comprenant - Google Patents

Composition de résine de cristaux liquides et article moulé la comprenant Download PDF

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Publication number
WO2022191099A1
WO2022191099A1 PCT/JP2022/009606 JP2022009606W WO2022191099A1 WO 2022191099 A1 WO2022191099 A1 WO 2022191099A1 JP 2022009606 W JP2022009606 W JP 2022009606W WO 2022191099 A1 WO2022191099 A1 WO 2022191099A1
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Prior art keywords
liquid crystalline
resin composition
parts
structural unit
polyester resin
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PCT/JP2022/009606
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English (en)
Japanese (ja)
Inventor
藤野慎吾
森脇和弘
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東レ株式会社
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Priority to JP2022533061A priority Critical patent/JPWO2022191099A1/ja
Publication of WO2022191099A1 publication Critical patent/WO2022191099A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • 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
    • 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
    • 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
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a liquid crystalline resin composition and a molded article made from it.
  • liquid crystalline resins such as optically anisotropic liquid crystalline polyester resins, characterized by the parallel arrangement of molecular chains, have attracted attention due to their excellent moldability, mechanical properties, and insulating properties, and have been used in electrical and electronic parts.
  • Demand is expanding mainly for injection molding applications. Due to their liquid crystal structure, these liquid crystalline polyester resins are excellent in heat resistance, fluidity and dimensional stability. Modularization that combines each part is progressing. When modularizing, the chances of contact between parts increase, so in addition to the conventional required properties, high surface hardness and surface smoothness are required. Due to the thinning and complication of the shape of steel, higher performance than ever before is required for the above characteristics.
  • Patent Document 1 has the problem that the improvement in surface hardness is insufficient because the shape of the filler to be blended is irregular or spherical powder. Further, in the technique described in Patent Document 2, since the shape of the filler to be blended is needle-like, there is a problem that improvement in surface smoothness and surface hardness is insufficient.
  • the present invention provides a liquid crystalline resin composition that solves the above-mentioned problems and can obtain a molded article that achieves both high surface hardness and excellent surface smoothness at a high level.
  • the task is to
  • the liquid crystalline resin composition of the present invention is a liquid crystalline resin composition containing 5 to 50 parts by weight of (B) glass flakes relative to 100 parts by weight of (A) a liquid crystalline polyester resin,
  • the average particle size is 1-8 ⁇ m.
  • the molded article of the present invention is made of the liquid crystal resin composition of the present invention.
  • liquid crystalline resin composition of the present invention it is possible to obtain a molded article that achieves both high surface hardness and excellent surface smoothness at a high level.
  • the liquid crystalline polyester resin consists of structural units selected from, for example, aromatic oxycarbonyl units, aromatic and/or aliphatic dioxy units, aromatic and/or aliphatic dicarbonyl units, etc., and is anisotropic A liquid crystalline polyester resin that forms a melt phase can be mentioned.
  • aromatic oxycarbonyl units examples include structural units generated from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, etc. Structural units generated from p-hydroxybenzoic acid are preferred.
  • Aromatic and/or aliphatic dioxy units include, for example, 4,4′-dihydroxybiphenyl, hydroquinone, 3,3′,5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl ether, ethylene glycol, 1,3-propylene glycol, 1, Structural units generated from 4-butanediol and the like can be mentioned, and structural units generated from 4,4'-dihydroxybiphenyl and hydroquinone are preferred.
  • Aromatic and/or aliphatic dicarbonyl units include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-4, Structural units generated from 4'-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, adipic acid, sebacic acid, and the like. , terephthalic acid and isophthalic acid are preferred.
  • liquid crystal polyester resin examples include a liquid crystal polyester resin composed of a structural unit generated from p-hydroxybenzoic acid and a structural unit generated from 6-hydroxy-2-naphthoic acid, and a liquid crystal polyester resin generated from p-hydroxybenzoic acid.
  • a liquid crystalline polyester resin comprising a structural unit, a structural unit generated from 6-hydroxy-2-naphthoic acid, a structural unit generated from an aromatic dihydroxy compound, and a structural unit generated from an aromatic dicarboxylic acid and/or an aliphatic dicarboxylic acid, Structural units generated from p-hydroxybenzoic acid, structural units generated from 4,4′-dihydroxybiphenyl, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and/or aliphatic dicarboxylic acids such as adipic acid and sebacic acid
  • Liquid crystalline polyester resin composed of structural units produced, structural units produced from p-hydroxybenzoic acid, structural units produced from 4,4'-dihydroxybiphenyl, structural units produced from hydroquinone, aromatics such as terephthalic acid and isophthalic acid
  • Liquid crystalline polyester resin composed of structural units generated from aliphatic dicarboxylic acids such as dicarboxy
  • liquid crystal polyester resins containing the following structural units (I), (II), (III), (IV) and (V) are preferable from the viewpoint of low dust generation. This is because such a liquid crystalline polyester resin has a large number of copolymerized units, so that the liquid crystallinity is low and fibrillation, which is a characteristic of the liquid crystalline polyester resin, is less likely to occur.
  • Structural unit (I) is a structural unit generated from p-hydroxybenzoic acid
  • structural unit (II) is a structural unit generated from 4,4'-dihydroxybiphenyl
  • structural unit (III) is a structural unit generated from hydroquinone
  • structural unit (IV) represents a structural unit generated from terephthalic acid
  • structural unit (V) represents a structural unit generated from isophthalic acid.
  • Structural unit (I) is preferably 65 to 80 mol%, more preferably 68 to 72 mol%, relative to the total of structural units (I), (II) and (III).
  • the lower limit is preferably 65 mol %, more preferably 68 mol %, since the amount of generated gas can be further reduced.
  • the upper limit is preferably 80 mol%, more preferably 78 mol%, and even more preferably 72 mol%.
  • the structural unit (II) is preferably 55 to 85 mol% relative to the total of the structural units (II) and (III).
  • the lower limit is more preferably 60 mol % or more, most preferably 70 mol % or more, because the amount of generated gas is reduced.
  • the upper limit is more preferably 82 mol% or less, most preferably 80 mol% or less.
  • the structural unit (IV) is preferably 50 to 95 mol% relative to the total of the structural units (IV) and (V).
  • the lower limit is preferably 55 mol % or more, most preferably 60 mol % or more, because the amount of generated gas is reduced.
  • the upper limit is more preferably 85 mol % or less, most preferably 75 mol % or less, from the viewpoint of toughness.
  • the sum of structural units (II) and (III) and the sum of (IV) and (V) are preferably substantially equimolar.
  • substantially equimolar means that the structural units constituting the polymer main chain excluding the terminal are equimolar, and when the structural unit constituting the terminal is included, it is not necessarily equimolar. Not exclusively. Excess dicarboxylic acid or dihydroxy moieties may be added to control the end groups of the polymer.
  • the content of each structural unit in (A) the liquid crystal polyester resin can be calculated by the following process. That is, (A) liquid crystalline polyester resin is weighed into an NMR (nuclear magnetic resonance) test tube, and (A) liquid crystalline polyester resin is dissolved in a soluble solvent (for example, pentafluorophenol/heavy tetrachloroethane-d 2 mixed solvent). Then, 1 H-NMR spectrum measurement is performed. The content of each structural unit can be calculated from the peak area ratio derived from each structural unit.
  • a soluble solvent for example, pentafluorophenol/heavy tetrachloroethane-d 2 mixed solvent
  • the melting point of (A) the liquid crystal polyester resin in the present invention is preferably 300 to 350° C. from the viewpoint of workability and fluidity, and the lower limit thereof is more preferably 310° C. or higher, particularly preferably 320° C. or higher, from the viewpoint of workability. . From the viewpoint of fluidity, the upper limit is more preferably 340°C or lower, particularly preferably 330°C or lower. Such a melting point is preferable because generation of decomposition gas during processing can be suppressed and fluidity is sufficiently exhibited.
  • the melting point (Tm) of (A) the liquid crystal polyester resin can be measured by the following method.
  • the temperature is Tm 1 +20° C. for 5 minutes.
  • the temperature is once cooled to room temperature under the condition of temperature decrease of 20°C/min, and the endothermic peak temperature (Tm 2 ) observed when measured again under the condition of temperature increase of 20°C/min is defined as the melting point (Tm).
  • the melt viscosity of (A) the liquid crystalline polyester resin in the present invention is preferably 1 to 100 Pa ⁇ s, and from the viewpoint of workability, the lower limit thereof is more preferably 3 Pa ⁇ s or more, and particularly preferably 5 Pa ⁇ s or more. From the viewpoint of fluidity, the upper limit of the melt viscosity is more preferably 50 Pa ⁇ s or less, particularly preferably 30 Pa ⁇ s or less.
  • the melt viscosity is a value measured with a Koka-type flow tester under conditions of (A) the melting point of the liquid crystal polyester resin +10° C. and a shear rate of 1,000/s.
  • the liquid crystalline polyester resin can be obtained, for example, by a known polyester polycondensation method.
  • the liquid crystalline polyester resin composed of the structural units (I), (II), (III), (IV) and (V) described above, the following production methods are preferred.
  • Method for producing liquid crystalline polyester by dephenol polycondensation reaction from phenyl ester of p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, and diphenyl esters of terephthalic acid and isophthalic acid (4) p-hydroxybenzoic acid and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid are reacted with a predetermined amount of diphenyl carbonate to form diphenyl esters, respectively, and then 4,4'-dihydroxybiphenyl and an aromatic dihydroxy compound such as hydroquinone are added to dephenolate.
  • a method for producing a liquid crystalline polyester by a polycondensation reaction is reacted with a predetermined amount of diphenyl carbonate to form diphenyl esters, respectively, and then 4,4'-dihydroxybiphenyl and an aromatic dihydroxy compound such as hydroquinone are added to dephenolate.
  • the liquid crystalline polyester resin when the liquid crystalline polyester resin is produced by the deacetic acid polycondensation reaction, it is preferable to use a melt polymerization method in which the reaction is performed under reduced pressure at a temperature at which the liquid crystalline polyester resin melts to complete the polycondensation reaction.
  • a predetermined amount of p-hydroxybenzoic acid, 4,4'- Dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid, and acetic anhydride are charged into a reaction vessel equipped with a stirring blade, a distillation tube, and a discharge port at the bottom, and heated with stirring under a nitrogen gas atmosphere to remove hydroxyl groups. is acetylated, the temperature is raised to the melting temperature of the liquid crystalline polyester resin, and polycondensation is performed under reduced pressure to complete the reaction.
  • the obtained polymer is pressurized in the reaction vessel at a temperature at which it melts, for example, to about 1.0 kg/cm 2 (0.1 MPa), and is discharged in a strand form from a discharge port provided at the bottom of the reaction vessel.
  • the melt polymerization method is an advantageous method for producing a homogeneous polymer, and is preferred because it can obtain a superior polymer with less outgassing.
  • the polycondensation reaction in the production of the liquid crystalline polyester resin proceeds without a catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate, sodium acetate, antimony trioxide, and metallic magnesium can also be used. can.
  • liquid crystal polyester resin can be used by mixing two or more liquid crystal polyester resins.
  • the liquid crystalline resin composition of the present invention contains 5 to 50 parts by weight of (B) glass flakes per 100 parts by weight of (A) the liquid crystal polyester resin.
  • the content of (B) glass flakes is preferably 10 to 45 parts by weight, more preferably 15 to 35 parts by weight, per 100 parts by weight of the liquid crystal polyester resin. If the content is less than 5 parts by weight, the surface hardness will be insufficient. Moreover, when the content is more than 50 parts by weight, the surface smoothness is lowered.
  • the (B) glass flakes have an average particle size of 1 to 8 ⁇ m, preferably 2 to 7 ⁇ m.
  • the average particle size referred to here is the number average particle size.
  • the number average particle size is measured with a laser diffraction/scattering particle size distribution analyzer ("LA-300" manufactured by HORIBA).
  • the cumulative degree is less than 10% for those having a particle size of 1 ⁇ m or less, and the cumulative degree for those having a particle size of 20 ⁇ m or more is less than 10%.
  • the particle size exceeds 10% or the particle size exceeds 10%, the surface hardness and surface smoothness are both insufficient.
  • the thickness of the (B) glass flakes is preferably 0.1 to 5 ⁇ m, more preferably 0.1 to 3 ⁇ m, still more preferably 0.3 to 1 ⁇ m.
  • 10 pieces are randomly selected from the image of the glass flakes observed with a scanning electron microscope (SEM), the thickness is measured, and the average value is taken as the thickness of the (B) glass flakes.
  • glass flakes having a thickness within the above range include MEG005FY manufactured by Nippon Sheet Glass Co., Ltd., and the like.
  • the thickness of the glass flakes is 0.1 ⁇ m or more, it becomes easier to obtain a higher surface hardness. Moreover, when it is 5 ⁇ m or less, the surface smoothness is likely to be improved.
  • the (B) glass flakes are preferably E glass having a low alkaline component content from the viewpoint of improving the dispersibility in the resin of the liquid crystalline resin composition of the present invention. Glass can also be used.
  • the method for producing (B) glass flakes as described above includes, for example, a method in which molten glass is inflated like a balloon, rapidly cooled and then crushed, or a method in which the glass is heated and melted in a melting tank, and the molten glass base material is discharged from the bottom of the tank. is pulled out, and a gas is blown into the molten glass base to form a hollow thin film, which is pulverized by a pressure roller.
  • the (B) glass flakes may be surface-treated with a coupling agent, specifically ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - Silane coupling agents such as mercaptopropyltrimethoxysilane, methyltrimethoxysilane, ⁇ -anilinopropyltrimethoxysilane, hydroxypropyltrimethoxysilane, ⁇ -ureidopropyltriethoxysilane, vinylacetoxysilane, and isopropyltrisisostearoyl titanate , isopropyltris(dioctylpyrophosphate)titanate, tetraoctylbis(ditridecylphosphite)titanate, bis(dioctylpyrophosphate)ethylenetitanate, isopropyl
  • glass flakes examples include MEG005FY manufactured by Nippon Sheet Glass Co., Ltd., and the like. Also, other commercially available products can be used as long as they have a shape that meets the requirements of the present invention.
  • the liquid crystalline resin composition of the present invention may further contain (C) a non-fibrous filler.
  • C) Non-fibrous fillers include, for example, plate-like fillers, powdery fillers, granular fillers, and the like.
  • plate-like fillers include mica, talc, kaolin, clay, molybdenum disulfide, and the like.
  • Powdered and particulate fillers include silica, glass beads, titanium oxide, zinc oxide, calcium polyphosphate and graphite.
  • a plate-like filler is preferable, and mica or talc is more preferable, from the viewpoint of fluidity during molding and suppression of warpage. Mica is more preferable in terms of surface hardness and surface smoothness.
  • Two or more types of the above (C) non-fibrous filler may be used in combination.
  • the total content of (A) the liquid crystal polyester resin and (B) the glass flakes is , preferably 0 to 30 parts by weight, more preferably 5 to 30 parts by weight.
  • the surface of the (C) non-fibrous filler may be treated with a known coupling agent (eg, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agent.
  • a known coupling agent eg, silane coupling agent, titanate coupling agent, etc.
  • liquid crystalline resin composition of the present invention may contain antioxidants and heat stabilizers (for example, hindered phenols, hydroquinones, phosphites and substituted products thereof), ultraviolet Absorbents (e.g. resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and release agents (montanic acid and its salts, its esters, its half-esters, stearyl alcohol, stearamide and polyethylene waxes, etc.), dyes (e.g.
  • nitrosine, etc. and conventional additives such as colorants, plasticizers, antistatic agents, including pigments (e.g., cadmium sulfide, phthalocyanine, carbon black, etc.), and other thermoplastics can also be added to impart desired properties.
  • colorants plasticizers
  • antistatic agents including pigments (e.g., cadmium sulfide, phthalocyanine, carbon black, etc.), and other thermoplastics can also be added to impart desired properties.
  • pigments e.g., cadmium sulfide, phthalocyanine, carbon black, etc.
  • other thermoplastics can also be added to impart desired properties.
  • Melt-kneading is preferable as a method of adding these, and known methods can be used for melt-kneading.
  • a Banbury mixer, roll mill, kneader, single-screw or twin-screw extruder, etc. can be used to melt and knead the composition at a temperature of 200 to 350°C.
  • (B) glass flakes and (D) inorganic fibrous filler are homogeneously kneaded with good dispersibility, so it is preferable to use an extruder.
  • the liquid crystal polyester resin and the filler it is preferable to provide one or more kneading portions, more preferably two or more locations.
  • the filler is added from the side feeder, (A) one or more locations upstream of the side feeder of the filler in order to promote plasticization of the liquid crystal polyester resin, (A )
  • the side feeder it is preferable to install the side feeder at one or more locations downstream of the side feeder, that is, a total of two or more locations.
  • vents more preferably two or more vents.
  • the vent section is installed at one or more points upstream of the side feeder into which the filler is introduced in order to remove the moisture adhering to the liquid crystal polyester resin (A).
  • the side feeder In order to remove the cracked gas during kneading and the air brought in during the supply of the filler, it is preferable to install the side feeder at one or more locations downstream of the side feeder, a total of two or more locations.
  • the vent section may be under normal pressure or under reduced pressure.
  • liquid crystalline resin composition of the present invention is excellent in thin wall fluidity and does not impair mechanical properties, it can be molded into various molded articles by a known molding method, for example, and the excellent thin wall fluidity can be utilized. and injection molding is preferred.
  • liquid crystalline resin composition of the present invention various molded articles having high surface hardness and excellent surface smoothness can be obtained by, for example, a known molding method.
  • the molded article of the present invention is made of the liquid crystalline resin composition of the present invention.
  • Molded articles of the present invention include, for example, various gears, various cases, sensors, LED parts, liquid crystal backlight bobbins, connectors, sockets, resistors, relay cases, relay spools and bases, switches, coil bobbins, capacitors, and variable condenser cases.
  • the molded article of the present invention since the molded article of the present invention is excellent in surface hardness and surface smoothness, it has a structure in which thin parts are in contact with each other. It is preferably a molded article selected from the group consisting of
  • the polymerization temperature was maintained at 320° C.
  • the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour
  • the reaction was continued for 90 minutes, and polymerization was completed when the torque required for stirring reached 15 kg ⁇ cm.
  • the inside of the reaction vessel is pressurized to 1.0 kg/cm 2 (0.1 MPa), and the polymer is discharged into strands through a mouthpiece having a circular discharge port with a diameter of 10 mm, and pelletized by a cutter.
  • a liquid crystalline polyester resin (A-1) was obtained.
  • a composition analysis of this liquid crystal polyester resin (A-1) revealed that a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) and a structural unit derived from 4,4′-dihydroxybiphenyl (structural unit (II) )) and the structural unit derived from hydroquinone (structural unit (III)), the ratio of the structural unit derived from p-hydroxybenzoic acid (structural unit (I)) was 70 mol %. 4,4'-dihydroxybiphenyl-derived structural unit (structural unit (II )) was 70 mol %.
  • the ratio of the terephthalic acid-derived structural unit (structural unit (IV)) to the total of the terephthalic acid-derived structural unit (structural unit (IV)) and the isophthalic acid-derived structural unit (structural unit (V)) was 65 mol%. Met.
  • the total of structural units derived from 4,4′-dihydroxybiphenyl (structural unit (II)) and structural units derived from hydroquinone (structural unit (III)) is 23 mol% of all structural units, and terephthalic acid-derived
  • the structural unit (structural unit (IV)) and the isophthalic acid-derived structural unit (structural unit (V)) were 23 mol % of the total structural units.
  • the melting point (Tm) of the liquid crystal polyester resin (A-2) was 314°C.
  • the melt viscosity measured at a temperature of 324° C. and a shear rate of 1,000/s using a Koka flow tester (orifice 0.5 ⁇ 10 mm) was 20 Pa ⁇ s.
  • the jacket temperature was raised from 145°C to 270°C at an average temperature increase rate of 0.68°C/min, and from 270°C to 350°C at an average temperature increase rate of 1.4°C/min. .
  • the heating time was 4 hours.
  • the polymerization temperature was maintained at 350° C.
  • the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued, and polymerization was completed when the torque required for stirring reached 10 kg ⁇ cm.
  • the inside of the reaction vessel is pressurized to 1.0 kg/cm 2 (0.1 MPa), and the polymer is discharged into strands through a mouthpiece having a circular discharge port with a diameter of 10 mm, and pelletized by a cutter.
  • a liquid crystalline polyester resin (A-2) was obtained.
  • a composition analysis of this liquid crystal polyester resin (A-2) revealed that a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) and a structural unit derived from 4,4'-dihydroxybiphenyl (structural unit (II) )) and the structural unit derived from hydroquinone (structural unit (III)), the ratio of the structural unit derived from p-hydroxybenzoic acid (structural unit (I)) was 75 mol%. 4,4'-dihydroxybiphenyl-derived structural unit (structural unit (II )) was 60 mol %.
  • the ratio of the terephthalic acid-derived structural unit (structural unit (IV)) to the total of the terephthalic acid-derived structural unit (structural unit (IV)) and the isophthalic acid-derived structural unit (structural unit (V)) was 76 mol%. Met.
  • the total of structural units derived from 4,4'-dihydroxybiphenyl (structural unit (II)) and structural units derived from hydroquinone (structural unit (III)) is 20 mol% of all structural units, and terephthalic acid-derived
  • the structural unit (structural unit (IV)) and the isophthalic acid-derived structural unit (structural unit (V)) were 20 mol % of the total structural units.
  • the melting point (Tm) of the liquid crystal polyester resin (A-2) was 325°C.
  • the melt viscosity measured at a temperature of 335° C. and a shear rate of 1,000/s using a Koka flow tester (orifice 0.5 ⁇ 10 mm) was 8 Pa ⁇ s.
  • the inorganic filler containing the (B) glass flakes used is as follows.
  • the cumulative degree was 1% or less for particles with a particle size of 1 ⁇ m or less, and the cumulative degree was 5% or less for particles with a particle size of 20 ⁇ m or more.
  • Examples 1 to 9, Comparative Examples 1 to 3 Using a twin-screw extruder with a coaxially rotating vent having a screw diameter of 30 mm (manufactured by Japan Steel Works, Ltd., TEX30 ⁇ ), (A) liquid crystalline polyester resin was charged from a hopper in the amount shown in Table 1, and (B) glass flakes and (C) A non-fibrous filler was added in the amount shown in Table 1 through an intermediate supply port. The cylinder temperature was set to the melting point of (A) the liquid crystalline polyester resin +10° C., and melt-kneading was performed to obtain pellets of the liquid crystalline resin composition. Various characteristic values were evaluated using the obtained pellets. Table 1 shows the test results.
  • the liquid crystalline resin composition of the present invention achieves both high surface hardness and excellent surface smoothness at a high level. Therefore, the liquid crystalline resin composition of the present invention is particularly useful for electric and electronic parts such as connectors, relays, switches, coil bobbins, lamp sockets, camera modules, and integrated circuit encapsulants, which have a structure in which thin parts are in contact with each other. It can be said that it is suitable for machine parts.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

Afin de fournir une composition de résine de cristaux liquides capable d'obtenir un produit moulé ayant à la fois une dureté de surface élevée et un niveau élevé de lissé de surface, la composition de résine de cristaux liquides selon la présente invention contient de 5 à 50 parties en poids de paillettes de verre (B) par rapport à 100 parties en poids d'une résine de polyester de cristaux liquides (A), la taille de particule moyenne des paillettes de verre (B) étant de 1 à 8 µm.
PCT/JP2022/009606 2021-03-11 2022-03-07 Composition de résine de cristaux liquides et article moulé la comprenant WO2022191099A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009155525A (ja) * 2007-12-27 2009-07-16 Polyplastics Co 液晶性ポリマー組成物
JP2011074301A (ja) * 2009-10-01 2011-04-14 Toray Ind Inc 液晶性ポリエステル樹脂組成物
JP2018168320A (ja) * 2017-03-30 2018-11-01 住友化学株式会社 液晶ポリエステル組成物および成形体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009155525A (ja) * 2007-12-27 2009-07-16 Polyplastics Co 液晶性ポリマー組成物
JP2011074301A (ja) * 2009-10-01 2011-04-14 Toray Ind Inc 液晶性ポリエステル樹脂組成物
JP2018168320A (ja) * 2017-03-30 2018-11-01 住友化学株式会社 液晶ポリエステル組成物および成形体

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