TW202530296A - Liquid crystal polyester composition, molded article, and method for producing the molded article - Google Patents

Abstract

This liquid crystal polyester composition comprises a liquid crystal polyester, an inorganic filler containing a hollow glass filler, and a styrene-based resin.

Description

Liquid crystal polyester composition, molded article, and method for producing the molded article

The present invention relates to a liquid crystal polyester composition, a molded product, and a method for producing the molded product.

Molded articles containing liquid crystal polyesters are used in a variety of fields, particularly in electrical and electronic components. The industry is researching various compositions tailored to the desired properties of these molded articles. For example, Patent Document 1 discloses a composition comprising liquid crystal polyester and hollow spheres as a material for lightweighting molded articles. [Prior Art Document] [Patent Document]

Patent document 1: Japanese Patent Publication No. 2004-323705

[Problem the Invention Is Aiming to Solve] In recent years, the reuse and regrinding of scrap material from injection molding parts, such as runners and sprues, has gained attention to reduce environmental impact.

Regarding the composition described in Patent Document 1, there is room for improvement in that the amount of fine powder generated when pulverizing scrap materials containing the composition is large, and the material loss during regrinding is large.

An object of the present invention is to provide a liquid crystal polyester composition having high fluidity and a low dielectric constant, and capable of forming a molded article with minimal fine powder dispersion upon crushing, and a molded article containing the composition. Another object of the present invention is to provide a method for producing the aforementioned molded article. [Technical Means for Solving the Problem]

The present invention provides, for example, the following. [1] A liquid crystal polyester composition comprising a liquid crystal polyester, an inorganic filler containing a hollow glass filler, and a styrene-based resin. [2] The liquid crystal polyester composition as described in [1], wherein the styrene-based resin is polystyrene. [3] The liquid crystal polyester composition as described in [1] or [2], wherein the content of the hollow glass filler is from 5 parts by mass to 60 parts by mass relative to 100 parts by mass of the liquid crystal polyester. [4] The liquid crystal polyester composition as described in any one of [1] to [3], wherein the content of the styrene-based resin is from 5 parts by mass to 60 parts by mass relative to 100 parts by mass of the liquid crystal polyester. [5] The liquid crystal polyester composition as described in any one of [1] to [4], wherein the ratio of the content _C2 of the above-mentioned styrene-based resin to the content _C1 of the above-mentioned inorganic filler ( _C2 / _C1 ) is 0.1 or more and 10 or less. [6] The liquid crystal polyester composition as described in any one of [1] to [5], wherein the above-mentioned inorganic filler further contains a non-hollow filler. [7] The liquid crystal polyester composition as described in [6], wherein the content of the above-mentioned non-hollow filler is 2 parts by mass or more and 25 parts by mass or less relative to 100 parts by mass of the above-mentioned liquid crystal polyester. [8] The liquid crystal polyester composition as described in any one of [1] to [7], wherein the ratio of the above-mentioned hollow glass filler to the above-mentioned inorganic filler is 50% by mass or more and 90% by mass or less. [9] A molded article comprising the liquid crystal polyester composition as described in any one of [1] to [8]. [10] A method for producing a molded article, comprising the step of obtaining a molded article by molding the liquid crystal polyester composition as described in any one of [1] to [8]. [11] The method for producing a molded article as described in [10], wherein the molding is injection molding. [Effects of the Invention]

The present invention provides a liquid crystal polyester composition having high fluidity and a low dielectric constant, and capable of forming a molded article with minimal fine powder scattering upon crushing, and a molded article containing the composition. Furthermore, the present invention provides a method for producing the molded article.

The following describes in detail the preferred embodiments of the present invention.

The liquid crystal polyester composition of this embodiment (hereinafter also referred to as "liquid crystal polyester composition" or "composition") includes a liquid crystal polyester, an inorganic filler including a hollow glass filler, and a styrene resin.

The liquid crystal polyester composition of this embodiment has high fluidity and a low dielectric constant. Furthermore, molded articles formed from the liquid crystal polyester composition of this embodiment produce less fine powder during crushing, resulting in less loss during regrinding.

In this embodiment, the dielectric constant of the composition is believed to be lowered by the addition of a hollow glass filler. Furthermore, in this embodiment, the addition of a styrene-based resin, which has superior toughness to that of the liquid crystal polyester, mitigates the impact of crushing on the molded article and suppresses the dispersion of fine powder. Furthermore, in this embodiment, the addition of a styrene-based resin is believed to improve the wettability of the liquid crystal polyester and the hollow glass filler, thereby enhancing fluidity during melting.

The liquid crystal polyester may be any polyester that exhibits liquid crystallinity in a molten state. The liquid crystal polyester composition may contain only one type of liquid crystal polyester or two or more types.

Liquid crystal polyesters have structural units (also called monomers) derived from raw material monomers. The majority of the monomers in the liquid crystal polyester (e.g., 90 mol%, 95 mol%, or 99 mol%, preferably all of the monomers, relative to the total of all monomers) can be monomers derived from aromatic compounds. Liquid crystal polyesters whose entire monomers are derived from aromatic compounds are also referred to as wholly aromatic liquid crystal polyesters.

Aromatic compounds are compounds having an aromatic ring. Aromatic compounds suitable as starting monomers may have an aromatic ring and two or more polymerizable groups (e.g., hydroxyl, amino, or carboxyl groups, preferably hydroxyl or carboxyl groups) bonded to the aromatic ring.

The aromatic compound may be, for example, a compound represented by the following formula (1-1) (hereinafter also referred to as an aromatic compound (1-1)), a compound represented by the following formula (1-2) (hereinafter also referred to as an aromatic compound (1-2)), or a compound represented by the following formula (1-3) (hereinafter also referred to as an aromatic compound (1-3)). X ¹ -Ar ¹ -Y ¹ (1-1) X ² -Ar ² -X ³ (1-2) Y ² -Ar ³ -Y ³ (1-3) [wherein, Ar ¹ , Ar ² , and Ar ³ independently represent a phenylene group, a biphenylene group, a condensed polycyclic aromatic hydrocarbon group, or a group represented by formula (Z-1). Some or all of the hydrogen atoms possessed by Ar ¹ , Ar ² , and Ar ³ may be substituted with a halogen atom, an alkyl group, or an aryl group.] X ¹ , X ² , and X ³ each independently represent a hydroxyl group or an amino group. ^{Y 1} , Y ² , and Y ³ each represent a carboxyl group. -Ar ⁴ -Z ¹ -Ar ⁵ - (Z-1) [Wherein, Ar ⁴ and Ar ⁵ each independently represent a phenylene group or a condensed polycyclic aromatic hydrocarbon group. Z ¹ - represents an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ -), or an alkanediyl group.]

The monomer unit derived from an aromatic compound may be, for example, a monomer unit represented by the following formula (2-1) (hereinafter also referred to as monomer unit (2-1)), a structural unit represented by the following formula (2-2) (hereinafter also referred to as monomer unit (2-2)), or a structural unit represented by the following formula (2-3) (hereinafter also referred to as monomer unit (2-3)). Furthermore, monomer unit (2-1) may be referred to as a monomer unit derived from the aromatic compound (1-1), monomer unit (2-2) may be referred to as a monomer unit derived from the aromatic compound (1-2), and monomer unit (2-3) may be referred to as a monomer unit derived from the aromatic compound (1-3). ^-X11 - ^Ar1 - ^Y11- (2-1)-X12- ^Ar2 - ^X13- (2-2) ^-Y12 - ^Ar3 - ^Y13- (2-3) [In the formula, ^Ar1 , ^Ar2 , and ^Ar3 have ^the same meanings as above. ^X11 , ^X12 , and ^X13 each independently represent an oxygen atom (—O—) or an imino group (—NH—). ^Y11 , ^Y12 , and ^Y13 represent a carbonyl group (—CO—).]

The phenylene group may be, for example, 1,4-phenylene or 1,3-phenylene, and is preferably 1,4-phenylene.

The biphenylene group may be, for example, 4,4'-biphenylene group.

A condensed polycyclic aromatic hydrocarbon group is formed by removing two hydrogen atoms from a condensed polycyclic aromatic hydrocarbon. Examples of condensed polycyclic aromatic hydrocarbons include naphthalene, anthracene, phenanthrene, tetracene, pyrene, terphenyl, perylene, and fluorene. Among these, naphthalene is preferred from the perspectives of availability and price.

The condensed polycyclic aromatic hydrocarbon group may be a naphthylene group. The naphthylene group may be, for example, a 2,6-naphthylene group or a 2,7-naphthylene group, preferably a 2,6-naphthylene group.

Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group as a substituent may be linear, branched, or cyclic. For example, the alkyl group may be an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tertiary butyl, n-hexyl, 2-ethylhexyl, n-octyl, and n-decyl.

The aryl group as a substituent may be monocyclic or condensed. Examples of the aryl group include 6-20 carbon atoms. Examples of the aryl group include phenyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, and 2-naphthyl. The aryl group may be a group in which the hydrogen atom of the aromatic ring of a tolyl group is replaced by an alkyl group.

The number of substituents possessed by Ar ¹ , Ar ² and Ar ³ may be, for example, 0 to 2, 0 or 1, or even 0.

The alkanediyl group in Z ¹ - may be linear or branched. The alkanediyl group may be an alkanediyl group having 1 to 10 carbon atoms. Examples of the alkanediyl group include methylene, ethanediyl, propanediyl (e.g., propane-2,2-diyl), butanediyl, and octanediyl (e.g., octane-3,3-diyl).

X ¹ , X ² , and X ³ are preferably hydroxyl groups. That is, the aromatic compound (1-1) may be an aromatic hydroxycarboxylic acid, the aromatic compound (1-2) may be an aromatic diol, and the aromatic compound (1-3) may be an aromatic dicarboxylic acid.

X ¹¹ , X ¹² and X ¹³ are preferably oxygen atoms (—O—).

The liquid crystal polyester may be a polymer having the monomer unit (2-1), a polymer having the monomer unit (2-2) and the monomer unit (2-3), or a polymer having the monomer unit (2-1), the monomer unit (2-2), and the monomer unit (2-3).

When the liquid crystal polyester comprises monomer unit (2-1), monomer unit (2-2), and monomer unit (2-3), the content of monomer unit (2-1) relative to the total of all monomer units in the liquid crystal polyester may be, for example, 30 mol% or more, 40 mol% or more, 45 mol% or more, 50 mol% or more, or 55 mol% or more. Furthermore, when the liquid crystal polyester comprises monomer unit (2-1), monomer unit (2-2), and monomer unit (2-3), the content of monomer unit (2-1) relative to the total of all monomer units in the liquid crystal polyester may be, for example, 80% or less, or 70% or less. That is, when the liquid crystal polyester comprises monomer unit (2-1), monomer unit (2-2), and monomer unit (2-3), the content of monomer unit (2-1) relative to the total of all monomer units of the liquid crystal polyester may be, for example, 30 mol% to 80 mol%, 30 mol% to 70 mol%, 40 mol% to 80 mol%, 40 mol% to 70 mol%, 45 mol% to 80 mol%, 45 mol% to 70 mol%, 50 mol% to 80 mol%, 50 mol% to 70 mol%, 55 mol% to 80 mol%, or 55 mol% to 70 mol%.

When the liquid crystal polyester comprises monomer unit (2-1), monomer unit (2-2), and monomer unit (2-3), the content of monomer unit (2-2) and the content of monomer unit (2-3) relative to the total of all monomer units in the liquid crystal polyester may be, for example, 35 mol% or less, or 30 mol% or less. Furthermore, when the liquid crystal polyester comprises monomer unit (2-1), monomer unit (2-2), and monomer unit (2-3), the content of monomer unit (2-2) and the content of monomer unit (2-3) relative to the total of all monomer units in the liquid crystal polyester may be, for example, 5 mol% or more, 10 mol% or more, or 15 mol% or more. That is, when the liquid crystal polyester comprises monomer unit (2-1), monomer unit (2-2), and monomer unit (2-3), the content of monomer unit (2-2) and the content of monomer unit (2-3), respectively, relative to the total of all monomer units of the liquid crystal polyester, may be, for example, 5 mol% to 35 mol%, 5 mol% to 30 mol%, 10 mol% to 35 mol%, 10 mol% to 30 mol%, 15 mol% to 35 mol%, or 15 mol% to 30 mol%.

The liquid crystal polyester may have monomer units other than the monomer unit (2-1), the monomer unit (2-2), and the monomer unit (2-3), and the amount of monomer units other than the monomer unit (2-1), the monomer unit (2-2), and the monomer unit (2-3), relative to the total of all monomer units in the liquid crystal polyester, may be 10 mol% or less, 5 mol% or less, 2 mol% or less, 1 mol% or less, or 0 mol%. That is, in the liquid crystal polyester, the total amount of the monomer unit (2-1), the monomer unit (2-2), and the monomer unit (2-3), relative to the total of all monomer units constituting the liquid crystal polyester, may be, for example, 90 mol% or more, 95 mol% or more, 99 mol% or more, or 100 mol%.

The liquid crystal polyester may be a polymer comprising a monomer unit (A-1) having a condensed aromatic ring and a monomer unit (A-2) having no condensed aromatic ring but having a benzene ring.

Examples of the condensed aromatic ring possessed by the monomer unit (A-1) include a naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, pyrene ring, terphenyl ring, perylene ring, and fluorene ring. Among these, a naphthalene ring is preferred from the viewpoint of availability and price.

The monomer unit (A-1) may be a monomer unit represented by formula (2-1) (wherein Ar ¹ is a condensed polycyclic aromatic alkyl group, or at least one of Ar ⁴ and Ar ⁵ is a group represented by formula (Z-1) in which a polycyclic aromatic alkyl group is condensed), or a monomer unit represented by formula (2-2) (wherein Ar ² is a condensed polycyclic aromatic alkyl group, or at least one of Ar ⁴ and Ar ⁵ is a group represented by formula (Z-1) in which a polycyclic aromatic alkyl group is condensed), or a monomer unit represented by formula (2-3) (wherein Ar ³ is a condensed polycyclic aromatic alkyl group, or at least one of Ar ⁴ and Ar ⁵ is a group represented by formula (Z-1) in which a polycyclic aromatic alkyl group is condensed).

When the liquid crystal polyester is a polymer containing the monomer unit (A-1), the liquid crystal polyester preferably contains at least the monomer unit (A-1) as the monomer unit (2-1), and more preferably contains the monomer unit (A-1) as the monomer unit (2-1) and the monomer unit (2-3).

The monomer unit (A-1) can also be considered a monomer unit derived from an aromatic compound (A-1') having a condensed aromatic ring. Examples of the aromatic compound (A-1') include 2-hydroxy-6-naphthoic acid, 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 2-hydroxy-3-naphthoic acid, 1-hydroxy-5-naphthoic acid, and 2,7-naphthalenediol.

The monomer unit (A-2) may be a monomer unit represented by formula (2-1) (wherein Ar ¹ is a phenylene group, a biphenylene group, or Ar ⁴ and Ar ⁵ are a group represented by formula (Z-1) in which they are phenylene groups), or a monomer unit represented by formula (2-2) (wherein Ar ² is a phenylene group, a biphenylene group, or Ar ⁴ and Ar ⁵ are a group represented by formula (Z-1) in which they are phenylene groups), or a monomer unit represented by formula (2-3) (wherein Ar ³ is a phenylene group, a biphenylene group, or Ar ⁴ and Ar ⁵ are a group represented by formula (Z-1) in which they are phenylene groups).

When the liquid crystal polyester is a polymer containing the monomer unit (A-2), the liquid crystal polyester preferably contains at least the monomer unit (A-2) as the monomer unit (2-2), and more preferably contains the monomer unit (A-2) as the monomer unit (2-2) and the monomer unit (2-3).

The monomer unit (A-2) may be a monomer unit derived from an aromatic compound (A-2') having a benzene ring instead of a condensed aromatic ring. Examples of the aromatic compound (A-2') include p-hydroxybenzoic acid, terephthalic acid, hydroquinone, isophthalic acid, and 4,4'-biphenol.

When the liquid crystal polyester comprises monomer units (A-1) and monomer units (A-2), the content of monomer units (A-1) relative to the total of all monomer units constituting the liquid crystal polyester may be, for example, 20 mol% or greater, 30 mol% or greater, 40 mol% or greater, 50 mol% or greater, 60 mol% or greater, or even 70 mol% or greater. A higher content of monomer units (A-1) tends to further improve dielectric properties. Alternatively, the content of monomer units (A-1) relative to the total of all monomer units constituting the liquid crystal polyester may be, for example, 90 mol% or less, 85 mol% or less, or even 80 mol% or less. This tends to improve moldability and processability at low temperatures. That is, the content of the monomer unit (A-1) relative to the total of all monomer units constituting the liquid crystal polyester may be, for example, 20 mol% to 90 mol%, 20 mol% to 85 mol%, 20 mol% to 80 mol%, 30 mol% to 90 mol%, 30 mol% to 85 mol%, 30 mol% to 80 mol%, 40 mol% to 40 mol%, 40 mol% to 85 mol%, % or less, 40 mol% or more and 80 mol% or less, 50 mol% or more and 90 mol% or less, 50 mol% or more and 85 mol% or less, 50 mol% or more and 80 mol% or less, 60 mol% or more and 90 mol% or less, 60 mol% or more and 85 mol% or less, 60 mol% or more and 80 mol% or less, 70 mol% or more and 90 mol% or less, 70 mol% or more and 85 mol% or less, or 70 mol% or more and 80 mol% or less.

When the liquid crystal polyester comprises monomer units (A-1) and monomer units (A-2), the content of monomer units (A-2) relative to the total of all monomer units constituting the liquid crystal polyester may be, for example, 10 mol% or greater, 15 mol% or greater, or 20 mol% or greater. Furthermore, the content of monomer units (A-2) relative to the total of all monomer units constituting the liquid crystal polyester may be, for example, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, or 30 mol% or less. That is, the content of the monomer unit (A-2) may be, for example, 10 mol% to 80 mol%, 10 mol% to 70 mol%, 10 mol% to 60 mol%, 10 mol% to 50 mol%, 10 mol% to 40 mol%, 10 mol% to 30 mol%, 15 mol% to 80 mol%, 15 mol% to 70 mol%, 15 mol% to 60 mol% or less, 15 mol% or more and 50 mol% or less, 15 mol% or more and 40 mol% or less, 15 mol% or more and 30 mol% or less, 20 mol% or more and 80 mol% or less, 20 mol% or more and 70 mol% or less, 20 mol% or more and 60 mol% or less, 20 mol% or more and 50 mol% or less, 20 mol% or more and 40 mol% or less, or 20 mol% or more and 30 mol% or less.

In the liquid crystal polyester, the total amount of monomer units (A-1) and monomer units (A-2) relative to the total of all monomer units constituting the liquid crystal polyester can be, for example, 90 mol% or more, 95 mol% or more, 99 mol% or more, or 100 mol%.

In this specification, the number of each monomer unit in a liquid crystal polyester can be determined using the analytical method described in Japanese Patent Application Laid-Open No. 2000-19168. Specifically, the liquid crystal polyester can be depolymerized by reacting it with a lower alcohol in a supercritical state, and the depolymerization product (the monomer from which each monomer unit is derived) can be quantified by liquid chromatography to calculate the number of each monomer unit relative to the total monomer units.

Liquid crystal polyester can be produced by polymerizing raw monomers corresponding to the monomer units constituting the liquid crystal polyester. For example, it can be produced according to the method described in Japanese Patent No. 6439027.

The flow initiation temperature of the liquid crystal polyester may be, for example, 250°C or higher, or 270°C or higher. Furthermore, the flow initiation temperature of the liquid crystal polyester may be, for example, 400°C or lower, 360°C or lower, or 340°C or lower. That is, the flow initiation temperature of the liquid crystal polyester may be, for example, 250°C to 400°C, 250°C to 360°C, 250°C to 340°C, 270°C to 400°C, 270°C to 360°C, or 270°C to 340°C.

In this specification, the flow initiation temperature of liquid crystal polyester is measured using a flow tester. The temperature at which the viscosity of the liquid crystal polyester reaches 4800 Pa·s (48,000 poise) is measured by melting the liquid crystal polyester while heating it at a rate of 4°C/min under a load of 9.8 MPa (100 kg/cm ² ). The melted liquid crystal polyester is then extruded from a nozzle with an inner diameter of 1 mm and a length of 10 mm.

The dielectric dissipation factor of the liquid crystal polyester at 10 GHz can be, for example, 0.006 or less, preferably 0.004 or less, and more preferably 0.002 or less. This facilitates obtaining the composition described below having a favorable dielectric dissipation factor.

The relative dielectric constant of the liquid crystal polyester at 10 GHz may be, for example, 4.0 or less, or 3.8 or less. Furthermore, the relative dielectric constant of the liquid crystal polyester at 10 GHz may be, for example, 2.8 or more, or 3.0 or more.

In this specification, the dielectric dissipation factor and relative permittivity of liquid crystal polyester at 10 GHz were measured using the following method. Liquid crystal polyester pellets were molded using an injection molding machine (ROBOSHOT S-2000i 30B, manufactured by FANUC Corporation) at a barrel temperature of 330°C, a mold temperature of 130°C, and an injection speed of 100 mm/s. Test pieces with a width of 50 mm, a length of 50 mm, and a thickness of 0.5 mm were produced. The relative permittivity and dielectric dissipation factor of these test pieces at 10 GHz were measured using a vector network analyzer (N5290A, manufactured by Keysight Technologies, Inc.) and a split cylinder resonator (CR710, manufactured by EM Labs, Inc.). The measurement environment was set at 23°C and 50% relative humidity.

The liquid crystal polyester composition of this embodiment contains at least a hollow glass filler as an inorganic filler.

Hollow glass filler is a glass filler that contains an air layer inside, and can also be called hollow glass beads or hollow glass balls.

The average particle size (median particle size, D50) of the hollow glass filler can be, for example, 5 μm or greater, or 8 μm or greater, 10 μm or greater, or 15 μm or greater. Furthermore, the average particle size (median particle size, D50) of the hollow glass filler can be, for example, 80 μm or less, or 50 μm or less, 35 μm or less, or 25 μm or less.

The content of the insulating glass filler relative to 100 parts by mass of the liquid crystal polyester can be, for example, 5 parts by mass or more. To facilitate achieving a lower dielectric constant, it can be 7 parts by mass or more, 10 parts by mass or more, or even 15 parts by mass or more. Furthermore, the content of the insulating glass filler relative to 100 parts by mass of the liquid crystal polyester can be, for example, 60 parts by mass or less. To facilitate achieving higher fluidity and a molded product that further suppresses the generation of fine powder during crushing, it can be 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, or even 25 parts by mass or less. That is, the content of the hollow glass filler relative to 100 parts by mass of the liquid crystal polyester can be, for example, 5 parts by mass to 60 parts by mass, 5 parts by mass to 50 parts by mass, 5 parts by mass to 40 parts by mass, 5 parts by mass to 30 parts by mass, 5 parts by mass to 25 parts by mass, 7 parts by mass to 60 parts by mass, 7 parts by mass to 50 parts by mass, 7 parts by mass to 40 parts by mass, 7 parts by mass to 30 parts by mass, 7 parts by mass to 70 parts by mass, or more. 25 parts by mass or less, 10 parts by mass or more but less than 60 parts by mass, 10 parts by mass or more but less than 50 parts by mass, 10 parts by mass or more but less than 40 parts by mass, 10 parts by mass or more but less than 30 parts by mass, 10 parts by mass or more but less than 25 parts by mass, 15 parts by mass or more but less than 60 parts by mass, 15 parts by mass or more but less than 50 parts by mass, 15 parts by mass or more but less than 40 parts by mass, 15 parts by mass or more but less than 30 parts by mass, or 15 parts by mass or more but less than 25 parts by mass.

The ratio of the hollow glass filler to the inorganic filler is, for example, 50% by mass or more. From the perspective of more significantly achieving the above-mentioned effect, it can be 60% by mass or more, 70% by mass or more, 75% by mass or more, or even 100% by mass.

The inorganic filler may further include an inorganic filler other than the hollow glass filler. The inorganic filler other than the hollow glass filler may be a non-hollow filler. By further including a non-hollow filler as the inorganic filler, the generation of fine powder during crushing tends to be more significantly suppressed.

Inorganic fillers other than hollow glass fillers may be fibrous fillers, plate fillers, or granular fillers.

Examples of fibrous fillers include glass fibers; carbon fibers such as PAN-based carbon fibers and PITCH-based carbon fibers; ceramic fibers such as silica fibers, alumina fibers, and aluminum silicon fibers; and metal fibers such as stainless steel fibers. Examples also include potassium titanium whiskers, barium titanium whiskers, wollastonite whiskers, aluminum borate whiskers, silicon nitride whiskers, and silicon carbide whiskers.

Examples of plate-like fillers include talc, mica, graphite, wollastonite, glass scales, barium sulfate, and calcium carbonate. Mica may be muscovite, phlogopite, fluorophlogopite, or tetrasilicon mica.

Examples of the particulate filler include silicon dioxide, aluminum oxide, titanium oxide, glass beads, boron nitride, silicon carbide, and calcium carbonate.

The content of the non-hollow filler relative to 100 parts by mass of the liquid crystal polyester may be, for example, 1 part by mass or more. From the perspective of more significantly achieving the aforementioned effects, it may be 2 parts by mass or more, 3 parts by mass or more, or even 4 parts by mass or more. Furthermore, the content of the non-hollow filler relative to 100 parts by mass of the liquid crystal polyester may be, for example, 25 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less. That is, the content of the non-hollow filler relative to 100 parts by mass of the liquid crystal polyester may be, for example, 1 part by mass to 25 parts by mass, 1 part by mass to 20 parts by mass, 1 part by mass to 15 parts by mass, 1 part by mass to 10 parts by mass, 1 part by mass to 5 parts by mass, 2 parts by mass to 25 parts by mass, 2 parts by mass to 20 parts by mass, 2 parts by mass to 15 parts by mass, or 2 parts by mass to 10 parts by mass. , 2 parts by mass or more but less than 5 parts by mass, 3 parts by mass or more but less than 25 parts by mass, 3 parts by mass or more but less than 20 parts by mass, 3 parts by mass or more but less than 15 parts by mass, 3 parts by mass or more but less than 10 parts by mass, 3 parts by mass or more but less than 5 parts by mass, 4 parts by mass or more but less than 25 parts by mass, 4 parts by mass or more but less than 20 parts by mass, 4 parts by mass or more but less than 15 parts by mass, 4 parts by mass or more but less than 10 parts by mass, or 4 parts by mass or more but less than 5 parts by mass.

The content of the inorganic filler relative to 100 parts by mass of the liquid crystal polyester may be, for example, 5 parts by mass or more, 7 parts by mass or more, 10 parts by mass or more, or 15 parts by mass or more. Furthermore, the content of the inorganic filler relative to 100 parts by mass of the liquid crystal polyester may be, for example, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less. That is, the content of the inorganic filler relative to 100 parts by mass of the liquid crystal polyester may be, for example, 5 parts by mass to 60 parts by mass, 5 parts by mass to 50 parts by mass, 5 parts by mass to 40 parts by mass, 5 parts by mass to 30 parts by mass, 5 parts by mass to 25 parts by mass, 7 parts by mass to 60 parts by mass, 7 parts by mass to 50 parts by mass, 7 parts by mass to 40 parts by mass, 7 parts by mass to 30 parts by mass, 7 parts by mass to 70 parts by mass, or more. 25 parts by mass or less, 10 parts by mass or more but less than 60 parts by mass, 10 parts by mass or more but less than 50 parts by mass, 10 parts by mass or more but less than 40 parts by mass, 10 parts by mass or more but less than 30 parts by mass, 10 parts by mass or more but less than 25 parts by mass, 15 parts by mass or more but less than 60 parts by mass, 15 parts by mass or more but less than 50 parts by mass, 15 parts by mass or more but less than 40 parts by mass, 15 parts by mass or more but less than 30 parts by mass, or 15 parts by mass or more but less than 25 parts by mass.

Styrenic resins are polymers with monomer units derived from styrene.

Styrene-based resins may have monomer units derived from monomers other than styrene. Examples of monomers other than styrene include acrylonitrile, butadiene, and ethylene.

Examples of the styrene-based resin include polystyrene and modified polystyrene. From the perspective of more significantly achieving the above-mentioned effects, polystyrene is preferred.

The polystyrene may be iso-, p- or hetero-reinforced polystyrene.

The dielectric dissipation factor of styrene-based resin at 10 GHz may be, for example, less than 0.001, or less than 0.0008.

Furthermore, the relative dielectric constant of the styrene-based resin at 10 GHz may be, for example, 3 or less, or 2.6 or less. Furthermore, the relative dielectric constant of the styrene-based resin at 10 GHz may be, for example, 2 or more, or 2.2 or more.

In this specification, the dielectric dissipation factor and relative permittivity of styrene-based resins at 10 GHz are measured using the following method. Using an injection molding machine (ROBOSHOT S-2000i 30B, manufactured by FANUC Corporation), styrene-based resin pellets were molded at a cylinder temperature of 290°C (XAREC 300ZC) or 300°C (XAREC 90ZC), a mold temperature of 130°C, and an injection speed of 100 mm/s. Test pieces with a width of 50 mm, a length of 50 mm, and a thickness of 0.5 mm were produced. The cylinder temperature was set to a temperature at which the resin being measured is fully plasticized and decomposition of the resin does not significantly proceed. The relative permittivity and dielectric dissipation factor of the obtained test pieces were measured at 10 GHz using a vector network analyzer (Keysight Technologies, Inc., N5290A) and a split cylinder resonator (EM Labs, Inc., CR710). The measurement environment was set at 23°C and 50% RH.

The number average molecular weight (Mn) of the styrene resin may be, for example, 10,000 or greater, or 20,000 or greater, 30,000 or greater, or 40,000 or greater. Furthermore, the number average molecular weight (Mn) of the styrene resin may be, for example, 200,000 or less, or 150,000 or less, 130,000 or less, or 100,000 or less.

The weight average molecular weight (Mw) of the styrene resin may be, for example, 20,000 or greater, or 40,000 or greater, 60,000 or greater, or 80,000 or greater. Furthermore, the weight average molecular weight (Mw) of the styrene resin may be, for example, 400,000 or less, or 300,000 or less, 250,000 or less, or 200,000 or less.

The molecular weight distribution (Mw/Mn) of the styrene resin may be, for example, 1.3 or greater, 1.6 or greater, 1.8 or greater, or 2 or greater. Furthermore, the molecular weight distribution (Mw/Mn) of the styrene resin may be, for example, 8 or less, 7 or less, 6 or less, or 5 or less.

In this specification, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn) of styrene resins are those measured by gel permeation chromatography at 135°C using 1,2,4-trichlorobenzene as a solvent.

The content of the styrene-based resin relative to 100 parts by mass of the liquid crystal polyester can be, for example, 5 parts by mass or more. From the perspective of achieving higher fluidity and more easily obtaining a molded product with further suppressed generation of fine powder during crushing, the content can be 7 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or even 20 parts by mass or more. Furthermore, the content of the styrene-based resin relative to 100 parts by mass of the liquid crystal polyester can be, for example, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less. That is, the content of the styrene-based resin relative to 100 parts by mass of the liquid crystal polyester may be, for example, 5 parts by mass to 60 parts by mass, 5 parts by mass to 50 parts by mass, 5 parts by mass to 40 parts by mass, 5 parts by mass to 30 parts by mass, 5 parts by mass to 25 parts by mass, 7 parts by mass to 60 parts by mass, 7 parts by mass to 50 parts by mass, 7 parts by mass to 40 parts by mass, 7 parts by mass to 30 parts by mass, 7 parts by mass to 25 parts by mass, 10 parts by mass to 60 parts by mass, 10 parts by mass to 50 parts by mass, or more. 10 parts by mass or less but less than 40 parts by mass, 10 parts by mass or more but less than 30 parts by mass, 10 parts by mass or more but less than 25 parts by mass, 15 parts by mass or more but less than 60 parts by mass, 15 parts by mass or more but less than 50 parts by mass, 15 parts by mass or more but less than 40 parts by mass, 15 parts by mass or more but less than 30 parts by mass, 15 parts by mass or more but less than 25 parts by mass, 20 parts by mass or more but less than 60 parts by mass, 20 parts by mass or more but less than 50 parts by mass, 20 parts by mass or more but less than 40 parts by mass, 20 parts by mass or more but less than 30 parts by mass, or 20 parts by mass or more but less than 25 parts by mass.

The ratio of the styrene resin content _C2 to the inorganic filler content _C1 ( _C2 / _C1 ) (mass ratio) can be, for example, 0.10 or greater. To achieve more significant effects, it can be 0.12 or greater, 0.14 or greater, or even 0.20 or greater. Furthermore, the ratio of the styrene resin content _C2 to the insulating glass filler content _C1 ( _C2 / _C1 ) (mass ratio) can be, for example, 10.0 or less. To achieve more significant effects, it can be 8.0 or less, 7.0 or less, or even 5.0 or less.

In the liquid crystal polyester composition, the total amount of the liquid crystal polyester, the inorganic filler, and the styrene resin may be, for example, 80% by mass or more, 85% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, or even 100% by mass.

The liquid crystal polyester composition may further contain other components in addition to the liquid crystal polyester, inorganic filler and styrene resin.

For example, the liquid crystal polyester composition may contain one or more resins other than the liquid crystal polyester and styrene resin. Examples of such resins include polyolefins, cyclic polyolefins, polyvinyl chloride, polysulfone, (meth)acrylic resins, polyphenylene ether resins, polyacetal resins, polyamide resins, imide resins, cellulose resins, polyetheretherketone resins, fluororesins, polycarbonate resins, and thermosetting resins.

Furthermore, the liquid crystal polyester composition may further contain a colorant, a dispersant, a plasticizer, an antioxidant, a curing agent, a flame retardant, a heat stabilizer, a UV absorber, an antistatic agent, a surfactant, a lubricant, a release agent, and the like.

The dielectric dissipation factor of the liquid crystal polyester composition at 1 GHz may be, for example, 0.004 or less, preferably 0.003 or less, and more preferably 0.001 or less.

The relative dielectric constant of the liquid crystal polyester composition at 1 GHz may be, for example, 3.4 or less, or 2.8 or less. Furthermore, the relative dielectric constant of the liquid crystal polyester composition at 1 GHz may be, for example, 2.3 or greater, or 2.7 or greater.

The dielectric dissipation factor and relative dielectric constant of the liquid crystal polyester composition were measured by the methods described in the Examples.

The specific gravity of the liquid crystal polyester composition may be, for example, 1.20 or less, preferably 1.18 or less, and more preferably 1.14 or less. Furthermore, the specific gravity of the liquid crystal polyester composition may be, for example, 1.05 or more, or 1.10 or more.

The specific gravity of the liquid crystal polyester composition is measured by the method described in the examples.

The liquid crystal polyester composition of this embodiment has excellent fluidity when melted and is therefore preferably used as a molding material. The liquid crystal polyester composition can be used, for example, in the form of pellets.

The molded article of this embodiment contains the above-mentioned liquid crystal polyester composition. The molded article of this embodiment can be, for example, a connector, a socket, a relay part, a coil frame, an optical pickup, an oscillator, a semiconductor package, an IC tray, a wafer carrier, a home appliance part, a lighting fixture part, an audio equipment part, a ferrule for an optical cable, a telephone part, a fax machine part, a modem part, a separation claw, a heater bracket, an impeller, a fan gear, a gear, a bearing, a motor part, a motor housing, an engine part, an interior of an aircraft cabin, Parts, electrical parts, automotive interior parts, microwave cookware, heat-resistant tableware, flooring materials, wall materials, beams, columns, roofing tiles, aircraft parts, spacecraft parts, space equipment parts, nuclear reactors, marine facility components, cleaning jigs, optical equipment parts, valves, tubes, nozzles, filters, membranes, medical equipment parts, medical materials, sensor parts, sanitary supplies, sporting goods, or recreational equipment.

The molded product of this embodiment can be obtained, for example, by forming the above-mentioned liquid crystal polyester composition into a desired shape and performing processing as needed.

As a molding method for the molded product, melt molding is preferred. Examples of melt molding include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, and press molding, with injection molding being preferred.

While preferred embodiments of the present invention have been described above, the present invention is not limited to the aforementioned embodiments. [Examples]

The following examples further illustrate the present invention in detail, but the present invention is not limited to these examples. The percentages and parts below that represent the content or usage amount are based on mass unless otherwise specified.

(Example 1-1) (1) Preparation of Liquid Crystal Polyester (LCP1) In a reactor equipped with a stirrer, a torque meter, a nitrogen inlet tube, a thermometer, and a reflux condenser, 994.5 g (7.2 mol) of p-hydroxybenzoic acid, 446.9 g (2.4 mol) of 4,4'-dihydroxybiphenyl, 299.0 g (1.8 mol) of terephthalic acid, 99.7 g (0.6 mol) of isophthalic acid, and 1347.6 g (13.2 mol) of acetic anhydride were added, and 0.2 g of 1-methylimidazole was added as a catalyst to fully replace the interior of the reactor with nitrogen. Thereafter, while stirring under a nitrogen flow, the temperature was raised from room temperature to 150°C over 30 minutes, and the temperature was maintained and refluxed for 30 minutes. Next, 0.9 g of 1-methylimidazole was added, and while distilling off the by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 320°C over 2 hours and 50 minutes. After holding at 320°C for 30 minutes, the contents were removed and cooled to room temperature. The resulting solid was pulverized to a particle size of 0.1-1 mm using a grinder. Solid-state polymerization was then carried out under a nitrogen atmosphere by heating from room temperature to 250°C over 1 hour, then from 250°C to 285°C over 5 hours, and then held at 285°C for 3 hours. The solid was cooled to obtain a powdered liquid crystal polyester (LCP1). The flow onset temperature of the obtained liquid crystal polyester (LCP1) was 327°C. Furthermore, the flow initiation temperature is measured by the following method.

<Flow Initiation Temperature Determination> Using a flow tester (Shimadzu Corporation, "CFT-500EX"), approximately 2 g of liquid crystal polyester was filled into a cylinder equipped with a die having an inner diameter of 1 mm and a length of 10 mm. The liquid crystal polyester was melted while being heated at a rate of 4°C/min under a load of 9.8 MPa. The liquid crystal polyester was then extruded from the nozzle. The temperature at which a viscosity of 4800 Pa·s was measured and designated as the flow initiation temperature of the liquid crystal polyester.

(2) Preparation of liquid crystal polyester composition Glass hollow spheres (iM16K, manufactured by 3M, average particle size (median particle size, D50): 21 μm) (referred to as "GB1" in Table 1) were prepared as hollow glass fillers. In addition, styrene resin 1 (XAREC 300ZC, manufactured by Idemitsu Kosan Co., Ltd., weight average molecular weight (Mw): 140,000) was prepared as styrene resin (referred to as "PS1" in Table 1). The raw materials listed in Table 1 were blended in the mass ratios shown in Table 1, dry-blended, and melt-kneaded using a twin-screw extruder ("PCM-30" manufactured by Ikegai Iron Works Co., Ltd., barrel temperature: 330°C, screw speed: 150 rpm). The extruder was then ejected in the form of strands through a 3 mm diameter circular nozzle (nozzle). After being immersed in a water bath at 30°C for 1.5 seconds, the strands were passed through a take-up roll at a take-up speed of 40 m/min and pelletized using a strand cutter (manufactured by Tanabe Plastics Machinery Co., Ltd.) to obtain pellets of the liquid crystal polyester composition.

The obtained liquid crystal polyester composition was evaluated for fluidity, specific gravity, dielectric properties, and fine powder production using the following methods. The results are shown in Table 1.

<Flowability Evaluation> Figure 1 is a perspective view of the mold used for thin-wall flow length measurement. The values in Figure 1 are in mm. Here, a mold with a thickness (X) of 0.3 mm, as shown in Figure 1, was used. Using the mold shown in Figure 1, a liquid crystal polyester composition was molded using an injection molding machine ("Roboshot S2000i-30B," manufactured by FANUC Corporation) under the following injection molding conditions. For the molded article removed from the mold, the length from the pouring gate to the end of the flow in the direction of resin flow (i.e., the 0.3 mmt flow length) was measured. This measurement was performed 10 times, and the average 0.3 mmt flow length was calculated. The obtained results are shown in Table 1 as "Flow Length." If the flow length is too short, it may be difficult to mold fine molded parts from the resin, which is not ideal. On the other hand, if the flow length is too long, the resin viscosity will be low, making it difficult to handle the resin during molding, which is not ideal. [Injection Molding Conditions] Cylinder Temperature: 350°C Mold Temperature: 120°C Metering Value: 20 mm Injection Speed: 200 mm/s Maximum Injection Pressure: 100 MPa Holding Pressure: 20 MPa

<Specific Gravity Measurement> Using an injection molding machine ("PNX40-5A" manufactured by Nissei Resin Industrial Co., Ltd.), ASTM No. 4 test pieces with a thickness of 2.5 mm were produced from the liquid crystal polyester composition under the following injection molding conditions. Then, using the obtained test pieces, the specific gravity of the molded test pieces was measured at 23°C using an automatic specific gravity measuring device ("ASG-320K" manufactured by Kanto Measure). [Injection Molding Conditions] Cylinder Temperature: 350°C Mold Temperature: 130°C Injection Speed: 75 mm/s Dwelling Pressure: 30 MPa

<Evaluation of Dielectric Properties> Using an injection molding machine ("PNX40-5A" manufactured by Nissei Resin Industrial Co., Ltd.), rod-shaped test pieces with a width of 64 mm, a length of 64 mm, and a thickness of 1.0 mm were produced from the liquid crystal polyester composition under the following injection molding conditions. Ten test pieces were produced using the same method. The dielectric constant and dielectric dissipation factor at 1 GHz were measured for each test piece using the following measurement conditions and method, and the average values were calculated. [Injection Molding Conditions] Cylinder Temperature: 350°C Mold Temperature: 130°C Injection Speed: 75 mm/s Dwelling Pressure: 30 MPa [Measurement Conditions and Method] Method: Capacitive Method Equipment: Impedance Analyzer (Agilent, Model "E4991A") Electrode Model: 16453A Measurement Environment: 23°C, 50% RH Applied Voltage: 500 mV

<Evaluation of Fine Powder Production> Using an injection molding machine ("PNX40-5A," manufactured by Nissei Resin Industrial Co., Ltd.), rod-shaped test pieces with a width of 12.7 mm, a length of 127 mm, and a thickness of 6.4 mm were produced from the liquid crystal polyester composition under the following injection molding conditions. The resulting test pieces were then subjected to an Izod impact test according to ASTM D256. After the impact test, the rod-shaped test piece was separated into two test pieces. The weight of the rod-shaped test piece before the test was subtracted from the combined weight of the two test pieces after the test. This value was used as the evaluation of fine powder production. [Injection Molding Conditions] Cylinder Temperature: 350°C Mold Temperature: 130°C Injection Speed: 75 mm/s Holding Pressure: 25 MPa

(Example 1-2) A liquid crystal polyester composition was produced in the same manner as in Example 1-1, except that the raw material ratios were changed as shown in Table 1. The fluidity, specific gravity, dielectric properties, and fine powder yield of the resulting liquid crystal polyester composition were evaluated in the same manner as in Example 1-1. The results are shown in Table 1.

(Comparative Example 1-1) A liquid crystal polyester composition was prepared in the same manner as in Example 1-1, except that the styrene resin was omitted and the ratio of the liquid crystal polyester to the insulating glass filler was changed as shown in Table 1. The resulting liquid crystal polyester composition was evaluated for fluidity, specific gravity, dielectric properties, and fine powder production in the same manner as in Example 1-1. The results are shown in Table 1.

[Table 1] Example 1-1 Example 1-2 Comparative example 1-1 Liquid crystal polyester LCP1 100 100 100 Inorganic fillers GB1 twenty one 18 18 Styrene resin PS1 twenty one 4 - Flow length (mm) 53 45 42 proportion 1.07 1.13 1.13 Relative dielectric constant (1 GHz) 2.64 2.69 2.72 Dielectric dissipation factor (1 GHz) 0.003 0.004 0.004 Micro powder production (mg) 3.94 24.30 38.30

(Example 2-1) (1) Preparation of Liquid Crystal Polyester (LCP2) In a reactor equipped with a stirrer, a torque meter, a nitrogen inlet tube, a thermometer, and a reflux condenser, 994.5 g (7.2 mol) of p-hydroxybenzoic acid, 446.9 g (2.4 mol) of 4,4'-dihydroxybiphenyl, 272.1 g (1.64 mol) of terephthalic acid, 126.6 g (0.76 mol) of isophthalic acid, and 1347.6 g (13.2 mol) of acetic anhydride were added. 0.2 g of 1-methylimidazole was added as a catalyst, and the inside of the reactor was fully replaced with nitrogen. Thereafter, while stirring under a nitrogen flow, the temperature was raised from room temperature to 150°C over 30 minutes, and the temperature was maintained and refluxed for 30 minutes. Next, 0.9 g of 1-methylimidazole was added, and while distilling off the by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 320°C over 2 hours and 50 minutes. After holding at 320°C for 30 minutes, the contents were removed and cooled to room temperature. The resulting solid was pulverized to a particle size of 0.1-1 mm using a grinder. Solid-state polymerization was then carried out under a nitrogen atmosphere by heating from room temperature to 250°C over 1 hour, then from 250°C to 285°C over 5 hours, and then held at 285°C for 3 hours. The solid was cooled to obtain a powdered liquid crystal polyester (LCP2). The flow onset temperature of the obtained liquid crystal polyester (LCP2) was 312°C. Furthermore, the flow initiation temperature was measured using the same method as in Example 1-1.

(2) Preparation of Liquid Crystal Polyester Composition Glass hollow spheres (iM16K, manufactured by 3M Company, average particle size (median particle size, D50): 21 μm) were prepared as a hollow glass filler (in Table 2, "GB1"). In addition, styrene resin 1 (XAREC 300ZC, manufactured by Idemitsu Kosan Co., Ltd., weight average molecular weight (Mw): 140,000) was prepared as a styrene resin (in Table 2, "PS1"). In addition, mica powder (manufactured by Yamaguchi Mica Co., Ltd., "AB-25S", average particle size 24 μm, thickness 0.45 μm) was prepared as an inorganic filler (in Table 2, " ^X1 "). Glass fiber (FDE90-01, manufactured by Central Glass Fiber Co., Ltd., with an average fiber length of 90 μm and an average fiber diameter of 6 μm) was also prepared as an inorganic filler (represented as " ^X2 " in Table 2). A liquid crystal polyester composition was prepared in the same manner as in Example 1-1, except that the raw materials listed in Table 2 were blended in the mass ratios shown in Table 2. The resulting liquid crystal polyester composition was evaluated for fluidity, specific gravity, dielectric properties, and fine powder production in the same manner as in Example 1-1. The results are shown in Table 2.

(Examples 2-2 to 2-5) Liquid crystal polyester compositions were produced in the same manner as in Example 2-1, except that the raw material ratios were modified as shown in Table 2. The resulting liquid crystal polyester compositions were evaluated for fluidity, specific gravity, dielectric properties, and fine powder production in the same manner as in Example 1-1. The results are shown in Table 2.

(Comparative Example 2-1) A liquid crystal polyester composition was prepared in the same manner as in Example 2-1, except that the styrene resin was omitted and the ratio of the liquid crystal polyester to the insulating glass filler was changed as shown in Table 3. The resulting liquid crystal polyester composition was evaluated for fluidity, specific gravity, dielectric properties, and fine powder production in the same manner as in Example 1-1. The results are shown in Table 3.

(Comparative Example 2-2) A liquid crystal polyester composition was prepared in the same manner as in Example 2-1, except that the hollow glass filler was omitted and the ratio of the liquid crystal polyester to the styrene resin was changed as shown in Table 3. The resulting liquid crystal polyester composition was evaluated for fluidity, specific gravity, dielectric properties, and fine powder production in the same manner as in Example 1-1. The results are shown in Table 3.

[Table 2] Example 2-1 Example 2-2 Example 2-3 Examples 2-4 Examples 2-5 Liquid crystal polyester LCP2 100 100 100 100 100 Inorganic fillers GB1 twenty one twenty two 16 17 17 X1 - 4 - 4 - X2 - - - - 4 Styrene resin PS1 twenty one twenty two twenty one twenty one twenty one Flow length (mm) 63 60 76 74 74 proportion 1.08 1.09 1.12 1.13 1.14 Relative dielectric constant (1 GHz) 2.63 2.67 2.71 2.72 2.72 Dielectric dissipation factor (1 GHz) 0.003 0.003 0.003 0.003 0.003 Micro powder production (mg) 3.00 0.07 0.21 0.13 0.11

[Table 3] Comparative example 2-1 Comparative example 2-2 Liquid crystal polyester LCP2 100 100 Inorganic fillers GB1 18 - X1 - - X2 - - Styrene resin PS1 - 17.65 Flow length (mm) 56 115 proportion 1.12 1.32 Relative dielectric constant (1 GHz) 2.71 3.01 Dielectric dissipation factor (1 GHz) 0.004 0.004 Micro powder production (mg) 65.00 -

Furthermore, regarding the liquid crystal polyester composition of Comparative Example 2-2, the rod-shaped test piece remained unbroken in the Izod impact test.

(Example 3-1) (1) Preparation of Liquid Crystal Polyester (LCP3) In a reactor equipped with a stirrer, a torque meter, a nitrogen inlet tube, a thermometer, and a reflux condenser, 1034.99 g (5.5 mol) of 6-hydroxy-2-naphthoic acid, 378.33 g (1.75 mol) of 2,6-naphthalenedicarboxylic acid, 83.07 g (0.5 mol) of terephthalic acid, 272.52 g (2.475 mol, 0.225 mol excess relative to the total amount of 2,6-naphthalenedicarboxylic acid and terephthalic acid), and 1226.87 g (12 mol) of acetic anhydride were added. 0.17 g of 1-methylimidazole was added as a catalyst, and the gas in the reactor was replaced with nitrogen. Thereafter, while stirring under a nitrogen flow, the reactor temperature was raised from room temperature to 140°C over 15 minutes, and refluxed at 140°C for 1 hour. While distilling off by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 145°C to 310°C over 3.5 hours. After holding at 310°C for 3 hours, the contents were removed and cooled to room temperature. The resulting solids were pulverized to a particle size of approximately 0.1-1 mm using a mill. Solid-phase polymerization was then carried out under a nitrogen atmosphere by raising the temperature from room temperature to 250°C over 1 hour, then from 250°C to 310°C over 9 hours, and then held at 310°C for 5 hours. The solid product after solid-phase polymerization was cooled to obtain a liquid crystal polyester (LCP3) in powder form. The flow onset temperature of the obtained liquid crystal polyester (LCP3) was 322°C. The flow onset temperature was measured using the same method as in Example 1-1.

(2) Preparation of liquid crystal polyester composition Glass hollow spheres (iM16K, manufactured by 3M Company, average particle size (median particle size, D50): 21 μm) were prepared as hollow glass fillers (in Table 2, "GB1"). In addition, styrene resin 1 (XAREC 300ZC, manufactured by Idemitsu Kosan Co., Ltd., weight average molecular weight (Mw): 140,000) was prepared as styrene resin (in Table 2, "PS1"). In addition, mica powder (manufactured by Yamaguchi Mica Co., Ltd., "AB-25S", average particle size 24 μm, thickness 0.45 μm) was prepared as an inorganic filler (in Table 2, "X1"). Glass fiber (FDE90-01, manufactured by Central Glass Fiber Co., Ltd., average fiber length 90 μm, average fiber diameter 6 μm) was prepared as an inorganic filler ("X2" in Table 2). A liquid crystal polyester composition was prepared in the same manner as in Example 1-1, except that the raw materials listed in Table 4 were blended in the mass ratios shown in Table 4. The resulting liquid crystal polyester composition was evaluated for fluidity, specific gravity, dielectric properties, and fine powder production in the same manner as in Example 1-1. The results are shown in Table 4.

(Examples 3-2 to 3-4) Liquid crystal polyester compositions were produced in the same manner as in Example 3-1, except that the raw material ratios were modified as shown in Table 4. The resulting liquid crystal polyester compositions were evaluated for fluidity, specific gravity, dielectric properties, and fine powder production in the same manner as in Example 1-1. The results are shown in Table 4.

(Comparative Example 3-1) A liquid crystal polyester composition was prepared in the same manner as in Example 3-1, except that the styrene resin was omitted and the ratio of the liquid crystal polyester to the insulating glass filler was changed as shown in Table 5. The resulting liquid crystal polyester composition was evaluated for fluidity, specific gravity, dielectric properties, and fine powder production in the same manner as in Example 1-1. The results are shown in Table 5.

(Comparative Example 3-2) A liquid crystal polyester composition was prepared in the same manner as in Example 3-1, except that the hollow glass filler was not added and the ratio of the liquid crystal polyester to the styrene resin was changed as shown in Table 5. The resulting liquid crystal polyester composition was evaluated for fluidity, specific gravity, dielectric properties, and fine powder production in the same manner as in Example 1-1. The results are shown in Table 5.

[Table 4] Example 3-1 Example 3-2 Example 3-3 Examples 3-4 Liquid crystal polyester LCP3 100 100 100 100 Inorganic fillers GB1 twenty one 16 17 17 X1 - - 4 - X2 - - - 4 Styrene resin PS1 twenty one twenty one twenty one twenty one Flow length (mm) 39 39 44 41 proportion 1.08 1.14 1.15 1.15 Relative dielectric constant (1 GHz) 2.67 2.71 2.72 2.74 Dielectric dissipation factor (1 GHz) 0.001 0.001 0.001 0.001 Micro powder production (mg) 0.23 0.18 0.05 0.04

[Table 5] Comparative example 3-1 Comparative example 3-2 Liquid crystal polyester LCP3 100 100 Inorganic fillers GB1 18 - X1 - - X2 - - Styrene resin PS1 - 18 Flow length (mm) 33 80 proportion 1.14 1.31 Relative dielectric constant (1 GHz) 2.76 2.93 Dielectric dissipation factor (1 GHz) 0.002 0.001 Micro powder production (mg) 91.40 -

Furthermore, regarding the liquid crystal polyester composition of Comparative Example 3-2, the rod-shaped test piece remained unbroken in the Izod impact test.

Figure 1 is a three-dimensional diagram of the mold used to measure thin-wall flow length.

Claims (11)

A liquid crystal polyester composition comprising a liquid crystal polyester, an inorganic filler containing a hollow glass filler, and a styrene resin. The liquid crystal polyester composition of claim 1, wherein the styrene resin is polystyrene. The liquid crystal polyester composition of claim 1, wherein the content of the hollow glass filler is not less than 5 parts by mass and not more than 60 parts by mass relative to 100 parts by mass of the liquid crystal polyester. The liquid crystal polyester composition of claim 1, wherein the content of the styrene resin is not less than 5 parts by mass and not more than 60 parts by mass relative to 100 parts by mass of the liquid crystal polyester. The liquid crystal polyester composition of claim 1, wherein the ratio of the content C ₂ of the styrene resin to the content C ₁ of the inorganic filler (C ₂ /C ₁ ) is 0.1 or more and 10 or less. The liquid crystal polyester composition of claim 1, wherein the inorganic filler further contains a non-hollow filler. The liquid crystal polyester composition of claim 6, wherein the content of the non-hollow filler is not less than 2 parts by mass and not more than 25 parts by mass relative to 100 parts by mass of the liquid crystal polyester. The liquid crystal polyester composition of claim 1, wherein the ratio of the hollow glass filler to the inorganic filler is not less than 50 mass % and not more than 95 mass %. A molded article comprising the liquid crystal polyester composition according to any one of claims 1 to 8. A method for producing a molded article, comprising the step of obtaining the molded article by molding the liquid crystal polyester composition according to any one of claims 1 to 8. A manufacturing method as claimed in claim 10, wherein the above-mentioned molding is injection molding.