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

Abstract

To provide a liquid crystal polyester composition that features high fluidity and a low dielectric constant and enables formation of a molded article having suppressed scattering of fine dust upon breakage.SOLUTION: A liquid crystal polyester composition comprises a liquid crystal polyester, an inorganic filler containing a hollow glass filler, and a styrene-based resin.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a liquid crystal polyester composition, a molded article, and a method for producing a molded article.

Background Art

[0002] Molded articles containing liquid crystal polyester are used in various fields, particularly in applications for electrical and electronic components, and various compositions have been studied according to the required characteristics of the molded articles. For example, Patent Document 1 discloses a composition in which a liquid crystal polyester and hollow spheres are blended as a composition for the purpose of reducing the weight of a molded article.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In recent years, for the purpose of reducing the environmental load, regrind, which reuses the end materials of molded articles such as runners and sprues during injection molding, has attracted attention.

[0005] In the composition described in Patent Document 1, there is room for improvement in that a large amount of fine powder is generated during the pulverization of the end material containing the composition, and the material loss during regrind is large.

[0006] An object of the present disclosure is to provide a liquid crystal polyester composition capable of forming a molded article having high fluidity, a low dielectric constant, and little scattering of fine powder during breakage, and a molded article containing the composition. Another object of the present disclosure is to provide a method for producing the above molded article.

Means for Solving the Problems

[0007] The present disclosure provides, for example, the following. [1] A liquid crystal polyester, an inorganic filler containing hollow glass fillers, a styrene resin, and a liquid crystal polyester composition containing the same. [2] The liquid crystal polyester composition according to [1], wherein the styrene resin is polystyrene. [3] The liquid crystal polyester composition according to [1] or [2], wherein the content of the hollow glass fillers is 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester. [4] The liquid crystal polyester composition according to any one of [1] to [3], wherein the content of the styrene resin is 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester. [5] The content C of the inorganic filler 1 and the content C of the styrene resin with respect to the same 2 The ratio (C 2 / C 1 ) is 0.1 or more and 10 or less. The liquid crystal polyester composition according to any one of [1] to [4]. [6] The liquid crystal polyester composition according to any one of [1] to [5], wherein the inorganic filler further contains non-hollow fillers. [7] The liquid crystal polyester composition according to [6], wherein the content of the non-hollow fillers is 2 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester. [8] The ratio of the hollow glass fillers in the inorganic filler is 50% by mass or more and 90% by mass or less. The liquid crystal polyester composition according to any one of [1] to [7]. [9] A molded article containing the liquid crystal polyester composition according to any one of [1] to [8].

[10] A method for manufacturing a molded article, including a step of obtaining a molded article by molding the liquid crystal polyester composition according to any one of [1] to [8].

[11] The manufacturing method according to

[10] , wherein the molding is injection molding.

Advantages of the Invention

[0008] According to the present disclosure, there are provided a liquid crystal polyester composition capable of forming a molded article having high fluidity, a low dielectric constant, and little scattering of fine powder at the time of breakage, and a molded article containing the composition. Further, according to the present disclosure, there is provided a method for manufacturing the above molded article.

Brief Description of the Drawings

[0009]

Figure 1

Modes for Carrying Out the Invention

[0010] Hereinafter, preferred embodiments of the present disclosure will be described in detail.

[0011] The liquid crystal polyester composition of the present embodiment (hereinafter, also simply referred to as "liquid crystal polyester composition" or "composition") includes a liquid crystal polyester, an inorganic filler containing a hollow glass filler, and a styrene resin.

[0012] The liquid crystal polyester composition of the present embodiment has high fluidity and a low dielectric constant. Further, the molded article formed from the liquid crystal polyester composition of the present embodiment generates little fine powder at the time of crushing, so the loss during regrinding is small.

[0013] In the present embodiment, it is considered that the dielectric constant of the composition is lowered by blending the hollow glass filler. Further, in the present embodiment, it is considered that the impact applied to the molded article at the time of crushing is alleviated and the scattering of fine powder is suppressed by blending a styrene resin having excellent toughness as compared with the liquid crystal polyester. Furthermore, in the present embodiment, it is considered that the wettability between the liquid crystal polyester and the hollow glass filler is improved and the fluidity during melting is improved by blending the styrene resin.

[0014] 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 kind of liquid crystal polyester or may contain two or more kinds.

[0015] The liquid crystal polyester has structural units (also referred to as monomer units) derived from raw material monomers. The liquid crystal polyester may have main monomer units (for example, monomer units of 90 mol% or more, 95 mol% or more, or 99 mol% or more based on the total of all monomer units, preferably all monomer units) that are monomer units derived from aromatic compounds. A liquid crystal polyester in which all monomer units are monomer units derived from aromatic compounds is also referred to as an all-aromatic liquid crystal polyester.

[0016] An aromatic compound is a compound having an aromatic ring. Aromatic compounds suitable as raw material monomers may have an aromatic ring and two or more polymerizable groups (for example, a hydroxy group, an amino group, or a carboxy group, preferably a hydroxy group or a carboxy group) bonded to the aromatic ring.

[0017] The aromatic compound may be, for example, a compound represented by the following formula (1-1) (hereinafter also referred to as aromatic compound (1-1)), a compound represented by the following formula (1-2) (hereinafter also referred to as aromatic compound (1-2)), or a compound represented by the following formula (1-3) (hereinafter also referred to as 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) [In the formula, Ar 1 , Ar 2 and Ar 3 each independently represents a phenylene group, a biphenylene group, a condensed polycyclic aromatic hydrocarbon group, or a group represented by the formula (Z-1). Ar1 and Ar 2 and Ar 3 Some or all of the hydrogen atoms possessed by may be substituted with a halogen atom, an alkyl group, or an aryl group. X 1 X 2 and X 3 each independently represents a hydroxy group or an amino group. Y 1 Y 2 and Y 3 each represents a carboxy group.] -Ar 4 -Z 1 -Ar 5 - (Z-1) [In the formula, Ar 4 and Ar 5 each independently represents 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.]

[0018] The monomer unit derived from the aromatic compound may be, for example, the monomer unit represented by the following formula (2-1) (hereinafter also referred to as monomer unit (2-1)), the structural unit represented by the following formula (2-2) (hereinafter also referred to as monomer unit (2-2)), or the structural unit represented by the following formula (2-3) (hereinafter also referred to as monomer unit (2-3)). It can be said that monomer unit (2-1) is a monomer unit derived from aromatic compound (1-1), monomer unit (2-2) is a monomer unit derived from aromatic compound (1-2), and monomer unit (2-3) is a monomer unit derived from aromatic compound (1-3). -X 11 -Ar 1 -Y 11 - (2-1) -X 12 -Ar 2 -X 13 - (2-2) -Y 12 -Ar 3 -Y 13 - (2-3) [In the formula, Ar 1 Ar2 and Ar 3 is synonymous with the above. X 11 X 12 and X 13 each independently represents an oxygen atom (-O-) or an imino group (-NH-). Y 11 Y 12 and Y 13 represents a carbonyl group (-CO-).]

[0019] The phenylene group may be, for example, a 1,4-phenylene group or a 1,3-phenylene group, and preferably a 1,4-phenylene group.

[0020] The biphenylene group may be, for example, a 4,4'-biphenylene group.

[0021] The condensed polycyclic aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from a condensed polycyclic aromatic hydrocarbon. Examples of the condensed polycyclic aromatic hydrocarbon include naphthalene, anthracene, phenanthrene, tetracene, pyrene, triphenylene, perylene, fluorene, etc. Among these, naphthalene is preferred from the viewpoints of availability and price.

[0022] 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, and preferably a 2,6-naphthylene group.

[0023] Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0024] The alkyl group as the substituent may be linear, branched, or cyclic. The alkyl group may be, for example, an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-hexyl group, a 2-ethylhexyl group, an n-octyl group, an n-decyl group, etc.

[0025] The aryl group as a substituent may be a single ring or a condensed ring. The aryl group may be, for example, an aryl group having 6 to 20 carbon atoms. Examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group. The aryl group may be a group in which a hydrogen atom of an aromatic ring is substituted with an alkyl group, such as a tolyl group.

[0026] Ar 1 , Ar 2 and Ar 3 The number of substituents that the has may be, for example, 0 to 2, may be 0 or 1, or may be 0.

[0027] Z 1 The alkanediyl group in 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 a methylene group, an ethanediyl group, a propanediyl group (e.g., a propane-2,2-diyl group), a butanediyl group, and an octanediyl group (e.g., an octane-3,3-diyl group).

[0028] X 1 , X 2 and X 3 is preferably a hydroxy group. That is, the aromatic compound (1-1) may be an aromatic hydroxycarboxylic acid, and the aromatic compound (1-2) may be an aromatic diol. The aromatic compound (1-3) may be an aromatic dicarboxylic acid.

[0029] X 11 , X 12 and X 13 is preferably an oxygen atom (—O—).

[0030] The liquid crystal polyester may be a polymer having a monomer unit (2-1), may be a polymer having a monomer unit (2-2) and a monomer unit (2-3), or may be a polymer having a monomer unit (2-1), a monomer unit (2-2) and a monomer unit (2-3).

[0031] When the liquid crystal polyester has monomer unit (2-1), monomer unit (2-2), and monomer unit (2-3), the content of monomer unit (2-1) 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 with respect to the total of all monomer units of the liquid crystal polyester. Also, when the liquid crystal polyester has monomer unit (2-1), monomer unit (2-2), and monomer unit (2-3), the content of monomer unit (2-1) may be, for example, 80% or less, 70% or less with respect to the total of all monomer units of the liquid crystal polyester. That is, when the liquid crystal polyester has monomer unit (2-1), monomer unit (2-2), and monomer unit (2-3), the content of monomer unit (2-1) may be, for example, 30 mol% or more and 80 mol% or less, 30 mol% or more and 70 mol% or less, 40 mol% or more and 80 mol% or less, 40 mol% or more and 70 mol% or less, 45 mol% or more and 80 mol% or less, 45 mol% or more and 70 mol% or less, 50 mol% or more and 80 mol% or less, 50 mol% or more and 70 mol% or less, 55 mol% or more and 80 mol% or less, or 55 mol% or more and 70 mol% or less with respect to the total of all monomer units of the liquid crystal polyester.

[0032] When the liquid crystal polyester has 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) may each be, for example, 35 mol% or less, 30 mol% or less with respect to the total of all monomer units of the liquid crystal polyester. Also, when the liquid crystal polyester has 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) may each be, for example, 5 mol% or more, 10 mol% or more, 15 mol% or more with respect to the total of all monomer units of the liquid crystal polyester. That is, when the liquid crystal polyester has 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) are each, based on the total of all monomer units of the liquid crystal polyester, for example, 5 mol% or more and 35 mol% or less, 5 mol% or more and 30 mol% or less, 10 mol% or more and 35 mol% or less, 10 mol% or more and 30 mol% or less, 15 mol% or more and 35 mol% or less, or 15 mol% or more and 30 mol% or less.

[0033] The liquid crystal polyester may have monomer units other than monomer unit (2-1), monomer unit (2-2) and monomer unit (2-3), but the number thereof may be 10 mol% or less, 5 mol% or less, 2 mol% or less or 1 mol% or less, or even 0 mol% based on the total of all monomer units of the liquid crystal polyester. That is, in the liquid crystal polyester, the total amount of monomer unit (2-1), monomer unit (2-2) and monomer unit (2-3) may be, for example, 90 mol% or more, 95 mol% or more, 99 mol% or more, or even 100 mol% based on the total of all monomer units constituting the liquid crystal polyester.

[0034] The liquid crystal polyester may be a polymer containing 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.

[0035] Examples of the condensed aromatic ring of monomer unit (A-1) include a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a pyrene ring, a triphenylene ring, a perylene ring, a fluorene ring, etc. Among these, from the viewpoints of availability and price, the naphthalene ring is preferable.

[0036] Monomer unit (A-1) is a monomer unit represented by formula (2-1) (wherein Ar 1 is a condensed polycyclic aromatic hydrocarbon group, or Ar 4 and Ar 5a group represented by formula (Z-1) in which at least one of them is a condensed polycyclic aromatic hydrocarbon group), or a monomer unit represented by formula (2-2) (wherein Ar 2 is a condensed polycyclic aromatic hydrocarbon group, or Ar 4 and Ar 5 a group represented by formula (Z-1) in which at least one of them is a condensed polycyclic aromatic hydrocarbon group), or a monomer unit represented by formula (2-3) (wherein Ar 3 is a condensed polycyclic aromatic hydrocarbon group, or Ar 4 and Ar 5 a group represented by formula (Z-1) in which at least one of them is a condensed polycyclic aromatic hydrocarbon group) may also be used.

[0037] When the liquid crystal polyester is a polymer containing the monomer unit (A-1), it is preferable that the liquid crystal polyester contains the monomer unit (A-1) as at least 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).

[0038] The monomer unit (A-1) can also be said to be 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, 2,7-naphthalenediol and the like.

[0039] 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 is a group represented by formula (Z-1) in which is a phenylene group), 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 is a group represented by formula (Z-1) in which is a phenylene group), or a monomer unit represented by formula (2-3) (wherein Ar3 is a phenylene group, a biphenylene group, or Ar 4 and Ar 5 may be a group represented by formula (Z-1) in which Ar is a phenylene group).

[0040] When the liquid crystal polyester is a polymer containing the monomer unit (A-2), the liquid crystal polyester preferably contains the monomer unit (A-2) as at least the monomer unit (2-2), and more preferably contains the monomer unit (A-2) as the monomer units (2-2) and (2-3).

[0041] The monomer unit (A-2) may be a monomer unit derived from an aromatic compound (A-2') having no condensed aromatic ring and having a benzene ring. Examples of the aromatic compound (A-2') include p-hydroxybenzoic acid, terephthalic acid, hydroquinone, isophthalic acid, 4,4'-biphenol, and the like.

[0042] When the liquid crystal polyester has the monomer unit (A-1) and the monomer unit (A-2), the content of the monomer unit (A-1) may be, for example, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more with respect to the total of all the monomer units constituting the liquid crystal polyester. When the content of the monomer unit (A-1) is large, the dielectric properties tend to be more improved. Also, the content of the monomer unit (A-1) may be, for example, 90 mol% or less, 85 mol% or less, or 80 mol% or less with respect to the total of all the monomer units constituting the liquid crystal polyester. Thereby, the moldability and processability at low temperatures tend to be good. That is, the content of the monomer unit (A-1) may be, for example, 20 mol% or more and 90 mol% or less, 20 mol% or more and 85 mol% or less, 20 mol% or more and 80 mol% or less, 30 mol% or more and 90 mol% or less, 30 mol% or more and 85 mol% or less, 30 mol% or more and 80 mol% or less, 40 mol% or more and 40 mol% or less, 40 mol% or more and 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, based on the total of all monomer units constituting the liquid crystal polyester.

[0043] When the liquid crystal polyester has the monomer unit (A-1) and the monomer unit (A-2), the content of the monomer unit (A-2) may be, for example, 10 mol% or more, 15 mol% or more, or 20 mol% or more, based on the total of all monomer units constituting the liquid crystal polyester. Also, the content of the monomer unit (A-2) 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, based on the total of all monomer units constituting the liquid crystal polyester. That is, the content of the monomer unit (A-2) may be, for example, 10 mol% or more and 80 mol% or less, 10 mol% or more and 70 mol% or less, 10 mol% or more and 60 mol% or less, 10 mol% or more and 50 mol% or less, 10 mol% or more and 40 mol% or less, 10 mol% or more and 30 mol% or less, 15 mol% or more and 80 mol% or less, 15 mol% or more and 70 mol% or less, 15 mol% or more and 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.

[0044] In the liquid crystal polyester, the total amount of the monomer unit (A-1) and the monomer unit (A-2) may be, for example, 90 mol% or more, 95 mol% or more, 99 mol% or more, or 100 mol% with respect to the total of all the monomer units constituting the liquid crystal polyester.

[0045] In this specification, the number of each monomer unit possessed by the liquid crystal polyester is determined by the analysis method described in JP-A-2000-19168. Specifically, the liquid crystal polyester is reacted with a lower alcohol in a supercritical state for depolymerization, and the depolymerization product (monomer inducing each monomer unit) is quantified by liquid chromatography, whereby the number of each monomer unit with respect to all the monomer units can be calculated.

[0046] The liquid crystal polyester can be produced by polymerizing a raw material monomer corresponding to the monomer unit constituting it. For example, it can be produced according to the method described in Japanese Patent No. 6439027.

[0047] The flow start temperature of the liquid crystal polyester may be, for example, 250°C or higher, or 270°C or higher. Also, the flow start 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 start temperature of the liquid crystal polyester may be, for example, 250°C or higher and 400°C or lower, 250°C or higher and 360°C or lower, 250°C or higher and 340°C or lower, 270°C or higher and 400°C or lower, 270°C or higher and 360°C or lower, or 270°C or higher and 340°C or lower.

[0048] In this specification, the flow start temperature of the liquid crystal polyester is measured using a flow tester, and the liquid crystal polyester is melted while raising the temperature at a rate of 4°C / min under a load of 9.8 MPa (100 kg / cm 2 )), and the molten liquid crystal polyester is extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm, and it is the temperature at which the viscosity shows 4800 Pa·s (48000 poise).

[0049] The dielectric tangent of the liquid crystal polyester at 10 GHz may be, for example, 0.006 or less, preferably 0.004 or less, and more preferably 0.002 or less. Thereby, a composition having a preferable dielectric tangent described later can be easily obtained.

[0050] The relative permittivity of the liquid crystal polyester at 10 GHz may be, for example, 4.0 or less, and may also be 3.8 or less. Further, the relative permittivity of the liquid crystal polyester at 10 GHz may be, for example, 2.8 or more, and may also be 3.0 or more.

[0051] In this specification, the dielectric tangent and relative permittivity of the liquid crystal polyester at 10 GHz are measured by the following method. Using an injection molding machine (manufactured by FANUC Corporation, ROBOSHOT S-2000i 30B), under the conditions of a cylinder temperature of 330 ° C, a mold temperature of 130 ° C, and an injection speed of 100 mm / s, using pellets of liquid crystal polyester as a molding material, a test piece having a width of 50 mm, a length of 50 mm, and a thickness of 0.5 mm is obtained. For the obtained test piece, the relative permittivity and dielectric tangent at 10 GHz are measured using a vector network analyzer (manufactured by Keysight Technologies, Inc., N5290A) and a split cylinder resonator (manufactured by EM Lab Co., Ltd., CR710). The measurement environment shall be 23 ° C and 50% RH.

[0052] The liquid crystal polyester composition of this embodiment contains at least hollow glass filler as an inorganic filler.

[0053] The hollow glass filler is a glass filler containing an air layer inside, and can also be referred to as hollow glass beads or glass balloons.

[0054] The average particle diameter (median diameter, D50) of the hollow glass filler may be, for example, 5 μm or more, and may also be 8 μm or more, 10 μm or more, or 15 μm or more. Further, the average particle diameter (median diameter, D50) of the hollow glass filler may be, for example, 80 μm or less, and may also be 50 μm or less, 35 μm or less, or 25 μm or less.

[0055] The content of the hollow glass filler may be, for example, 5 parts by mass or more relative to 100 parts by mass of the liquid crystal polyester, and from the viewpoint of easily obtaining a lower dielectric constant, it may be 7 parts by mass or more, 10 parts by mass or more, or 15 parts by mass or more. The content of the hollow glass filler may be, for example, 60 parts by mass or less relative to 100 parts by mass of the liquid crystal polyester, and from the viewpoint of easily obtaining higher fluidity and easily obtaining a molded product in which the generation of fine powder at the time of breakage is further suppressed, it may be 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 hollow glass filler may be, for example, 5 parts by mass or more and 60 parts by mass or less, 5 parts by mass or more and 50 parts by mass or less, 5 parts by mass or more and 40 parts by mass or less, 5 parts by mass or more and 30 parts by mass or less, 5 parts by mass or more and 25 parts by mass or less, 7 parts by mass or more and 60 parts by mass or less, 7 parts by mass or more and 50 parts by mass or less, 7 parts by mass or more and 40 parts by mass or less, 7 parts by mass or more and 30 parts by mass or less, 7 parts by mass or more and 25 parts by mass or less, 10 parts by mass or more and 60 parts by mass or less, 10 parts by mass or more and 50 parts by mass or less, 10 parts by mass or more and 40 parts by mass or less, 10 parts by mass or more and 30 parts by mass or less, 10 parts by mass or more and 25 parts by mass or less, 15 parts by mass or more and 60 parts by mass or less, 15 parts by mass or more and 50 parts by mass or less, 15 parts by mass or more and 40 parts by mass or less, 15 parts by mass or more and 30 parts by mass or less, or 15 parts by mass or more and 25 parts by mass or less.

[0056] The proportion of the hollow glass filler in the inorganic filler may be, for example, 50% by mass or more, and from the viewpoint of obtaining the above-mentioned effects more significantly, it may be 60% by mass or more, 70% by mass or more, 75% by mass or more, or it may be 100% by mass.

[0057] The inorganic filler may further contain 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 containing a non-hollow filler as the inorganic filler, the generation of fine powder during crushing tends to be more significantly suppressed.

[0058] Inorganic fillers other than the hollow glass filler may be fibrous fillers, plate-like fillers, or granular fillers.

[0059] Examples of the fibrous filler include glass fiber; carbon fibers such as PAN-based carbon fiber and pitch-based carbon fiber; ceramic fibers such as silica fiber, alumina fiber, and silica alumina fiber; and metal fibers such as stainless steel fiber. Further, whiskers such as potassium titanate whisker, barium titanate whisker, wollastonite whisker, aluminum borate whisker, silicon nitride whisker, and silicon carbide whisker are also included.

[0060] Examples of the plate-like filler include talc, mica, graphite, wollastonite, glass flake, barium sulfate, and calcium carbonate. Mica may be muscovite, phlogopite, fluorophlogopite, or tetrasilicate mica.

[0061] Examples of the granular filler include silica, alumina, titanium oxide, glass beads, boron nitride, silicon carbide, and calcium carbonate.

[0062] The content of the non-hollow filler may be, for example, 1 part by mass or more with respect to 100 parts by mass of the liquid crystal polyester. From the viewpoint of obtaining the above-described effects more remarkably, it may be 2 parts by mass or more, 3 parts by mass or more, or 4 parts by mass or more. Further, the content of the non-hollow filler may be, for example, 25 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester, and may be 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 may be, for example, 1 part by mass or more and 25 parts by mass or less, 1 part by mass or more and 20 parts by mass or less, 1 part by mass or more and 15 parts by mass or less, 1 part by mass or more and 10 parts by mass or less, 1 part by mass or more and 5 parts by mass or less, 2 parts by mass or more and 25 parts by mass or less, 2 parts by mass or more and 20 parts by mass or less, 2 parts by mass or more and 15 parts by mass or less, 2 parts by mass or more and 10 parts by mass or less, 2 parts by mass or more and 5 parts by mass or less, 3 parts by mass or more and 25 parts by mass or less, 3 parts by mass or more and 20 parts by mass or less, 3 parts by mass or more and 15 parts by mass or less, 3 parts by mass or more and 10 parts by mass or less, 3 parts by mass or more and 5 parts by mass or less, 4 parts by mass or more and 25 parts by mass or less, 4 parts by mass or more and 20 parts by mass or less, 4 parts by mass or more and 15 parts by mass or less, 4 parts by mass or more and 10 parts by mass or less, or 4 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester.

[0063] The content of the inorganic filler 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 with respect to 100 parts by mass of the liquid crystal polyester. Also, the content of the inorganic filler 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 with respect to 100 parts by mass of the liquid crystal polyester. That is, the content of the inorganic filler may be, for example, 5 parts by mass or more and 60 parts by mass or less, 5 parts by mass or more and 50 parts by mass or less, 5 parts by mass or more and 40 parts by mass or less, 5 parts by mass or more and 30 parts by mass or less, 5 parts by mass or more and 25 parts by mass or less, 7 parts by mass or more and 60 parts by mass or less, 7 parts by mass or more and 50 parts by mass or less, 7 parts by mass or more and 40 parts by mass or less, 7 parts by mass or more and 30 parts by mass or less, 7 parts by mass or more and 25 parts by mass or less, 10 parts by mass or more and 60 parts by mass or less, 10 parts by mass or more and 50 parts by mass or less, 10 parts by mass or more and 40 parts by mass or less, 10 parts by mass or more and 30 parts by mass or less, 10 parts by mass or more and 25 parts by mass or less, 15 parts by mass or more and 60 parts by mass or less, 15 parts by mass or more and 50 parts by mass or less, 15 parts by mass or more and 40 parts by mass or less, 15 parts by mass or more and 30 parts by mass or less, or 15 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester.

[0064] The styrene resin is a polymer having monomer units derived from styrene.

[0065] The styrenic resin may have monomer units derived from monomers other than styrene. Examples of monomers other than styrene include acrylonitrile, butadiene, ethylene, and the like.

[0066] The styrenic resin may be, for example, polystyrene, modified polystyrene, etc., and polystyrene is preferred from the viewpoint of more significantly obtaining the above-described effects.

[0067] The polystyrene may be isotactic polystyrene, syndiotactic polystyrene, or atactic polystyrene.

[0068] The dielectric loss tangent of the styrenic resin at 10 GHz may be, for example, 0.001 or less, and may also be 0.0008 or less.

[0069] Also, the relative permittivity of the styrenic resin at 10 GHz may be, for example, 3 or less, and may also be 2.6 or less. Also, the relative permittivity of the styrenic resin at 10 GHz may be, for example, 2 or more, and may also be 2.2 or more.

[0070] In this specification, the dielectric loss tangent and relative permittivity of the styrenic resin at 10 GHz are measured by the following method. Using an injection molding machine (manufactured by FANUC Corporation, ROBOSHOT S-2000i 30B), under the conditions of a cylinder temperature of 290 °C (Zarec 300ZC), 300 °C (Zarec 90ZC), a mold temperature of 130 °C, and an injection speed of 100 mm / s, with pellets of the styrenic resin as the molding material, a test piece with a width of 50 mm, a length of 50 mm, and a thickness of 0.5 mm is obtained. The cylinder temperature is set to a temperature at which the resin to be measured is sufficiently plasticized and the decomposition of the resin does not proceed significantly. For the obtained test piece, using a vector network analyzer (manufactured by Keysight Technologies, Inc., N5290A) and a split cylinder resonator (manufactured by EM Lab Co., Ltd., CR710), the relative permittivity and dielectric loss tangent at 10 GHz are measured. The measurement environment is 23 °C and 50% RH.

[0071] The number average molecular weight (Mn) of the styrene resin may be, for example, 10,000 or more, and may also be 20,000 or more, 30,000 or more, or 40,000 or more. Further, the number average molecular weight (Mn) of the styrene resin may be, for example, 200,000 or less, and may also be 150,000 or less, 130,000 or less, or 100,000 or less.

[0072] The weight average molecular weight (Mw) of the styrene resin may be, for example, 20,000 or more, and may also be 40,000 or more, 60,000 or more, or 80,000 or more. Further, the weight average molecular weight (Mw) of the styrene resin may be, for example, 400,000 or less, and may also be 300,000 or less, 250,000 or less, or 200,000 or less.

[0073] The molecular weight distribution (Mw / Mn) of the styrene resin may be, for example, 1.3 or more, and may also be 1.6 or more, 1.8 or more, or 2 or more. Further, the molecular weight distribution (Mw / Mn) of the styrene resin may be, for example, 8 or less, and may also be 7 or less, 6 or less, or 5 or less.

[0074] In this specification, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the styrene resin indicate the values measured by gel permeation chromatography at 135 °C using 1,2,4-trichlorobenzene as a solvent.

[0075] The content of the styrene resin may be, for example, 5 parts by mass or more with respect to 100 parts by mass of the liquid crystal polyester. From the viewpoints of easily obtaining higher fluidity and easily obtaining a molded product in which the generation of fine powder at the time of breakage is more suppressed, it may also be 7 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more. Further, the content of the styrene resin may be, for example, 60 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester, and may also be 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 resin may be, for example, 5 parts by mass or more and 60 parts by mass or less, 5 parts by mass or more and 50 parts by mass or less, 5 parts by mass or more and 40 parts by mass or less, 5 parts by mass or more and 30 parts by mass or less, 5 parts by mass or more and 25 parts by mass or less, 7 parts by mass or more and 60 parts by mass or less, 7 parts by mass or more and 50 parts by mass or less, 7 parts by mass or more and 40 parts by mass or less, 7 parts by mass or more and 30 parts by mass or less, 7 parts by mass or more and 25 parts by mass or less, 10 parts by mass or more and 60 parts by mass or less, 10 parts by mass or more and 50 parts by mass or less, 10 parts by mass or more and 40 parts by mass or less, 10 parts by mass or more and 30 parts by mass or less, 10 parts by mass or more and 25 parts by mass or less, 15 parts by mass or more and 60 parts by mass or less, 15 parts by mass or more and 50 parts by mass or less, 15 parts by mass or more and 40 parts by mass or less, 15 parts by mass or more and 30 parts by mass or less, 15 parts by mass or more and 25 parts by mass or less, 20 parts by mass or more and 60 parts by mass or less, 20 parts by mass or more and 50 parts by mass or less, 20 parts by mass or more and 40 parts by mass or less, 20 parts by mass or more and 30 parts by mass or less, or 20 parts by mass or more and 25 parts by mass or less, based on 100 parts by mass of the liquid crystal polyester.

[0076] Content C of the inorganic filler 1 Content C of the styrene resin relative to 2 Ratio (C 2 / C 1 )(mass ratio) may be, for example, 0.10 or more, and from the viewpoint of obtaining the above effects more significantly, it may be 0.12 or more, 0.14 or more, or 0.20 or more. Further, the content C 1 of the styrene resin relative to the content C 2 of the hollow glass filler 2 Ratio (C 1 / C

[0077] 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, and may be 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 100% by mass.

[0078] The liquid crystal polyester composition may further contain components other than the liquid crystal polyester, the inorganic filler, and the styrene-based resin.

[0079] For example, the liquid crystal polyester composition may contain one or more resins other than the liquid crystal polyester and the styrene-based resin. Examples of the resin include polyolefin, cyclic polyolefin, polyvinyl chloride, polysulfone, (meth)acrylic resin, polyphenylene ether resin, polyacetal resin, polyamide resin, imide resin, cellulose resin, polyether ether ketone resin, fluororesin, polycarbonate resin, thermosetting resin, and the like.

[0080] 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, an ultraviolet absorber, an antistatic agent, a surfactant, a lubricant, a mold release agent, and the like.

[0081] The dielectric tangent 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.

[0082] The relative dielectric constant of the liquid crystal polyester composition at 1 GHz may be, for example, 3.4 or less, or may be 2.8 or less. Also, the relative dielectric constant of the liquid crystal polyester composition at 1 GHz may be, for example, 2.3 or more, or may be 2.7 or more.

[0083] The dielectric tangent and relative dielectric constant of the liquid crystal polyester composition are measured by the method described in the examples.

[0084] 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. Also, the specific gravity of the liquid crystal polyester composition may be, for example, 1.05 or more, or may be 1.10 or more.

[0085] The specific gravity of the liquid crystal polyester composition is measured by the method described in the examples.

[0086] Since the liquid crystal polyester composition of this embodiment is excellent in fluidity during melting, it can be suitably used as a molding material. The liquid crystal polyester composition may be used, for example, as pellets.

[0087] The molded article of this embodiment contains the above-described liquid crystal polyester composition. The molded article of this embodiment is, for example, a connector, socket, relay part, coil bobbin, optical pickup, oscillator, semiconductor package, IC tray, wafer carrier, household electric appliance part, lighting fixture part, audio product part, ferrule for optical cable, telephone part, facsimile part, modem part, separating claw, heater holder, impeller, fan gear, gear, bearing, motor part, motor case, engine part, engine room interior part, electrical component, automobile interior part, microwave cooking pot, heat-resistant tableware, floor material, wall material, beam, column, roofing material, aircraft part, spacecraft part, space equipment part, atomic reactor, marine facility member, cleaning jig, optical instrument part, valves, pipes, nozzles, filters, membranes, medical device parts, medical materials, sensor parts, sanitary fixtures, sports goods, or leisure goods.

[0088] The molded article of this embodiment can be obtained, for example, by molding the above-described liquid crystal polyester composition into a desired shape and performing a processing treatment as necessary.

[0089] As a molding method of the molded article, melt molding is preferable. Examples of melt molding include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, press molding, etc., and injection molding is preferably used.

[0090] As described above, the preferred embodiments of the present disclosure have been described, but the present disclosure is not limited to the above embodiments.

Examples

[0091] Hereinafter, examples are shown to more specifically explain the invention according to the present disclosure. However, the invention according to the present disclosure is not limited by these examples. Hereinafter, % and parts representing content or usage amount are based on mass unless otherwise specified.

[0092] (Example 1-1) (1) Production of liquid crystal polyester (LCP1) Into a reactor equipped with a stirrer, a torque meter, a nitrogen gas introduction 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 charged. 0.2 g of 1-methylimidazole was added as a catalyst, and the inside of the reactor was thoroughly replaced with nitrogen gas. Then, while stirring under a nitrogen gas stream, the temperature was raised from room temperature to 150°C over 30 minutes, and the temperature was maintained at the same temperature and refluxed for 30 minutes. Next, 0.9 g of 1-methylimidazole was added, and while distilling off by-produced acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 320°C over 2 hours and 50 minutes, and after holding at 320°C for 30 minutes, the content was taken out and cooled to room temperature. The obtained solid was pulverized to a particle size of 0.1 to 1 mm with a pulverizer, and then the temperature was raised from room temperature to 250°C over 1 hour under a nitrogen atmosphere, the temperature was raised from 250°C to 285°C over 5 hours, and held at 285°C for 3 hours to perform solid-phase polymerization. The solid after solid-phase polymerization was cooled to obtain a powdery liquid crystal polyester (LCP1). The flow start temperature of the obtained liquid crystal polyester (LCP1) was 327°C. The flow start temperature was measured by the following method.

[0093] <Measurement of flow start temperature> Using a flow tester (manufactured by Shimadzu Corporation, model "CFT-500EX"), approximately 2 g of liquid crystal polyester was filled into a cylinder equipped with a die having a nozzle with an inner diameter of 1 mm and a length of 10 mm. While raising the temperature at a rate of 4 °C / min under a load of 9.8 MPa, the liquid crystal polyester was melted, extruded from the nozzle, and the temperature at which the viscosity was 4800 Pa·s was measured, which was taken as the flow start temperature of the liquid crystal polyester.

[0094] (2) Production of liquid crystal polyester composition As the hollow glass filler, glass balloons (iM16K, manufactured by 3M Company, average particle size (median diameter, D50): 21 μm) were prepared (designated as "GB1" in Table 1). Also, as the styrene resin, styrene resin 1 (XAREC 300ZC, manufactured by Idemitsu Kosan Co., Ltd., weight average molecular weight (Mw): 140,000) was prepared (designated as "PS1" in Table 1). Each raw material shown in Table 1 was blended at the mass ratio shown in Table 1 and dry blended, and then melt-kneaded with a twin-screw extruder (manufactured by Ikegai Tekko Kabushiki Kaisha, model "PCM-30", cylinder temperature: 330 °C, screw rotation speed: 150 rpm), extruded in a strand shape through a circular nozzle (discharge port) with a diameter of 3 mm, passed through a water bath at a water temperature of 30 °C for 1.5 seconds, and then pelletized with a strand cutter (manufactured by Tanabe Plastic Machinery Co., Ltd.) through a take-up roller with a take-up speed of 40 m / min to obtain pellets of the liquid crystal polyester composition.

[0095] Regarding the obtained liquid crystal polyester composition, the fluidity, specific gravity, dielectric properties, and the amount of fine powder generation were evaluated by the following methods. The results are shown in Table 1.

[0096] <Evaluation of fluidity> Figure 1 is a perspective view showing a mold for measuring the thin-wall flow length. The unit of the numerical values in Figure 1 is mm. Here, the mold with a thickness (X) of 0.3 mm shown in Figure 1 was used. Using the mold shown in Fig. 1, a liquid crystal polyester composition was molded on an injection molding machine (manufactured by Fanuc Corporation, "Roboshot S2000i-30B") under the following injection molding conditions. For the molded article taken out of the mold, the length from the gate to the flow end in the resin flow direction (i.e., the 0.3 mm t flow length) was measured. This measurement was performed 10 times, and the average value of the 0.3 mm t flow length was calculated. The obtained results were shown in Table 1 as "flow length". If the flow length is too short, it may be difficult to mold a fine molded article with resin, which is not preferable. On the other hand, if the flow length is too long, the viscosity of the resin is small, and it may be difficult to handle the resin during molding, which is not preferable. [Injection Molding Conditions] Cylinder Temperature: 350 °C Mold Temperature: 120 °C Measured Value: 20 mm Injection Speed: 200 mm / second Maximum Injection Pressure: 100 MPa Holding Pressure: 20 MPa

[0097] [Measurement of Specific Gravity] Using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., "PNX40-5A"), an ASTM No. 4 test piece with a thickness of 2.5 mm was produced from the liquid crystal polyester composition under the following injection molding conditions. Next, using the obtained test piece and an automatic specific gravity measuring device (manufactured by Kanto Major Co., Ltd., "ASG-320K"), the specific gravity of the molded test piece was measured under the condition of 23 °C. [Injection Molding Conditions] Cylinder Temperature: 350 °C Mold Temperature: 130 °C Injection Speed: 75 mm / second Holding Pressure: 30 MPa

[0098] [Evaluation of Dielectric Properties] Using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., "PNX40-5A"), a rod-shaped test piece with a width of 64 mm, a length of 64 mm, and a thickness of 1.0 mm was produced from the liquid crystal polyester composition under the following injection molding conditions. Ten test pieces were prepared in the same manner, and for each test piece, the dielectric constant and dielectric tangent at 1 GHz were measured under the following measurement conditions and measurement methods, and the average value was obtained. [Injection molding conditions] Cylinder temperature: 350 °C Mold temperature: 130 °C Injection speed: 75 mm / second Holding pressure: 30 MPa [Measurement conditions and measurement methods] Measurement method: Capacitance method Equipment: Impedance analyzer (manufactured by Agilent, model "E4991A") Electrode type: 16453A Measurement environment: 23 °C, 50% RH Applied voltage: 500 mV

[0099] [Evaluation of the amount of fine powder generated] Using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., "PNX40-5A"), 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. Next, using the obtained test pieces, an Izod impact test was conducted according to ASTM D256. After the impact test, the rod-shaped test piece was separated into two test pieces. The weight obtained by subtracting the total weight of the two test pieces after the test from the weight of the rod-shaped test piece before the test was measured, and the measured value was evaluated as the amount of fine powder generated. [Injection molding conditions] Cylinder temperature: 350 °C Mold temperature: 130 °C Injection speed: 75 mm / second Holding pressure: 25 MPa

[0100] (Example 1-2) Except for changing the blending ratio of each raw material as shown in Table 1, the liquid crystal polyester composition was produced in the same manner as in Example 1-1. For the obtained liquid crystal polyester composition, the fluidity, specific gravity, dielectric properties, and evaluation of the amount of fine powder generated were carried out in the same manner as in Example 1-1. The results are shown in Table 1.

[0101] (Comparative Example 1-1) The production of the liquid crystal polyester composition was carried out in the same manner as in Example 1-1, except that the blending ratios of the liquid crystal polyester and the hollow glass filler were changed as shown in Table 1 without blending the styrene resin. For the obtained liquid crystal polyester composition, the fluidity, specific gravity, dielectric properties, and the amount of fine powder generation were evaluated in the same manner as in Example 1-1. The results are shown in Table 1.

[0102]

Table 1

[0103] (Example 2-1) (1) Production of liquid crystal polyester (LCP2) Into a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and 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 charged. 0.2 g of 1-methylimidazole was added as a catalyst, and the inside of the reactor was thoroughly purged with nitrogen gas. Then, while stirring under a nitrogen gas stream, the temperature was raised from room temperature to 150°C over 30 minutes and maintained at the same temperature for 30 minutes for reflux. Next, 0.9 g of 1-methylimidazole was added, and while distilling off the by-produced acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 320°C over 2 hours and 50 minutes and maintained at 320°C for 30 minutes. Then, the content was taken out and cooled to room temperature. The obtained solid was pulverized to a particle size of 0.1 to 1 mm with a pulverizer, and then the temperature was raised from room temperature to 250°C over 1 hour under a nitrogen atmosphere, the temperature was raised from 250°C to 285°C over 5 hours, and solid-phase polymerization was carried out by maintaining at 285°C for 3 hours. The solid after solid-phase polymerization was cooled to obtain a powdery liquid crystal polyester (LCP2). The flow start temperature of the obtained liquid crystal polyester (LCP2) was 312°C. The flow start temperature was measured by the same method as in Example 1-1.

[0104] (2) Production of Liquid Crystal Polyester Composition As the hollow glass filler, glass balloons (iM16K, manufactured by 3M Company, average particle size (median diameter, D50): 21 μm) were prepared (designated as "GB1" in Table 2). Also, as the styrene resin, styrene resin 1 (XAREC 300ZC, manufactured by Idemitsu Kosan Co., Ltd., weight average molecular weight (Mw): 140,000) was prepared (designated as "PS1" in Table 2). Further, as the inorganic filler, mica powder (manufactured by Yamaguchi Mica Co., Ltd., "AB-25S", average particle size 24 μm, thickness 0.45 μm) was prepared (designated as "X1" in Table 2). Also, as the inorganic filler, glass fiber (manufactured by Central Glass Fiber Co., Ltd., "FDE90-01", average fiber length 90 μm, average fiber diameter 6 μm) was prepared (designated as "X2" in Table 2). The production of the liquid crystal polyester composition was carried out in the same manner as in Example 1-1, except that the respective raw materials shown in Table 2 were blended at the mass ratios shown in Table 2. For the obtained liquid crystal polyester composition, the evaluation of fluidity, specific gravity, dielectric properties, and the amount of fine powder generation was carried out in the same manner as in Example 1-1. The results are shown in Table 2.

[0105] (Examples 2-2 to 2-5) The production of the liquid crystal polyester composition was carried out in the same manner as in Example 2-1, except that the blending ratio of each raw material was changed as shown in Table 2. For the obtained liquid crystal polyester composition, the evaluation of fluidity, specific gravity, dielectric properties, and the amount of fine powder generation was carried out in the same manner as in Example 1-1. The results are shown in Table 2.

[0106] (Comparative Example 2-1) The production of the liquid crystal polyester composition was carried out in the same manner as in Example 2-1, except that the styrene resin was not blended and the blending ratio of the liquid crystal polyester and the hollow glass filler was changed as shown in Table 3. For the obtained liquid crystal polyester composition, the evaluation of fluidity, specific gravity, dielectric properties, and the amount of fine powder generation was carried out in the same manner as in Example 1-1. The results are shown in Table 3.

[0107] (Comparative Example 2-2) A liquid crystal polyester composition was produced in the same manner as in Example 2-1, except that the hollow glass filler was not compounded and the compounding ratios of the liquid crystal polyester and the styrene resin were changed as shown in Table 3. For the obtained liquid crystal polyester composition, the fluidity, specific gravity, dielectric properties, and the amount of fine powder generated were evaluated in the same manner as in Example 1-1. The results are shown in Table 3.

[0108] [Table 2]

[0109] [Table 3]

[0110] Note that the liquid crystal polyester composition of Comparative Example 2-2 was in a state where the bar-shaped test piece was not broken in the Izod impact test.

[0111] (Example 3-1) (1) Production of Liquid Crystal Polyester (LCP3) Into a reactor equipped with a stirrer, a torque meter, a nitrogen gas 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 in excess with respect to the total amount of 2,6-naphthalenedicarboxylic acid and terephthalic acid) of hydroquinone, and 1226.87 g (12 mol) of acetic anhydride were charged, 0.17 g of 1-methylimidazole was added as a catalyst, and the gas in the reactor was replaced with nitrogen gas. Then, while stirring under a nitrogen gas stream, the temperature inside the reactor was raised from room temperature to 140 °C over 15 minutes and refluxed at 140 °C for 1 hour. Next, while distilling off the by-produced acetic acid and the unreacted acetic anhydride, the temperature was raised from 145 °C to 310 °C over 3.5 hours, held at 310 °C for 3 hours, and then the content was taken out and cooled to room temperature. The obtained solid was pulverized with a pulverizer to a particle size of about 0.1 to 1 mm, and then heated from room temperature to 250°C over 1 hour under a nitrogen atmosphere, heated from 250°C to 310°C over 9 hours, and held at 310°C for 5 hours to carry out solid-phase polymerization. The solid after solid-phase polymerization was cooled to obtain a powdery liquid crystal polyester (LCP3). The flow start temperature of the obtained liquid crystal polyester (LCP3) was 322°C. The flow start temperature was measured by the same method as in Example 1-1.

[0112] (2) Production of liquid crystal polyester composition As the hollow glass filler, glass balloons (iM16K, manufactured by 3M Company, average particle size (median diameter, D50): 21 μm) were prepared (designated as "GB1" in Table 2). Also, as the styrene resin, styrene resin 1 (XAREC 300ZC, manufactured by Idemitsu Kosan Co., Ltd., weight average molecular weight (Mw): 140,000) was prepared (designated as "PS1" in Table 2). Further, as the inorganic filler, mica powder (manufactured by Yamaguchi Mica Co., Ltd., "AB-25S", average particle size 24 μm, thickness 0.45 μm) was prepared (designated as "X1" in Table 2). Also, as the inorganic filler, glass fiber (manufactured by Central Glass Fiber Co., Ltd., "FDE90-01", average fiber length 90 μm, average fiber diameter 6 μm) was prepared (designated as "X2" in Table 2). A liquid crystal polyester composition was produced in the same manner as in Example 1-1 except that the respective raw materials shown in Table 4 were blended at the mass ratios shown in Table 4. For the obtained liquid crystal polyester composition, the fluidity, specific gravity, dielectric properties, and the amount of fine powder generation were evaluated in the same manner as in Example 1-1. The results are shown in Table 4.

[0113] (Examples 3-2 to 3-4) A liquid crystal polyester composition was produced in the same manner as in Example 3-1 except that the blending ratio of each raw material was changed as shown in Table 4. For the obtained liquid crystal polyester composition, the fluidity, specific gravity, dielectric properties, and the amount of fine powder generation were evaluated in the same manner as in Example 1-1. The results are shown in Table 4.

[0114] (Comparative Example 3-1) A liquid crystal polyester composition was produced in the same manner as in Example 3-1, except that the blending ratios of the liquid crystal polyester and the hollow glass filler were changed as shown in Table 5 without blending a styrene resin. For the obtained liquid crystal polyester composition, the fluidity, specific gravity, dielectric properties, and the amount of fine powder generation were evaluated in the same manner as in Example 1-1. The results are shown in Table 5.

[0115] (Comparative Example 3-2) A liquid crystal polyester composition was produced in the same manner as in Example 3-1, except that the blending ratios of the liquid crystal polyester and the styrene resin were changed as shown in Table 5 without blending a hollow glass filler. For the obtained liquid crystal polyester composition, the fluidity, specific gravity, dielectric properties, and the amount of fine powder generation were evaluated in the same manner as in Example 1-1. The results are shown in Table 5.

[0116] [Table 4]

[0117] [Table 5]

[0118] Note that the liquid crystal polyester composition of Comparative Example 3-2 was in a state where the bar-shaped test piece was not broken in the Izod impact test.

Claims

1. A liquid crystal polyester, an inorganic filler containing hollow glass fillers, a styrene resin, and a liquid crystal polyester composition containing the same.

2. The liquid crystal polyester composition according to Claim 1, wherein the styrene resin is polystyrene.

3. The liquid crystal polyester composition according to Claim 1, wherein the content of the hollow glass fillers is 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester.

4. The liquid crystal polyester composition according to Claim 1, wherein the content of the styrene resin is 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester.

5. The content C of the inorganic filler １ to the content C of the styrene resin ２ ratio (C ２ / C １ ) is 0.1 or more and 10 or less, The liquid crystal polyester composition according to claim 1

6. The liquid crystal polyester composition according to Claim 1, wherein the inorganic filler further contains non-hollow fillers.

7. The liquid crystal polyester composition according to Claim 6, wherein the content of the non-hollow fillers is 2 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester.

8. The liquid crystal polyester composition according to Claim 1, wherein the ratio of the hollow glass fillers in the inorganic filler is 50% by mass or more and 95% by mass or less.

9. A molded article containing the liquid crystal polyester composition according to any one of Claims 1 to 8.

10. A method for manufacturing a molded article, including a step of obtaining a molded article by molding the liquid crystal polyester composition according to any one of Claims 1 to 8.

11. The manufacturing method according to Claim 10, wherein the molding is injection molding.

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