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

Abstract

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

Description

Technical Field

[0001] This disclosure relates to liquid crystal polyester compositions, molded articles, and methods for manufacturing molded articles. Background Technology

[0002] Molded articles containing liquid crystal polyester are used in various fields, especially in electrical and electronic components, and various compositions corresponding to the required characteristics of the molded articles have been studied. For example, in Patent Document 1, a composition combining liquid crystal polyester and hollow spheres is disclosed as a composition for the purpose of lightweighting the molded article.

[0003] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2004-323705 Summary of the Invention

[0004] The problem that the invention aims to solve In recent years, in order to reduce the environmental impact, the re-grinding of end materials of injection-molded products, such as runners and sprues, has received attention.

[0005] Regarding the composition described in Patent Document 1, there is room for improvement in the large amount of fine powder generated during the crushing of the end material containing the composition and the large material loss during regrinding.

[0006] The purpose of this disclosure is to provide a liquid crystal polyester composition and a molded article comprising the composition, which have high fluidity and low dielectric constant and can form a molded article with minimal powder dispersion upon breakage. Furthermore, another purpose of this disclosure is to provide a method for manufacturing the aforementioned molded article.

[0007] Methods for solving problems This disclosure provides, for example, the following.

[0008] [1] A liquid crystal polyester composition, comprising: Liquid crystal polyester, Inorganic fillers containing hollow glass fillers, and Styrene-based resins.

[0009] [2] According to the liquid crystal polyester composition of [1], wherein, The styrene-based resin mentioned above is polystyrene.

[0010] [3] The liquid crystal polyester composition according to [1] or [2], wherein, The content of the above-mentioned insulating glass filler is 5 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the above-mentioned liquid crystal polyester.

[0011] [4] The liquid crystal polyester composition according to any one of [1] to [3], wherein, The content of the styrene-based resin is 5 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the liquid crystal polyester.

[0012] [5] The liquid crystal polyester composition according to any one of [1] to [4], wherein, The ratio (C2 / C1) of the content of the styrene-based resin C2 to the content of the inorganic filler C1 is 0.1 or more and 10 or less.

[0013] [6] The liquid crystal polyester composition according to any one of [1] to [5], wherein, The aforementioned inorganic packing material further includes non-hollow packing material.

[0014] [7] The liquid crystal polyester composition according to [6], wherein, The content of the aforementioned non-hollow filler is 2 parts by mass and 25 parts by mass relative to 100 parts by mass of the aforementioned liquid crystal polyester.

[0015] [8] The liquid crystal polyester composition according to any one of [1] to [7], wherein, The proportion of the above-mentioned hollow glass filler in the above-mentioned inorganic filler is more than 50% by mass and less than 90% by mass.

[0016] [9] A molded article, It comprises any one of the liquid crystal polyester compositions described in [1] to [8].

[0017]

[10] A method for manufacturing a molded article, It includes a process of obtaining a molded article by molding the liquid crystal polyester composition described in any one of [1] to [8].

[0018]

[11] According to the manufacturing method described in

[10] , wherein, The above molding process is injection molding.

[0019] Invention Effects According to this disclosure, a liquid crystal polyester composition having high fluidity and low dielectric constant, and capable of forming molded articles with minimal powder scattering upon breakage, and a molded article comprising the composition, are provided. Furthermore, according to this disclosure, a method for manufacturing the aforementioned molded article is provided. Attached Figure Description

[0020] Figure 1 This is a three-dimensional diagram of a mold used for measuring the flow length of thin-walled materials. Detailed Implementation

[0021] The preferred embodiments of this disclosure will now be described in detail.

[0022] The liquid crystal polyester composition of this embodiment (hereinafter also simply referred to as "liquid crystal polyester composition" or "composition") comprises liquid crystal polyester, an inorganic filler containing hollow glass filler, and a styrene-based resin.

[0023] The liquid crystal polyester composition of this embodiment has high fluidity and low dielectric constant. Furthermore, the molded articles formed from the liquid crystal polyester composition of this embodiment produce less fine powder during breakage, resulting in less loss during regrinding.

[0024] In this embodiment, it is believed that the dielectric constant of the composition is reduced by incorporating hollow glass filler. Furthermore, in this embodiment, it is believed that by incorporating a styrene-based resin, which exhibits superior toughness compared to liquid crystal polyester, the impact on the molded article during breakage is mitigated, and the dispersion of microparticles is suppressed. Moreover, in this embodiment, it is believed that by incorporating a styrene-based resin, the wettability of the liquid crystal polyester and the hollow glass filler is improved, and the fluidity during melting is enhanced.

[0025] Liquid crystal polyesters are any polyesters that exhibit liquid crystal properties in the molten state. A liquid crystal polyester composition may contain only one type of liquid crystal polyester, or it may contain two or more types.

[0026] Liquid crystal polyesters have constituent units derived from raw material monomers (also called monomer units). Liquid crystal polyesters may also have monomer units whose main monomer units (e.g., monomer units whose total percentage relative to all monomer units is 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably all monomer units) are derived from aromatic compounds. Liquid crystal polyesters in which all monomer units are derived from aromatic compounds are also called fully aromatic liquid crystal polyesters.

[0027] Aromatic compounds are compounds having an aromatic ring. Preferred aromatic compounds as raw material 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.

[0028] Aromatic compounds can be, for example, compounds represented by the following formula (1-1) (hereinafter also referred to as aromatic compound (1-1)), compounds represented by the following formula (1-2) (hereinafter also referred to as aromatic compound (1-2)), or compounds represented by the following formula (1-3) (hereinafter also referred to as aromatic compound (1-3)).

[0029] 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 can be independently represented as a phenylene group, a biphenylene group, a fused polycyclic aromatic hydrocarbon group, or a group represented by formula (Z-1). Ar 1 Ar 2 and Ar 3 Some or all of the hydrogen atoms may be replaced by halogen atoms, alkyl groups, or aryl groups. X 1 X 2 and X 3 Each can be represented independently as either hydroxyl or amino. Y 1 Y 2 and Y 3 This indicates a carboxyl group. -Ar 4 -Z 1 -Ar 5 - (Z-1) [In the formula, Ar] 4 and Ar 5 Each can be used independently to represent either a phenylene group or a fused polycyclic aromatic hydrocarbon group. Z 1 This represents an oxygen atom (-O-), a sulfur atom (-S-), a carbonyl group (-CO-), a sulfonyl group (-SO2-), or an alkane dimethyl group. The monomeric unit derived from the aromatic compound can be, for example, the monomeric unit represented by the following formula (2-1) (hereinafter also referred to as monomeric unit (2-1))., the constituent unit represented by the following formula (2-2) (hereinafter also referred to as monomeric unit (2-2))., or the constituent unit represented by the following formula (2-3) (hereinafter also referred to as monomeric unit (2-3)). It should be noted that monomeric unit (2-1) can be said to be a monomeric unit derived from aromatic compound (1-1), monomeric unit (2-2) can be a monomeric unit derived from aromatic compound (1-2), and monomeric unit (2-3) can be a monomeric unit derived from aromatic compound (1-3).

[0030] -X 11 -Ar 1 -Y 11 - (2-1) -X 12 -Ar 2 -X 13 - (2-2) -Y 12 -Ar3 -Y 13 - (2-3) [In the formula, Ar] 1 Ar 2 and Ar 3 Same meaning as above. X 11 X 12 and X 13 Each can be represented independently as either an oxygen atom (-O-) or an imino atom (-NH-). Y 11 Y 12 and Y 13 This represents a carbonyl group (-CO-). The phenylene oxide can be, for example, 1,4-phenylene oxide or 1,3-phenylene oxide, preferably 1,4-phenylene oxide.

[0031] For example, a 4,4'-biphenylene oxide can be used.

[0032] A fused polycyclic aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from a fused polycyclic aromatic hydrocarbon. Examples of fused polycyclic aromatic hydrocarbons include naphthalene, anthracene, phenanthrene, butane, pyrene, tribenzobenzene, perylene, and fluorene. Among these, naphthalene is preferred from the viewpoint of availability and price.

[0033] The fused polycyclic aromatic hydrocarbon group can be naphthylene. The naphthylene group can be, for example, 2,6-naphthylene or 2,7-naphthylene, preferably 2,6-naphthylene.

[0034] Halogen atoms that can be used as substituents include fluorine, chlorine, bromine, and iodine.

[0035] The alkyl group used as a substituent can be straight-chain, branched, or cyclic. For example, the alkyl group can be an alkyl group having 1 to 10 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, n-octyl, and n-decyl.

[0036] The aryl group used as a substituent can be monocyclic or fused-ring. For example, aryl groups can have 6 to 20 carbon atoms. Examples of aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, and 2-naphthyl. Aryl groups can also be groups obtained by substituting the hydrogen atoms of the aromatic ring with alkyl groups, such as tolyl.

[0037] Ar 1 Ar 2 and Ar 3 The number of substituents can be, for example, 0 to 2, or 0 or 1, or even 0.

[0038] Z 1The alkane dimethyl group can be straight-chain or branched. The alkane dimethyl group can be an alkane dimethyl group with 1 to 10 carbon atoms. Examples of alkane dimethyl groups include methylene, ethane dimethyl, propane dimethyl (e.g., propane-2,2-dimethyl), butane dimethyl, octane dimethyl (e.g., octane-3,3-dimethyl), etc.

[0039] X 1 X 2 and X 3 Preferably, the hydroxyl group is used. That is, aromatic compound (1-1) can be an aromatic hydroxycarboxylic acid, and aromatic compound (1-2) can be an aromatic diol. It should be noted that aromatic compound (1-3) can be an aromatic dicarboxylic acid.

[0040] X 11 X 12 and X 13 Oxygen atoms (-O-) are preferred.

[0041] The liquid crystal polyester can be a polymer having monomer unit (2-1), a polymer having monomer unit (2-2) and monomer unit (2-3), or a polymer having monomer unit (2-1), monomer unit (2-2) and monomer unit (2-3).

[0042] When the liquid crystal polyester has monomer units (2-1), monomer units (2-2), and monomer units (2-3), the content of monomer unit (2-1) relative to the total of all monomer units in the liquid crystal polyester can, for example, be 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 has monomer units (2-1), monomer units (2-2), and monomer units (2-3), the content of monomer unit (2-1) relative to the total of all monomer units in the liquid crystal polyester can, for example, be 80% or less, or 70% or less.

[0043] That is, when the liquid crystal polyester has monomer units (2-1), monomer units (2-2), and monomer units (2-3), the content of monomer unit (2-1) relative to the total of all monomer units of the liquid crystal polyester can 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 70 mol% or less, 55 mol% or more and 80 mol% or less, or 55 mol% or more and 70 mol% or less.

[0044] When the liquid crystal polyester has monomer units (2-1), monomer units (2-2), and monomer units (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 of the liquid crystal polyester can, for example, be 35 mol% or less, or 30 mol% or less. Furthermore, when the liquid crystal polyester has monomer units (2-1), monomer units (2-2), and monomer units (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 of the liquid crystal polyester can, for example, be 5 mol% or more, 10 mol% or more, or 15 mol% or more.

[0045] That is, when the liquid crystal polyester has monomer units (2-1), monomer units (2-2), and monomer units (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 of the liquid crystal polyester can be, 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.

[0046] Liquid crystal polyesters may also have monomer units other than monomer units (2-1), monomer units (2-2), and monomer units (2-3), but their number relative to the total number of monomer units in the liquid crystal polyester may be less than 10 mol%, less than 5 mol%, less than 2 mol%, less than 1 mol%, or even 0 mol%. That is, in the liquid crystal polyester, the total amount of monomer units (2-1), monomer units (2-2), and monomer units (2-3) relative to the total number of monomer units constituting the liquid crystal polyester may, for example, be more than 90 mol%, more than 95 mol%, more than 99 mol%, or even 100 mol%.

[0047] Liquid crystal polyester can also be a polymer comprising monomer units (A-1) having fused aromatic rings and monomer units (A-2) having benzene rings but not fused aromatic rings.

[0048] The fused aromatic rings possessed by the monomer unit (A-1) can be naphthalene ring, anthracene ring, phenanthrene ring, butane ring, pyrene ring, tribenzobenzene ring, perylene ring, fluorene ring, etc. Among them, naphthalene ring is preferred from the viewpoint of availability and price.

[0049] The single-unit element (A-1) can also be the single-unit element represented by equation (2-1) (where Ar... 1 It is a fused polycyclic aromatic hydrocarbon group, or Ar 4 and Ar 5At least one of them is a group represented by formula (Z-1) of a fused polycyclic aromatic hydrocarbon group, or it can be a monomer unit represented by formula (2-2) (where Ar 2 It is a fused polycyclic aromatic hydrocarbon group, or Ar 4 and Ar 5 At least one of them is a group represented by formula (Z-1) of a fused polycyclic aromatic hydrocarbon group, or it can be a monomer unit represented by formula (2-3) (where Ar 3 It is a fused polycyclic aromatic hydrocarbon group, or Ar 4 and Ar 5 At least one of them is a group represented by formula (Z-1) of a fused polycyclic aromatic hydrocarbon group.

[0050] When the liquid crystal polyester is a polymer containing monomer units (A-1), the liquid crystal polyester preferably contains at least monomer units (A-1) as monomer units (2-1), and more preferably contains monomer units (A-1) as monomer units (2-1) and monomer units (2-3).

[0051] The monomer unit (A-1) can also be referred to as the monomer unit derived from an aromatic compound (A-1') having a fused aromatic ring. Examples of aromatic compounds (A-1') include 2-hydroxy-6-naphthoic acid, 2,6-naphthoic acid, 2,6-dihydroxynaphthoic acid, 2-hydroxy-3-naphthoic acid, 1-hydroxy-5-naphthoic acid, and 2,7-naphthodiol.

[0052] The single-unit element (A-2) can also be the single-unit element represented by equation (2-1) (where Ar... 1 It is phenylene, biphenylene, or Ar 4 and Ar 5 (The group represented by formula (Z-1) of the phenylene group) can also be a monomer unit represented by formula (2-2) (where Ar) 2 It is phenylene, biphenylene, or Ar 4 and Ar 5 (The group represented by formula (Z-1) of the phenylene group) can also be a monomer unit represented by formula (2-3) (where Ar) 3 It is phenylene, biphenylene, or Ar 4 and Ar 5 (The group represented by formula (Z-1) of the phenylene group).

[0053] When the liquid crystal polyester is a polymer containing monomer unit (A-2), the liquid crystal polyester preferably contains at least monomer unit (A-2) as monomer unit (2-2), and more preferably contains monomer unit (A-2) as monomer unit (2-2) and monomer unit (2-3).

[0054] The monomer unit (A-2) can be derived from an aromatic compound (A-2') that does not have a fused aromatic ring but has a benzene ring. Examples of aromatic compounds (A-2') include p-hydroxybenzoic acid, terephthalic acid, hydroquinone, isophthalic acid, and 4,4'-biphenol.

[0055] When the liquid crystal polyester has monomer units (A-1) and monomer units (A-2), the content of monomer units (A-1) relative to the total number of monomer units constituting the liquid crystal polyester can, for example, be 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. A higher content of monomer units (A-1) tends to result in improved dielectric properties. Furthermore, the content of monomer units (A-1) relative to the total number of monomer units constituting the liquid crystal polyester can, for example, be 90 mol% or less, 85 mol% or less, or 80 mol% or less. This tends to improve moldability and processability at low temperatures.

[0056] That is, the content of monomer unit (A-1) relative to the total of all monomer units constituting the liquid crystal polyester can 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 90 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 more, 60 mol% or more and 80 mol% or less, 70 mol% or more and 90 mol% or more, 70 mol% or more and 85 mol% or less, or 70 mol% or more and 80 mol% or less.

[0057] When the liquid crystal polyester has monomer units (A-1) and monomer units (A-2), the content of monomer units (A-2) relative to the total number of monomer units constituting the liquid crystal polyester can, for example, be 10 mol% or more, 15 mol% or more, or 20 mol% or more. Furthermore, the content of monomer units (A-2) relative to the total number of monomer units constituting the liquid crystal polyester can, for example, be 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.

[0058] 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.

[0059] In liquid crystal polyester, the total amount of monomer units (A-1) and monomer units (A-2) relative to the total amount 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%.

[0060] In this specification, the number of each monomer unit in the liquid crystal polyester is determined using the analytical method described in Japanese Patent Application Publication No. 2000-19168. Specifically, the liquid crystal polyester is depolymerized by reacting it with a lower alcohol in a supercritical state, and the depolymerization products (monomers from which each monomer unit is derived) are quantified by liquid chromatography, thereby allowing the calculation of the number of each monomer unit relative to all monomer units.

[0061] Liquid crystal polyesters can be manufactured by polymerizing raw material monomers corresponding to the monomer units constituting them. For example, they can be manufactured according to the method described in Japanese Patent No. 6439027.

[0062] The flow initiation temperature of the liquid crystal polyester can be, for example, above 250°C or above 270°C. Furthermore, the flow initiation temperature of the liquid crystal polyester can be, for example, below 400°C, below 360°C, or below 340°C.

[0063] That is, the flow start temperature of the liquid crystal polyester can be, for example, above 250°C and below 400°C, above 250°C and below 360°C, above 250°C and below 340°C, above 270°C and below 400°C, above 270°C and below 360°C, or above 270°C and below 340°C.

[0064] In this specification, the flow initiation temperature of the liquid crystal polyester was determined using a flow tester, with one side of the liquid crystal polyester subjected to a flow test at 9.8 MPa (100 kg / cm²).2 Under load, the liquid crystal polyester is heated at a rate of 4℃ / min to melt it, and then extruded from a nozzle with an inner diameter of 1mm and a length of 10mm to a temperature at which its viscosity shows 4800Pa·s (48000 poise).

[0065] The dielectric loss tangent 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. Therefore, it becomes easy to obtain a composition having the preferred dielectric loss tangent described later.

[0066] The relative permittivity of the liquid crystal polyester at 10 GHz can be, for example, 4.0 or less, or 3.8 or less. Alternatively, the relative permittivity of the liquid crystal polyester at 10 GHz can be, for example, 2.8 or more, or 3.0 or more.

[0067] In this specification, the dielectric loss tangent and relative permittivity of the liquid crystal polyester at 10 GHz are determined by the following method.

[0068] Using an injection molding machine (FANUC, ROBOSHOT S-2000i30B), with a barrel temperature of 330°C, a mold temperature of 130°C, and an injection speed of 100 mm / s, liquid crystal polyester granules were used as the molding material to obtain test pieces with a width of 50 mm, a length of 50 mm, and a thickness of 0.5 mm. For the obtained test pieces, the relative permittivity and dielectric loss tangent at 10 GHz were measured using a vector network analyzer (Keysight Technologies, N5290A) and a split cylindrical resonator (EM labs, CR710). It should be noted that the measurement environment was set at 23°C and 50% RH.

[0069] The liquid crystal polyester composition of this embodiment contains at least hollow glass filler as an inorganic filler.

[0070] Insulating glass filler is a glass filler that contains an air layer inside; it can also be called insulated glass beads or glass balloons.

[0071] The average particle size (median particle size, D50) of the insulating glass filler can be, for example, 5 μm or more, or 8 μm or more, 10 μm or more, or 15 μm or more. In addition, the average particle size (median particle size, D50) of the insulating glass filler can be, for example, 80 μm or less, or 50 μm or less, 35 μm or less, or 25 μm or less.

[0072] The content of the insulating glass filler relative to 100 parts by weight of liquid crystal polyester can be, for example, 5 parts by weight or more. From the viewpoint of easily obtaining a lower dielectric constant, it can also be 7 parts by weight or more, 10 parts by weight or more, or 15 parts by weight or more. Furthermore, the content of the insulating glass filler relative to 100 parts by weight of liquid crystal polyester can be, for example, 60 parts by weight or less. From the viewpoint of easily obtaining higher flowability and easily obtaining molded articles that better suppress the generation of micropowder upon breakage, it can also be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less.

[0073] That is, the content of the insulating glass filler relative to 100 parts by weight of liquid crystal polyester can be, for example, 5 parts by weight or more and 60 parts by weight, 5 parts by weight or more and 50 parts by weight, 5 parts by weight or more and 40 parts by weight, 5 parts by weight or more and 30 parts by weight, 5 parts by weight or more and 25 parts by weight, 7 parts by weight or more and 60 parts by weight, 7 parts by weight or more and 50 parts by weight, 7 parts by weight or more and 40 parts by weight, 7 parts by weight or more and 30 parts by weight, or 7 parts by weight or more and 30 parts by weight. More than 25 parts by weight or less, 10 parts by weight or more but less than 60 parts by weight, 10 parts by weight or more but less than 50 parts by weight, 10 parts by weight or more but less than 40 parts by weight, 10 parts by weight or more but less than 30 parts by weight, 10 parts by weight or more but less than 25 parts by weight, 15 parts by weight or more but less than 60 parts by weight, 15 parts by weight or more but less than 50 parts by weight, 15 parts by weight or more but less than 40 parts by weight, 15 parts by weight or more but less than 30 parts by weight, or 15 parts by weight or more but less than 25 parts by weight.

[0074] The proportion of the insulating glass filler in the inorganic filler can be, for example, 50% by mass or more. From the viewpoint of obtaining the above-mentioned effect more significantly, it can also be 60% by mass or more, 70% by mass or more, 75% by mass or more, or 100% by mass.

[0075] Inorganic fillers can further include inorganic fillers other than hollow glass fillers. These inorganic fillers, other than hollow glass fillers, can be non-hollow fillers. By further including non-hollow fillers as inorganic fillers, there is a tendency to more significantly suppress the generation of fine powder during crushing.

[0076] Inorganic fillers other than those used in hollow glass can be fibrous fillers, plate-shaped fillers, or granular fillers.

[0077] Examples of fibrous fillers include glass fibers; polyacrylonitrile (PAN) carbon fibers, pitch-based carbon fibers, and other carbon fibers; ceramic fibers such as silica fibers, alumina fibers, and silica-alumina fibers; and metal fibers such as stainless steel fibers. Additionally, examples include potassium titanate whiskers, barium titanate whiskers, wollastonite whiskers, aluminum borate whiskers, silicon nitride whiskers, and silicon carbide whiskers.

[0078] Examples of plate-shaped fillers include talc, mica, graphite, wollastonite, glass flakes, barium sulfate, and calcium carbonate. Mica can be muscovite, phlogopite, fluorophlogopite, or tetrasilica.

[0079] Examples of granular fillers include silica, alumina, titanium dioxide, glass beads, boron nitride, silicon carbide, and calcium carbonate.

[0080] The content of non-hollow filler relative to 100 parts by weight of liquid crystal polyester can, for example, be 1 part by weight or more, and from the viewpoint of obtaining the above-mentioned effect more significantly, it can also be 2 parts by weight or more, 3 parts by weight or more, or 4 parts by weight or more. Furthermore, the content of non-hollow filler relative to 100 parts by weight of liquid crystal polyester can, for example, be 25 parts by weight or less, or 20 parts by weight or less, 15 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0081] That is, the content of non-hollow filler relative to 100 parts by weight of liquid crystal polyester can be, for example, 1 part by weight or more and 25 parts by weight, 1 part by weight or more and 20 parts by weight, 1 part by weight or more and 15 parts by weight, 1 part by weight or more and 10 parts by weight, 1 part by weight or more and 5 parts by weight, 2 parts by weight or more and 25 parts by weight, 2 parts by weight or more and 20 parts by weight, 2 parts by weight or more and 15 parts by weight, 2 parts by weight or more and 10 parts by weight, 2 parts by weight or more and 5 parts by weight, 3 parts by weight or more and 25 parts by weight, 3 parts by weight or more and 20 parts by weight, 3 parts by weight or more and 15 parts by weight, 3 parts by weight or more and 10 parts by weight, 3 parts by weight or more and 5 parts by weight, 4 parts by weight or more and 25 parts by weight, 4 parts by weight or more and 20 parts by weight, 4 parts by weight or more and 15 parts by weight, 4 parts by weight or more and 10 parts by weight, or 4 parts by weight or more and 5 parts by weight.

[0082] The content of inorganic filler relative to 100 parts by weight of liquid crystal polyester can be, for example, 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, or 15 parts by weight or more. Furthermore, the content of inorganic filler relative to 100 parts by weight of liquid crystal polyester can be, for example, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less.

[0083] That is, the content of inorganic filler relative to 100 parts by weight of liquid crystal polyester can be, for example, 5 parts by weight or more and 60 parts by weight, 5 parts by weight or more and 50 parts by weight, 5 parts by weight or more and 40 parts by weight, 5 parts by weight or more and 30 parts by weight, 5 parts by weight or more and 25 parts by weight, 7 parts by weight or more and 60 parts by weight, 7 parts by weight or more and 50 parts by weight, 7 parts by weight or more and 40 parts by weight, 7 parts by weight or more and 30 parts by weight, or 7 parts by weight or more. And 25 parts by weight or less, 10 parts by weight or more but less than 60 parts by weight, 10 parts by weight or more but less than 50 parts by weight, 10 parts by weight or more but less than 40 parts by weight, 10 parts by weight or more but less than 30 parts by weight, 10 parts by weight or more but less than 25 parts by weight, 15 parts by weight or more but less than 60 parts by weight, 15 parts by weight or more but less than 50 parts by weight, 15 parts by weight or more but less than 40 parts by weight, 15 parts by weight or more but less than 30 parts by weight, or 15 parts by weight or more but less than 25 parts by weight.

[0084] Styrene-based resins are polymers containing monomer units derived from styrene.

[0085] Styrene-based resins can also contain monomer units derived from monomers other than styrene. Examples of monomers other than styrene include acrylonitrile, butadiene, and ethylene.

[0086] Styrene-based resins can be, for example, polystyrene, modified polystyrene, etc., and polystyrene is preferred from the viewpoint of obtaining the above-mentioned effects more significantly.

[0087] Polystyrene can be isotactic polystyrene, syndiotactic polystyrene, or atactic polystyrene.

[0088] The dielectric loss tangent of styrene-based resins at 10 GHz can be, for example, below 0.001 or below 0.0008.

[0089] Furthermore, the relative permittivity of styrene-based resins at 10 GHz can be, for example, 3 or less, or 2.6 or less. Conversely, the relative permittivity of styrene-based resins at 10 GHz can be, for example, 2 or more, or 2.2 or more.

[0090] In this specification, the dielectric loss tangent and relative permittivity of styrene-based resins at 10 GHz are determined by the following method.

[0091] Using an injection molding machine (FANUC, ROBOSHOT S-2000i30B), with barrel temperatures of 290°C (XAREC 300ZC) and 300°C (XAREC 90ZC), a mold temperature of 130°C, and an injection speed of 100 mm / s, styrene-based resin granules were used as the molding material to obtain test pieces with a width of 50 mm, a length of 50 mm, and a thickness of 0.5 mm. The barrel temperature was set to a temperature at which the resin being measured was sufficiently plasticized and resin decomposition did not progress significantly. For the obtained test pieces, the relative permittivity and dielectric loss tangent at 10 GHz were measured using a vector network analyzer (Keysight Technologies, N5290A) and a split cylindrical resonator (EM labs, CR710). It should be noted that the measurement environment was set at 23°C and 50% RH.

[0092] The number average molecular weight (Mn) of styrene-based resins can be, for example, 10,000 or more, or 20,000 or more, 30,000 or more, or 40,000 or more. Alternatively, the number average molecular weight (Mn) of styrene-based resins can be, for example, 200,000 or less, or 150,000 or less, 130,000 or less, or 100,000 or less.

[0093] The weight-average molecular weight (Mw) of styrene-based resins can be, for example, 20,000 or more, or 40,000 or more, 60,000 or more, or 80,000 or more. Alternatively, the weight-average molecular weight (Mw) of styrene-based resins can be, for example, 400,000 or less, or 300,000 or less, 250,000 or less, or 200,000 or less.

[0094] The molecular weight distribution (Mw / Mn) of styrene-based resins can be, for example, 1.3 or more, or 1.6 or more, 1.8 or more, or 2 or more. Furthermore, the molecular weight distribution (Mw / Mn) of styrene-based resins can be, for example, 8 or less, or 7 or less, 6 or less, or 5 or less.

[0095] In this specification, the number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of styrene-based resins are expressed as values ​​determined by gel permeation chromatography at 135°C using 1,2,4-trichlorobenzene as a solvent.

[0096] The content of styrene-based resin relative to 100 parts by weight of liquid crystal polyester can be, for example, 5 parts by weight or more. From the viewpoint of easily obtaining higher flowability and easier obtaining molded articles with more suppressed powder generation during breakage, it can also be 7 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more. Furthermore, the content of styrene-based resin relative to 100 parts by weight of liquid crystal polyester can be, for example, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less.

[0097] That is, the content of styrene-based resin relative to 100 parts by weight of liquid crystal polyester can be, for example, 5 parts by weight or more and 60 parts by weight or less, 5 parts by weight or more and 50 parts by weight or less, 5 parts by weight or more and 40 parts by weight or less, 5 parts by weight or more and 30 parts by weight or less, 5 parts by weight or more and 25 parts by weight or less, 7 parts by weight or more and 60 parts by weight or less, 7 parts by weight or more and 50 parts by weight or less, 7 parts by weight or more and 40 parts by weight or less, 7 parts by weight or more and 30 parts by weight or less, 7 parts by weight or more and 25 parts by weight or less, 10 parts by weight or more and 60 parts by weight or less, 10 parts by weight or more and 50 parts by weight or less. Below, 10 parts by weight and 40 parts by weight, 10 parts by weight and 30 parts by weight, 10 parts by weight and 25 parts by weight, 15 parts by weight and 60 parts by weight, 15 parts by weight and 50 parts by weight, 15 parts by weight and 40 parts by weight, 15 parts by weight and 30 parts by weight, 15 parts by weight and 25 parts by weight, 20 parts by weight and 60 parts by weight, 20 parts by weight and 50 parts by weight, 20 parts by weight and 40 parts by weight, 20 parts by weight and 30 parts by weight, or 20 parts by weight and 25 parts by weight.

[0098] The ratio (C2 / C1) of the styrene-based resin content to the inorganic filler content (C1) (mass ratio) can be, for example, 0.10 or more. From the viewpoint of obtaining the above-mentioned effect more significantly, it can also be 0.12 or more, 0.14 or more, or 0.20 or more. Furthermore, the ratio (C2 / C1) of the styrene-based resin content to the inorganic filler content (C1) (mass ratio) can be, for example, 10.0 or less. From the viewpoint of obtaining the above-mentioned effect more significantly, it can also be 8.0 or less, 7.0 or less, or 5.0 or less.

[0099] In the liquid crystal polyester composition, the total amount of liquid crystal polyester, inorganic filler and styrene resin can be, for example, 80% by mass or more, or 85% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, or 99% by mass or more, or 100% by mass.

[0100] The liquid crystal polyester composition may further contain liquid crystal polyester, inorganic fillers, and other components other than styrene-based resins.

[0101] For example, the liquid crystal polyester composition may contain one or more liquid crystal polyesters and resins other than styrene-based resins. 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, fluoropolymers, polycarbonate resins, and thermosetting resins.

[0102] In addition, the liquid crystal polyester composition may further include colorants, dispersants, plasticizers, antioxidants, curing agents, flame retardants, heat stabilizers, ultraviolet absorbers, antistatic agents, surfactants, lubricants, release agents, etc.

[0103] The dielectric loss tangent of the liquid crystal polyester composition at 1 GHz can be, for example, 0.004 or less, preferably 0.003 or less, and more preferably 0.001 or less.

[0104] The relative permittivity of the liquid crystal polyester composition at 1 GHz can be, for example, 3.4 or less, or 2.8 or less. Furthermore, the relative permittivity of the liquid crystal polyester composition at 1 GHz can be, for example, 2.3 or more, or 2.7 or more.

[0105] The dielectric loss tangent and relative permittivity of the liquid crystal polyester composition were determined by the methods described in the examples.

[0106] The specific gravity of the liquid crystal polyester composition can 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 can be, for example, 1.05 or more, or 1.10 or more.

[0107] The specific gravity of the liquid crystal polyester composition was determined by the method described in the examples.

[0108] The liquid crystal polyester composition of this embodiment has excellent flowability upon melting, and therefore can be suitably used as a molding material. For example, the liquid crystal polyester composition can be used as granules.

[0109] The molded articles of this embodiment include the liquid crystal polyester composition described above. Examples of the molded articles of this embodiment include connectors, sockets, relay components, coil frames, optical pickups, oscillators, semiconductor packages, IC trays, wafer carriers, household appliance components, lighting fixture components, audio product components, optical cable clamps, telephone components, fax components, modem components, release claws, heater brackets, impellers, fan gears, gears, bearings, motor components, motor housings, engine components, engine compartment components, electrical components, automotive interior components, microwave cooking pots, heat-resistant tableware, flooring materials, wall materials, beams, columns, roofing materials, aircraft components, spacecraft components, aerospace equipment components, nuclear reactors, marine facility components, washing fixtures, optical equipment components, valves, pipes, nozzles, filters, membranes, medical equipment components, medical materials, sensor components, hygiene supplies, sporting goods, or leisure goods.

[0110] The molded article of this embodiment can be obtained, for example, by molding the above-described liquid crystal polyester composition into the desired shape and performing processing as needed.

[0111] As a molding method for molded articles, melt molding is preferred. Examples of melt molding include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, and compression molding, with injection molding being preferred.

[0112] The preferred embodiments of this disclosure have been described above, but this disclosure is not limited to the above embodiments.

[0113] Example The invention disclosed herein is described in more detail below with reference to embodiments, but the invention is not limited to these examples. Hereinafter, percentages and parts of content or usage are used as mass references unless otherwise specified.

[0114] (Example 1-1) (1) Manufacturing of liquid crystal polyester (LCP1) In a reactor equipped with a stirrer, torque meter, nitrogen inlet pipe, thermometer, and reflux cooler, 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, along with 0.2 g of 1-methylimidazole as a catalyst. The reactor was then completely purged with nitrogen. Subsequently, while stirring under a nitrogen flow, the temperature was increased from room temperature to 150°C over 30 minutes, maintained at this temperature, and refluxed for 30 minutes.

[0115] 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 increased from 150°C to 320°C over 2 hours and 50 minutes. After maintaining the temperature at 320°C for 30 minutes, the contents were removed and cooled to room temperature.

[0116] The obtained solid was pulverized to a particle size of 0.1-1 mm using a pulverizer, and then heated from room temperature to 250°C in a nitrogen atmosphere for 1 hour, and from 250°C to 285°C in 5 hours, and held at 285°C for 3 hours to carry out solid-phase polymerization.

[0117] The solid product after solid-state polymerization was cooled to obtain powdered liquid crystal polyester (LCP1). The flow onset temperature of the obtained liquid crystal polyester (LCP1) was 327°C. It should be noted that the flow onset temperature was determined by the following method.

[0118] <Determination of Flow Onset Temperature> Using a flow tester (Shimadzu Corporation, "CFT-500EX type"), approximately 2g of liquid crystal polyester was filled into a barrel equipped with a nozzle having an inner diameter of 1mm and a length of 10mm. While heating at a rate of 4°C / min under a load of 9.8MPa, the liquid crystal polyester was melted and extruded from the nozzle. The temperature at which the viscosity was measured to be 4800Pa·s was taken as the flow start temperature of the liquid crystal polyester.

[0119] (2) Manufacturing of liquid crystal polyester composition As a filler for insulating glass, glass balloons (iM16K, manufactured by 3M Corporation, average particle size (median particle size, D50): 21 μm) were prepared (denoted as "GB1" in Table 1). Furthermore, as a styrene-based resin, styrene-based resin 1 (XAREC 300ZC, manufactured by Idemitsu Kosan Co., Ltd., weight-average molecular weight (Mw): 140,000) was prepared (denoted as "PS1" in Table 1).

[0120] The raw materials shown in Table 1 are combined in the mass ratios shown in Table 1, and then dry-blended. The mixture is then melt-blended using a twin-screw extruder (manufactured by Ikegai Iron Works Co., Ltd., "PCM-30", barrel temperature: 330°C, screw speed: 150 rpm). The mixture is then extruded as a filament through a 3 mm diameter circular nozzle (extrusion outlet), passes through a water bath at 30°C for 1.5 seconds, and is then granulated using a wire cutter (manufactured by Tanabe Plastics Machinery Co., Ltd.) via a take-up roller at a take-up speed of 40 m / min to obtain granules of the liquid crystal polyester composition.

[0121] The obtained liquid crystal polyester composition was evaluated for its flowability, specific gravity, dielectric properties, and micronization by the following methods. The results are shown in Table 1.

[0122] <Liquidity Assessment> Figure 1 This is a three-dimensional diagram of a mold used for measuring the flow length of thin-walled materials. Figure 1 The units for the values ​​in the text are mm. Here, we use... Figure 1 The mold shown has a thickness (X) of 0.3 mm.

[0123] use Figure 1 The mold shown is used to mold the liquid crystal polyester composition using an injection molding machine (FANUC Corporation, "Roboshot S2000i-30B") under the following injection molding conditions. For the molded body removed from the mold, the length from the gate to the end of the resin flow direction (i.e., 0.3 mmt flow length) is measured.

[0124] The measurement was performed 10 times, and the average flow length of 0.3 mmt was calculated. The results are shown in Table 1 as “flow length”. If the flow length is too short, it may become difficult to mold fine parts using resin, which is not preferable. On the other hand, if the flow length is too long, the resin viscosity is low, and it may become difficult to handle the resin during molding, which is also not preferable.

[0125] [Injection Molding Conditions] Barrel temperature: 350℃ Mold temperature: 120℃ Measurement value: 20mm Injection speed: 200 mm / s Maximum injection pressure: 100 MPa Pressure holding: 20MPa <Specific Gravity Measurement> Using an injection molding machine (Nissei Resin Kogyo Co., Ltd., “PNX40-5A”), ASTM No. 4 test pieces with a thickness of 2.5 mm were produced from a liquid crystal polyester composition under the following injection molding conditions.

[0126] Next, using the obtained test piece, the specific gravity of the formed test piece was measured at 23°C using an automatic specific gravity measuring device (Kanto Measure, "ASG-320K").

[0127] [Injection Molding Conditions] Barrel temperature: 350℃ Mold temperature: 130℃ Injection speed: 75 mm / s Pressure holding: 30MPa Evaluation of dielectric properties Using an injection molding machine (manufactured by Nissei Resin Kogyo Co., Ltd., "PNX40-5A"), 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.

[0128] Ten test pieces were prepared using the same method. The dielectric constant and dielectric loss tangent at 1 GHz were measured for each test piece under the following conditions and methods, and the average value was calculated.

[0129] [Injection Molding Conditions] Barrel temperature: 350℃ Mold temperature: 130℃ Injection speed: 75 mm / s Pressure holding: 30MPa [Determination Conditions and Methods] Determination method: Volumetric method Apparatus: Impedance analyzer (Agilent Technologies, model "E4991A") Electrode model: 16453A Test environment: 23℃, 50%RH Applied voltage: 500mV <Evaluation of Micronized Powder Production> Using an injection molding machine (manufactured by Nissei Resin Kogyo 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.

[0130] Next, the obtained test pieces were subjected to Izod impact tests 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 combined 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 used to evaluate the amount of fine powder produced.

[0131] [Injection Molding Conditions] Barrel temperature: 350℃ Mold temperature: 130℃ Injection speed: 75 mm / s Pressure holding: 25MPa (Examples 1-2) Except for changing the formulation of each raw material as shown in Table 1, the liquid crystal polyester composition was manufactured in the same manner as in Example 1-1. The fluidity, specific gravity, dielectric properties, and micronization amount of the obtained liquid crystal polyester composition were evaluated in the same manner as in Example 1-1. The results are shown in Table 1.

[0132] (Comparative Example 1-1) Without incorporating styrene-based resin, the formulation of the liquid crystal polyester and hollow glass filler was modified as shown in Table 1. Otherwise, the liquid crystal polyester composition was manufactured in the same manner as in Examples 1-1. The resulting liquid crystal polyester composition was evaluated for its flowability, specific gravity, dielectric properties, and micronization amount in the same manner as in Examples 1-1. The results are shown in Table 1.

[0133] (Example 2-1) (1) Manufacturing of liquid crystal polyester (LCP2) In a reactor equipped with a stirrer, torque meter, nitrogen inlet pipe, thermometer, and reflux cooler, 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, along with 0.2 g of 1-methylimidazole as a catalyst. The reactor was then completely purged with nitrogen. Subsequently, while stirring under a nitrogen flow, the temperature was increased from room temperature to 150°C over 30 minutes, maintained at this temperature, and refluxed for 30 minutes.

[0134] 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 increased from 150°C to 320°C over 2 hours and 50 minutes. After maintaining the temperature at 320°C for 30 minutes, the contents were removed and cooled to room temperature.

[0135] The obtained solid was pulverized to a particle size of 0.1-1 mm using a pulverizer, and then heated from room temperature to 250°C in a nitrogen atmosphere for 1 hour, and from 250°C to 285°C in 5 hours, and held at 285°C for 3 hours to carry out solid-phase polymerization.

[0136] The solid product after solid-state polymerization was cooled to obtain powdered liquid crystal polyester (LCP2). The flow start temperature of the obtained liquid crystal polyester (LCP2) was 312°C. It should be noted that the flow start temperature was determined by the same method as in Examples 1-1.

[0137] (2) Manufacturing of liquid crystal polyester composition As a filler for hollow glass, glass balloons (iM16K, manufactured by 3M Corporation, average particle size (median particle size, D50): 21 μm) were prepared (denoted as "GB1" in Table 2). Additionally, as a styrene-based resin, styrene-based resin 1 (XAREC 300ZC, manufactured by Idemitsu Kosan Co., Ltd., weight-average molecular weight (Mw): 140,000) was prepared (denoted as "PS1" in Table 2). Furthermore, as an inorganic filler, mica powder (manufactured by YAMAGUCHI MICA Co., Ltd., "AB-25S", average particle size 24 μm, thickness 0.45 μm) was prepared (denoted as "X1" in Table 2). Additionally, as an inorganic filler, glass fibers (manufactured by Central Glass Co., Ltd., "FDE90-01", average fiber length 90 μm, average fiber diameter 6 μm) were prepared (denoted as "X2" in Table 2).

[0138] Except that the raw materials shown in Table 2 are combined in the mass ratios shown in Table 2, the liquid crystal polyester composition was manufactured in the same manner as in Example 1-1. The fluidity, specific gravity, dielectric properties, and micronization amount of the obtained liquid crystal polyester composition were evaluated in the same manner as in Example 1-1. The results are shown in Table 2.

[0139] (Examples 2-2 to 2-5) Except for changing the formulation of each raw material as shown in Table 2, the liquid crystal polyester composition was manufactured in the same manner as in Example 2-1. The resulting liquid crystal polyester composition was evaluated for its flowability, specific gravity, dielectric properties, and micronization amount in the same manner as in Example 1-1. The results are shown in Table 2.

[0140] (Comparative Example 2-1) Without incorporating styrene-based resin, the formulation of the liquid crystal polyester and hollow glass filler was modified as shown in Table 3. Otherwise, the liquid crystal polyester composition was manufactured in the same manner as in Example 2-1. The resulting liquid crystal polyester composition was evaluated for its flowability, specific gravity, dielectric properties, and micronization amount in the same manner as in Example 1-1. The results are shown in Table 3.

[0141] (Comparative Example 2-2) Without the addition of hollow glass filler, the formulation of the liquid crystal polyester and styrene-based resin was modified as shown in Table 3. Otherwise, the liquid crystal polyester composition was manufactured in the same manner as in Example 2-1. The resulting liquid crystal polyester composition was evaluated for its flowability, specific gravity, dielectric properties, and micronization amount in the same manner as in Example 1-1. The results are shown in Table 3.

[0142] It should be noted that the liquid crystal polyester composition of Comparative Example 2-2 remained intact as a rod-shaped test piece in the Izod impact test.

[0143] (Example 3-1) (1) Manufacturing of liquid crystal polyester (LCP3) In a reactor equipped with a stirrer, torque meter, nitrogen inlet pipe, thermometer, and reflux cooler, 1034.99 g (5.5 mol) of 6-hydroxy-2-naphthoic acid, 378.33 g (1.75 mol) of 2,6-naphthoic acid, 83.07 g (0.5 mol) of terephthalic acid, 272.52 g (2.475 mol, 0.225 mol excess relative to the combined amount of 2,6-naphthoic 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. The gas inside the reactor was purged with nitrogen. Then, 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.

[0144] Next, while distilling away the by-product acetic acid and unreacted acetic anhydride, the temperature was increased from 145°C to 310°C over 3.5 hours. After maintaining the temperature at 310°C for 3 hours, the contents were removed and cooled to room temperature.

[0145] The obtained solid was pulverized to a particle size of about 0.1 to 1 mm using a pulverizer. Then, under a nitrogen atmosphere, the temperature was increased from room temperature to 250°C in 1 hour, and then increased from 250°C to 310°C in 9 hours. The temperature was then maintained at 310°C for 5 hours to carry out solid-phase polymerization.

[0146] The solid product after solid-state polymerization was cooled to obtain powdered liquid crystal polyester (LCP3). The flow start temperature of the obtained liquid crystal polyester (LCP3) was 322°C. It should be noted that the flow start temperature was determined by the same method as in Examples 1-1.

[0147] (2) Manufacturing of liquid crystal polyester composition As a filler for hollow glass, glass balloons (iM16K, manufactured by 3M Corporation, average particle size (median particle size, D50): 21 μm) were prepared (denoted as "GB1" in Table 2). Additionally, as a styrene-based resin, styrene-based resin 1 (XAREC 300ZC, manufactured by Idemitsu Kosan Co., Ltd., weight-average molecular weight (Mw): 140,000) was prepared (denoted as "PS1" in Table 2). Furthermore, as an inorganic filler, mica powder (manufactured by YAMAGUCHI MICA Co., Ltd., "AB-25S", average particle size 24 μm, thickness 0.45 μm) was prepared (denoted as "X1" in Table 2). Additionally, as an inorganic filler, glass fibers (manufactured by Central Glass Co., Ltd., "FDE90-01", average fiber length 90 μm, average fiber diameter 6 μm) were prepared (denoted as "X2" in Table 2).

[0148] Except that the raw materials shown in Table 4 are combined in the mass ratios shown in Table 4, the liquid crystal polyester composition was manufactured in the same manner as in Example 1-1. The fluidity, specific gravity, dielectric properties, and micronization amount of the obtained liquid crystal polyester composition were evaluated in the same manner as in Example 1-1. The results are shown in Table 4.

[0149] (Examples 3-2 to 3-4) Except for changing the formulation of each raw material as shown in Table 4, the liquid crystal polyester composition was manufactured in the same manner as in Example 3-1. The resulting liquid crystal polyester composition was evaluated for its flowability, specific gravity, dielectric properties, and micronization amount in the same manner as in Example 1-1. The results are shown in Table 4.

[0150] (Comparative Example 3-1) Without incorporating styrene-based resin, the formulation of the liquid crystal polyester and hollow glass filler was modified as shown in Table 5. Otherwise, the liquid crystal polyester composition was manufactured in the same manner as in Example 3-1. The resulting liquid crystal polyester composition was evaluated for its flowability, specific gravity, dielectric properties, and micronization amount in the same manner as in Example 1-1. The results are shown in Table 5.

[0151] (Comparative Example 3-2) Without the addition of hollow glass filler, the formulation of the liquid crystal polyester and styrene-based resin was modified as shown in Table 5. Otherwise, the liquid crystal polyester composition was manufactured in the same manner as in Example 3-1. The resulting liquid crystal polyester composition was evaluated for its flowability, specific gravity, dielectric properties, and micronization amount in the same manner as in Example 1-1. The results are shown in Table 5.

[0152] It should be noted that the liquid crystal polyester composition of Comparative Example 3-2 remained intact as a rod-shaped test piece in the Izod impact test.

Claims

1. A liquid crystal polyester composition, wherein, Include: Liquid crystal polyester, Inorganic fillers containing hollow glass fillers, and Styrene-based resins.

2. The liquid crystal polyester composition according to claim 1, wherein, The styrene-based resin is polystyrene.

3. The liquid crystal polyester composition according to claim 1, wherein, The content of the insulating glass filler is 5 parts by mass or more and 60 parts by mass or less relative 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-based resin is 5 parts by weight or more and 60 parts by weight or less relative to 100 parts by weight of the liquid crystal polyester.

5. The liquid crystal polyester composition according to claim 1, wherein, The ratio (C2 / C1) of the content of the styrene-based resin C2 to the content of the inorganic filler C1 is 0.1 or more and 10 or less.

6. The liquid crystal polyester composition according to claim 1, wherein, The inorganic packing further includes non-hollow packing.

7. The liquid crystal polyester composition according to claim 6, wherein, The content of the non-hollow filler is more than 2 parts by mass and less than 25 parts by mass relative to 100 parts by mass of the liquid crystal polyester.

8. The liquid crystal polyester composition according to claim 1, wherein, The hollow glass filler accounts for more than 50% by mass and less than 95% by mass in the inorganic filler.

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

10. A method for manufacturing 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.

11. The manufacturing method according to claim 10, wherein, The molding process is injection molding.

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