JP7156814B2 - Liquid crystalline polyester resin with excellent mechanical and dielectric properties - Google Patents

Description

TECHNICAL FIELD The present invention relates to a liquid crystalline polyester resin having excellent mechanical properties and excellent dielectric properties in a high frequency band.

In modern society, the use of multimedia in daily life and the use of ITS (Intelligent Transport Systems) typified by ETC devices and GPS on toll roads are rapidly progressing. In order to cope with the explosive increase in information communication traffic that accompanies this, frequencies for transmitting information are becoming higher.

Engineering plastic materials with excellent dielectric properties in high-frequency bands (especially gigahertz bands), productivity and lightness are considered promising materials for such high-frequency information communication devices. It is expected to be applied to laminates such as housings and packages for equipment and electronic devices, dielectric devices, and multilayer printed circuit boards in which films and metal layers are laminated.

Among the above engineering plastics, thermotropic liquid crystal polyester resin (hereinafter abbreviated as liquid crystal polyester resin or LCP) is
(1) Excellent dielectric properties such as a constant dielectric constant (εr) in the operating frequency band and a low dielectric loss tangent (tan δ).
(2) Excellent physical properties such as low expansion characteristics (environmental dimensional stability), heat resistance, flame retardancy, and mechanical properties such as rigidity.
(3) It has excellent fluidity during molding and can be easily processed into molded products with thin parts and fine parts.
It is a material that is particularly expected in high frequency applications because it has excellent properties such as.

Among the liquid crystal polyester resins described above, since the dielectric properties are particularly excellent, a wholly aromatic liquid crystal containing 6-oxy-2-naphthoyl repeating units, aromatic dioxy repeating units and aromatic dicarbonyl repeating units in a specific ratio In recent years, polyesters have been actively developed (Patent Documents 1 to 3).

Japanese Patent Application Laid-Open No. 2004-196930 Japanese Patent Application Laid-Open No. 2005-272810 Japanese Patent Application Laid-Open No. 2004-250687

However, although liquid crystalline polyesters containing a large amount of 6-oxy-2-naphthoyl repeating units have excellent dielectric properties, they are inferior in mechanical properties such as tensile strength and impact resistance, and are susceptible to impacts such as dropping in daily use. There was a problem that it was difficult to use for parts such as mobile phones and smartphones that are susceptible to damage. Moreover, there is a problem that it is not suitable for applications requiring flexibility such as films.

An object of the present invention is to provide a liquid crystalline polyester resin which is excellent in mechanical properties such as tensile strength and impact resistance and which is excellent in dielectric properties in a high frequency band.

In view of the above problems, the present inventors have made intensive studies and found that by using a specific repeating unit as a constituent component, the liquid crystal has excellent dielectric properties in a high frequency band and excellent mechanical properties such as tensile strength and impact resistance. The inventors have found that a polyester resin can be obtained, and have completed the present invention.

［式中、
Ａｒ_１およびＡｒ_２は、それぞれ１種または２種以上の２価の芳香族基を表し、ｐ、ｑ、ｒおよびｓは、それぞれ、液晶ポリエステル樹脂中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす；
０．０１≦ｐ≦７、
３５≦ｑ≦９０、
５≦ｒ≦３０、および
５≦ｓ≦３０］
で表される繰返し単位を含み、ＡＳＴＭ Ｄ６３８に準拠した２３℃における引張強度が１８０ＭＰａ以上である、液晶ポリエステル樹脂に関する。 That is, the present invention provides formulas (I) to (IV)

[In the formula,
Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r and s respectively represent the composition ratio of each repeating unit in the liquid crystal polyester resin (mol% ), satisfying the following conditions:
0.01≦p≦7,
35≤q≤90,
5≦r≦30, and 5≦s≦30]
It relates to a liquid crystalline polyester resin containing a repeating unit represented by and having a tensile strength of 180 MPa or more at 23° C. according to ASTM D638.

The liquid crystalline polyester resin of the present invention is excellent in mechanical properties such as tensile strength and Izod impact strength, and dielectric properties in a high frequency band. It can be suitably used as a material for parts.

The liquid crystalline polyester resins of the present invention are liquid crystalline polyesters that form an anisotropic melt phase, referred to by those skilled in the art as thermotropic liquid crystalline polyester resins.

The properties of the anisotropic melt phase of the liquid crystalline polyester resin can be confirmed by a normal deflection inspection method using crossed polarizers, that is, by observing a sample placed on a hot stage under a nitrogen atmosphere.

［式中、
Ａｒ_１およびＡｒ_２は、それぞれ１種または２種以上の２価の芳香族基を表し、ｐ、ｑ、ｒおよびｓは、それぞれ、液晶ポリエステル樹脂中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす：
０．０１≦ｐ≦７、
３５≦ｑ≦９０、
５≦ｒ≦３０、および
５≦ｓ≦３０］
で表される繰返し単位を含む。 The liquid crystalline polyester resin of the present invention has formulas (I) to (IV)

[In the formula,
Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r and s respectively represent the composition ratio of each repeating unit in the liquid crystal polyester resin (mol% ) and satisfies the following conditions:
0.01≦p≦7,
35≤q≤90,
5≦r≦30, and 5≦s≦30]
Contains repeating units represented by

The composition ratio p in formula (I) is preferably 0.05 to 6 mol %, more preferably 0.1 to 5 mol %.

The composition ratio q in formula (II) is preferably 40 to 85 mol %, more preferably 45 to 80 mol %.

The composition ratio r according to formula (III) and the composition ratio s according to formula (IV) are each preferably 7 to 28 mol %, more preferably 10 to 25 mol %. Preferably, r and s are in equimolar amounts.

In the above repeating unit, for example, Ar ₁ (or Ar ₂ ) represents two or more divalent aromatic groups, which means that the repeating unit represented by formula (III) (or (IV)) is a liquid crystal polyester resin It means that two or more types are contained therein depending on the type of divalent aromatic group. In this case, the composition ratio r according to formula (III) (or the composition ratio s according to formula (IV)) represents the total composition ratio of two or more repeating units.

Specific examples of monomers that give the repeating unit represented by formula (I) include 3-hydroxybenzoic acid and ester-forming derivatives such as acylates, ester derivatives and acid halides thereof.

Specific examples of monomers that give repeating units represented by formula (II) include 6-hydroxy-2-naphthoic acid, and its acylates, ester derivatives, and ester-forming derivatives such as acid halides. .

Specific examples of monomers that give repeating units represented by formula (III) include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, and 2,7-naphthalene. Dicarboxylic acids, 1,4-naphthalene dicarboxylic acid, 4,4′-dicarboxybiphenyl, etc., alkyl, alkoxy or halogen-substituted products thereof, ester derivatives thereof, and ester-forming derivatives such as acid halides. .

Specific examples of monomers that give repeating units represented by formula (IV) include hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether and the like, and alkyl, alkoxy or halogen substituted versions thereof; and ester-forming derivatives such as acylated products thereof.

Above all, the group in which Ar ₁ and Ar ₂ relating to the repeating units represented by formulas (III) and (IV) are independently aromatic groups represented by formulas (1) to (4) A liquid crystalline polyester resin containing one or more selected from is preferred.

Among these, Ar ₁ related to the repeating unit represented by the formula (III) is an aromatic group represented by the formula (1). And it is more preferable because it is easy to adjust the moldability to an appropriate level.

Monomers that provide these repeating units include terephthalic acid and ester-forming derivatives thereof.

Further, as Ar ₂ related to the repeating unit represented by formula (IV), the aromatic group represented by formula (1) and / or formula (3) is the reactivity during polymerization and the resulting liquid crystal polyester resin It is more preferable because the mechanical properties, heat resistance, crystal melting temperature, and moldability of the resin can be easily adjusted to appropriate levels.

Monomers that provide these repeating units include hydroquinone and 4,4'-dihydroxybiphenyl, and ester-forming derivatives thereof.

Among them, as the repeating unit represented by the formula (IV), at least two of the repeating unit containing the aromatic group represented by the formula (1) and the repeating unit containing the aromatic group represented by the formula (3) A liquid crystalline polyester resin containing a seed is particularly preferred. In this case, in 100 mol% of the repeating units represented by the formula (IV), the repeating units containing an aromatic group represented by the formula (3) are preferably 80 to 99 mol %, more preferably 85 to 99 mol %, still more preferably 90 to 99 mol %.

In the liquid crystalline polyester resin of the present invention, the total compositional ratio [p+q+r+s] of the repeating units is preferably 100 mol %, but other repeating units may be included as long as the object of the present invention is not impaired.

Examples of monomers that give other repeating units include other aromatic hydroxycarboxylic acids, aromatic hydroxyamines, aromatic diamines, aromatic aminocarboxylic acids, aromatic hydroxydicarboxylic acids, aliphatic diols, aliphatic dicarboxylic acids, Aromatic mercaptocarboxylic acids, aromatic dithiols, aromatic mercaptophenols and combinations thereof, and the like.

Specific examples of other aromatic hydroxycarboxylic acids include 2-hydroxybenzoic acid, 5-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid and their alkyl, alkoxy or halogen-substituted products, and their acylated products, ester derivatives, ester-forming derivatives such as acid halides is mentioned.

The total compositional ratio of repeating units provided by these other monomer components is preferably 10 mol % or less in the entire repeating units.

The method for producing the liquid crystalline polyester resin of the present invention is described below.
The method for producing the liquid crystalline polyester resin of the present invention is not particularly limited, and a known polycondensation method for forming an ester bond by the above monomer components, such as a melt acidolysis method and a slurry polymerization method, can be used.

The melt acidolysis method is a suitable method for producing the liquid crystalline polyester resin of the present invention, which method involves first heating the monomers to form a melt of reactants and continuing the reaction. to obtain molten polyester. A vacuum may be applied to facilitate removal of volatiles (eg, acetic acid, water, etc.) that are by-produced in the final stage of condensation.

Slurry polymerization is a process in which the reaction is carried out in the presence of a heat exchange fluid and the solid product is obtained in suspension in the heat exchange medium.

In both the melt acidolysis method and the slurry polymerization method, the polymerizable monomer component used in producing the liquid crystalline polyester resin reacts at room temperature as a modified form in which the hydroxyl group is acylated, that is, as a lower acylated product. can also be provided to The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. Particularly preferred is a method of using an acetylated product of the monomer component for the reaction.

The lower acylated monomer may be synthesized in advance by acylating separately, or may be produced in the reaction system by adding an acylating agent such as acetic anhydride to the monomer during production of the liquid crystalline polyester resin. can.

In either the melt acidolysis method or the slurry polymerization method, a catalyst may be used during the reaction, if necessary.

Specific examples of catalysts include organotin compounds (dialkyltin oxides such as dibutyltin oxide, diaryltin oxides, etc.), titanium dioxide, antimony trioxide, organotitanium compounds (alkoxytitanium silicates, titanium alkoxides, etc.), and carboxylic acid compounds. Alkali and alkaline earth metal salts (potassium acetate, sodium acetate, etc.), Lewis acids ( _BF3 , etc.), gaseous acid catalysts such as hydrogen halides (HCl, etc.), and the like.

The amount of catalyst used is preferably 10 to 1000 ppm, more preferably 20 to 200 ppm, relative to the monomer mass.

The liquid crystalline polyester resin obtained by such a polycondensation reaction is extracted from the polymerization reactor in a molten state, processed into pellets, flakes, or powder, and subjected to molding and melt-kneading. .

Pellet-shaped, flake-shaped, or powder-shaped liquid crystalline polyester resins are substantially solidified under reduced pressure, vacuum, or in an inert gas atmosphere such as nitrogen or helium for the purpose of increasing the molecular weight and improving the heat resistance. You may heat-process in a phase state.

The heat treatment temperature is not particularly limited as long as the liquid crystalline polyester resin does not melt, but is preferably 260 to 350°C, more preferably 280 to 320°C.

The thus obtained liquid crystalline polyester resin of the present invention has a tensile strength of 180 MPa or more, preferably 190 MPa or more, more preferably 200 MPa or more at 23° C. according to ASTM D638. The tensile strength of the liquid crystalline polyester resin of the present invention is usually 300 MPa or less.

Further, the liquid crystalline polyester resin of the present invention has an Izod impact strength of 175 J/m or more, preferably 180 J/m or more, more preferably 185 J/m or more at 23° C. according to ASTM D256. The Izod impact strength of the liquid crystalline polyester resin of the present invention is usually 300 J/m or less.

In addition, the dielectric constant measured at 10 GHz using a test piece of 85 mm × 1.7 mm × 1.7 mm by the cavity resonator perturbation method in accordance with JIS C2565 is preferably 3.60 or less, more preferably 3.58. 3.55 or less, more preferably 3.55 or less. The dielectric constant of the liquid crystalline polyester resin of the present invention is usually 3.0 or higher.

The liquid crystalline polyester resin of the present invention obtained as described above can be made into a liquid crystalline polyester resin composition containing inorganic fillers and/or organic fillers, additives and other resin components.

Specific examples of the inorganic filler and/or organic filler that the liquid crystalline polyester resin composition of the present invention may contain include, for example, glass fiber, silica alumina fiber, alumina fiber, carbon fiber, potassium titanate fiber, boron Aluminum acid fibers, aramid fibers, talc, mica, graphite, wollastonite, dolomite, clay, glass flakes, glass beads, glass balloons, calcium carbonate, barium sulfate, titanium oxide and the like. These fillers may be used alone or in combination of two or more.

Among these, talc and glass fiber are preferable because they have an excellent balance between mechanical properties and cost.

When an inorganic filler and/or an organic filler is contained, the content is preferably 1 to 150 parts by mass, more preferably 10 to 100 parts by mass, with respect to 100 parts by mass of the liquid crystal polyester resin. preferable.

When the content of the inorganic filler and/or the organic filler is 1 part by mass or more, the effect of improving the mechanical properties of the liquid crystalline polyester resin composition is likely to be obtained. If the content of the inorganic filler and/or the organic filler exceeds 150 parts by mass, the fluidity tends to decrease and the effect of improving the dielectric properties tends to be insufficient.

Specific examples of other additives that may be contained in the liquid crystalline polyester resin composition of the present invention include, for example, higher fatty acids, higher fatty acid esters, higher fatty acid amides, and higher fatty acid metal salts (here, the higher fatty acid means carbon Lubricants such as those with an atomic number of 10 to 25), release agents such as polysiloxanes and fluororesins, dyes, pigments, colorants such as carbon black, flame retardants, antistatic agents, surfactants, phosphorus oxidation Examples include antioxidants, antioxidants such as phenolic antioxidants and sulfur-based antioxidants, weathering agents, heat stabilizers, and neutralizers. These additives may be used alone or in combination of two or more.

When these additives are contained, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total amount of the liquid crystal polyester resin.

If the content of the additive is less than 0.01 part by mass, the function of the additive tends to be difficult to achieve, and if it exceeds 10 parts by mass, the thermal stability during molding of the liquid crystalline polyester resin composition is reduced. tends to get worse.

Further, among the above other additives, when using additives such as lubricants and release agents, they may be added when preparing the liquid crystalline polyester resin composition, or when molding the liquid crystalline polyester resin. may be attached to the surface of the pellet.

Specific examples of other resin components that the liquid crystalline polyester resin composition of the present invention may contain include, for example, polyamides, polyesters, polyacetals, polyphenylene ethers and modified products thereof, polysulfones, polyethersulfones, polyetherimides, and polyamides. Examples include thermoplastic resins such as imides, and thermosetting resins such as phenol resins, epoxy resins, and polyimide resins. These resin components may be used alone or in combination of two or more.

The content of the other resin component is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 80 parts by mass, based on 100 parts by mass of the liquid crystal polyester resin.

A liquid crystalline polyester resin composition is obtained by mixing a liquid crystalline polyester resin, an inorganic filler and/or a filler, an additive or other resin components, and using a Banbury mixer, a kneader, a single-screw or twin-screw extruder, or the like to produce a liquid crystal. It can be obtained by melt-kneading under temperature conditions from the vicinity of the crystal melting temperature of the polyester resin to the crystal melting temperature +50°C.

The thus-obtained liquid crystalline polyester resin or liquid crystalline polyester resin composition of the present invention can be processed into molded articles by known molding methods such as injection molding, compression molding, extrusion molding and blow molding.

INDUSTRIAL APPLICABILITY The liquid crystalline polyester resin or liquid crystalline polyester resin composition of the present invention has excellent dielectric properties such as a low dielectric constant, so that it can be suitably used as electric and electronic parts.

Examples of such electrical/electronic components include, but are not limited to, connectors, switches, relays, capacitors, coils, transformers, camera modules, antennas, and chip antennas. Among these, it can be used particularly preferably for connectors or antennas.

Further, the liquid crystalline polyester resin or liquid crystalline polyester resin composition of the present invention can be processed into a film by known methods such as melt extrusion molding and press molding. Extrusion methods include, for example, a T-die method and an inflation method.
Especially by the T-die method, it can be processed into a non-stretched film, a uniaxially stretched film or a biaxially stretched film.

The draw ratio of the uniaxially stretched film is preferably 1.5 to 20 times, more preferably 5 to 18 times, even more preferably 10 to 15 times.

Both the MD (extrusion direction or longitudinal direction) and TD (perpendicular to the MD) stretching ratios of the biaxially stretched film are preferably 1.1 to 20 times.

In the inflation method, the drawdown ratio (bubble take-up speed/resin discharge speed) in the MD direction of the blown film is preferably 1.5 to 30, more preferably 5 to 20, and the TD of the blown film. The blow ratio (bubble diameter/annular slit diameter) is preferably 1.5-10, more preferably 2-5.

The thickness of the film of the present invention is preferably 5-100 μm, more preferably 10-75 μm, even more preferably 15-75 μm. If the thickness of the film is less than 5 μm, the strength may be insufficient, and if it exceeds 100 μm, the flexibility may be insufficient.

The film of the present invention can be made into a laminate by laminating it with a metal layer. Methods for laminating a metal layer on the film of the present invention include, for example, a method of thermocompression bonding a metal foil to the film (using a press, a heating roll, etc.), a method of bonding a metal foil to the film with an adhesive (epoxy base containing ethylene copolymer), and a method of vapor-depositing a metal layer on a film (deposition method by high-frequency sputtering, glow discharge, etc.). The surface of the film on which the metal layer is to be laminated may be subjected to corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, or the like in order to increase adhesive strength.

Examples of metals used for the metal layer include gold, silver, copper, nickel, and aluminum. Such a laminate may have a two-layer structure of a liquid crystal polyester resin film and a metal layer, or a multi-layer structure in which these layers are alternately laminated. In addition, the film or laminate may be subjected to heat treatment as necessary.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these.
Melt viscosity, tensile strength, Izod impact strength and dielectric constant in the examples were measured by the methods described below.

(1) Melt Viscosity Melt viscosity was measured at 350° C. using a 0.7 mmφ×10 mm capillary with a melt viscosity measuring device (Toyo Seiki Co., Ltd., Capilograph 1D) at a shear rate of 1000 sec ⁻¹ .

(2) Tensile strength Using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), an ASTM No. 4 dumbbell test piece was molded at a cylinder setting temperature of 350 ° C. and a mold temperature of 70 ° C., using this Measured according to ASTM D638.

(3) Izod impact strength Using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), the cylinder setting temperature is 350 ° C., the mold temperature is 70 ° C., the length is 127.0 mm, the width is 12.7 mm, and the thickness is A strip-shaped test piece with a thickness of 3.2 mm was molded. Cut the center of this test piece perpendicular to the length direction, and use the obtained strip-shaped test piece with a length of 63.5 mm, a width of 12.7 mm, and a thickness of 3.2 mm, and measure according to ASTM D256. did.

(4) Dielectric constant Using an injection molding machine (Nissei Plastic Industry Co., Ltd. NEX-15-1E), the cylinder setting temperature is 350 ° C., the mold temperature is 80 ° C., the length is 85 mm, the width is 1.7 mm, and the thickness is 1. .7 mm stick specimens were molded.
Using this test piece, the dielectric constant (10 GHz) was measured by the cavity resonator perturbation method in accordance with JIS C2565 using a network analyzer (PNA series E8316A manufactured by Agilent Technologies).

In the examples, the following abbreviations represent the following compounds.
3HBA: 3-hydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid TPA: terephthalic acid BP: 4,4'-dihydroxybiphenyl HQ: hydroquinone

[Example 1]
3HBA: 4.5 g (0.5 mol%), BON6: 656.8 g (53.7 mol%), TPA: 247.3 g (22. 9 mol %), BP: 253.0 g (20.9 mol %), and HQ: 14.3 g (2 mol %) were charged, and further 1.03 times the amount of hydroxyl groups (mol) of the total monomer. of acetic anhydride was charged, and deacetic acid polymerization was carried out under the following conditions.
Under a nitrogen gas atmosphere, the temperature was raised from room temperature to 145° C. over 1 hour and maintained at 145° C. for 30 minutes. Next, the temperature was raised to 350° C. over 7 hours while acetic acid, which was produced as a by-product, was distilled off, and then the pressure was reduced to 5 mmHg over 80 minutes. When a predetermined stirring torque was exhibited, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and pellets of the liquid crystalline polyester resin were obtained with a pulverizer. The amount of acetic acid distilled off during polymerization was almost the same as the theoretical value. Using the obtained pellets, the melt viscosity, tensile strength, Izod impact strength and dielectric constant were measured by the methods described above. Table 1 shows the results.

[Examples 2 and 3 and Comparative Examples 1 to 3]
Liquid crystalline polyester resin pellets were obtained in the same manner as in Example 1 except that 3HBA, BON6, TPA, BP and HQ were used in the proportions (mol %) shown in Table 1. Using the obtained pellets, the melt viscosity, tensile strength, Izod impact strength and dielectric constant were measured by the methods described above. Table 1 shows the results.

The liquid crystalline polyester resin in each example (Examples 1 to 3) has a tensile strength of 207 to 245 MPa, an Izod impact strength of 185 to 197 J/m, and a dielectric constant of 3.52 to 3.53. It was excellent in dielectric properties.

In contrast, the liquid crystal polyester resins (Comparative Examples 1 to 3) in which the content of the repeating unit given by 3HBA was outside the range of the present invention were inferior in tensile strength and Izod impact strength.

本発明の好ましい態様は以下を包含する。
〔１〕式（Ｉ）～（ＩＶ）
［化１］

［式中、
Ａｒ_１およびＡｒ_２は、それぞれ１種または２種以上の２価の芳香族基を表し、ｐ、ｑ、ｒおよびｓは、それぞれ、液晶ポリエステル樹脂中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす：
０．０１≦ｐ≦７、
３５≦ｑ≦９０、
５≦ｒ≦３０、および
５≦ｓ≦３０］
で表される繰返し単位を含み、
ＡＳＴＭ Ｄ６３８に準拠した２３℃における引張強度が１８０ＭＰａ以上である、液晶ポリエステル樹脂。
〔２〕Ａｒ_１およびＡｒ_２が、互いに独立して、式（１）～（４）
［化２］

で表される芳香族基からなる群から選択される１種または２種以上を表す、〔１〕に記載の液晶ポリエステル樹脂。
〔３〕Ａｒ_１が式（１）で表される芳香族基であり、Ａｒ_２が式（１）および／または式（３）で表される芳香族基である、〔２〕に記載の液晶ポリエステル樹脂。
〔４〕ＡＳＴＭ Ｄ２５６に準拠したＩｚｏｄ衝撃強度が１７５Ｊ／ｍ以上である、〔１〕～〔３〕のいずれかに記載の液晶ポリエステル樹脂。
〔５〕ＪＩＳ Ｃ２５６５に準拠した空洞共振器摂動法で８５ｍｍ×１．７ｍｍ×１．７ｍｍの試験片を用いて１０ＧＨｚにて測定した誘電率が３．６０以下である、〔１〕～〔４〕のいずれかに記載の液晶ポリエステル樹脂。
〔６〕〔１〕～〔５〕のいずれかに記載の液晶ポリエステル樹脂と無機充填材および／または有機充填材を含む、液晶ポリエステル樹脂組成物。
〔７〕無機充填材および／または有機充填材が、ガラス繊維、シリカアルミナ繊維、アルミナ繊維、炭素繊維、チタン酸カリウム繊維、ホウ酸アルミニウム繊維、アラミド繊維、タルク、マイカ、グラファイト、ウォラストナイト、ドロマイト、クレイ、ガラスフレーク、ガラスビーズ、ガラスバルーン、炭酸カルシウム、硫酸バリウム、および酸化チタンからなる群から選択される１種以上である、〔６〕に記載の液晶ポリエステル樹脂組成物。
〔８〕〔１〕～〔５〕のいずれかに記載の液晶ポリエステル樹脂または〔６〕および〔７〕のいずれかに記載の液晶ポリエステル樹脂組成物から構成される成形品。
〔９〕成形品が、アンテナまたはコネクタである、〔８〕に記載の成形品。
〔１０〕〔１〕～〔５〕のいずれかに記載の液晶ポリエステル樹脂または〔６〕および〔７〕のいずれかに記載の液晶ポリエステル樹脂組成物から構成されるフィルム。
〔１１〕〔１０〕に記載のフィルムと金属層とを有する積層体。

Preferred embodiments of the invention include the following.
[1] Formulas (I) to (IV)
[Chemical 1]

[In the formula,
Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r and s respectively represent the composition ratio of each repeating unit in the liquid crystal polyester resin (mol% ) and satisfies the following conditions:
0.01≦p≦7,
35≤q≤90,
5≦r≦30, and 5≦s≦30]
containing a repeating unit represented by
A liquid crystalline polyester resin having a tensile strength of 180 MPa or more at 23° C. according to ASTM D638.
[2] Ar ₁ and Ar ₂ are, independently of each other, the formulas (1) to (4)
[Chemical 2]

The liquid crystalline polyester resin according to [1], which is one or more selected from the group consisting of aromatic groups represented by:
[3] Ar ₁ is an aromatic group represented by formula (1), and Ar ₂ is an aromatic group represented by formula (1) and/or formula (3), according to [2] Liquid crystal polyester resin.
[4] The liquid crystalline polyester resin according to any one of [1] to [3], which has an Izod impact strength of 175 J/m or more according to ASTM D256.
[5] The dielectric constant measured at 10 GHz using a test piece of 85 mm × 1.7 mm × 1.7 mm by the cavity resonator perturbation method in accordance with JIS C2565 is 3.60 or less, [1] to [4] ].
[6] A liquid crystalline polyester resin composition comprising the liquid crystalline polyester resin according to any one of [1] to [5] and an inorganic filler and/or an organic filler.
[7] The inorganic filler and/or organic filler includes glass fiber, silica alumina fiber, alumina fiber, carbon fiber, potassium titanate fiber, aluminum borate fiber, aramid fiber, talc, mica, graphite, wollastonite, The liquid crystalline polyester resin composition according to [6], which is at least one selected from the group consisting of dolomite, clay, glass flakes, glass beads, glass balloons, calcium carbonate, barium sulfate, and titanium oxide.
[8] A molded article composed of the liquid crystalline polyester resin according to any one of [1] to [5] or the liquid crystalline polyester resin composition according to any one of [6] and [7].
[9] The molded article according to [8], which is an antenna or a connector.
[10] A film composed of the liquid crystalline polyester resin according to any one of [1] to [5] or the liquid crystalline polyester resin composition according to any one of [6] and [7].
[11] A laminate comprising the film of [10] and a metal layer.

Claims (10)

Formulas (I)-(IV)

[In the formula,
Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r and s respectively represent the composition ratio of each repeating unit in the liquid crystal polyester resin (mol% ) and satisfies the following conditions:
0.01≦p≦7,
35≤q≤85,
5≦r≦30, and 5≦s≦30]
containing a repeating unit represented by
Ar ₁ and Ar ₂ , independently of each other, of formulas (1)-(4)

represents one or more selected from the group consisting of aromatic groups represented by
A liquid crystalline polyester resin having a tensile strength of 180 MPa or more at 23° C. according to ASTM D638. 2. The liquid crystalline polyester resin according to claim 1, wherein Ar ₁ is an aromatic group represented by formula (1), and Ar ₂ is an aromatic group represented by formula (1) and/or formula (3). . 3. The liquid crystalline polyester resin according to claim 1, which has an Izod impact strength of 175 J/m or more according to ASTM D256. Any one of claims 1 to 3, wherein the dielectric constant measured at 10 GHz using a test piece of 85 mm × 1.7 mm × 1.7 mm by the cavity resonator perturbation method in accordance with JIS C2565 is 3.60 or less. The liquid crystalline polyester resin described. A liquid crystalline polyester resin composition comprising the liquid crystalline polyester resin according to any one of claims 1 to 4 and an inorganic filler and/or an organic filler. Inorganic filler and/or organic filler is glass fiber, silica alumina fiber, alumina fiber, carbon fiber, potassium titanate fiber, aluminum borate fiber, aramid fiber, talc, mica, graphite, wollastonite, dolomite, clay , glass flakes, glass beads, glass balloons, calcium carbonate, barium sulfate, and titanium oxide. A molded article composed of the liquid crystalline polyester resin according to any one of claims 1 to 4 or the liquid crystalline polyester resin composition according to any one of claims 5 and 6. 8. The molded article according to claim 7, wherein the molded article is an antenna or connector. A film composed of the liquid crystalline polyester resin according to any one of claims 1 to 4 or the liquid crystalline polyester resin composition according to any one of claims 5 and 6. A laminate comprising the film according to claim 9 and a metal layer.