JP7111502B2 - Liquid crystalline polyester resin with excellent mechanical strength and dielectric properties - Google Patents

Description

TECHNICAL FIELD The present invention relates to a liquid crystalline polyester resin having excellent mechanical strength and dielectric properties.

Thermotropic liquid crystal polyester resin (hereinafter abbreviated as liquid crystal polyester resin or LCP) has excellent mechanical properties, moldability, chemical resistance, gas barrier properties, moisture resistance, electrical properties, etc., so it is used in parts in a wide variety of fields. used. In particular, due to its excellent heat resistance, thin moldability, and insulating properties, its use in electronic parts and the like is expanding.

2. Description of the Related Art In recent years, with the development of an advanced information society, the amount of information transmitted and the transmission speed of information communication devices have increased explosively in the field of information and communication such as personal computers and mobile phones. In particular, there is an increasing need for high-performance high-frequency electronic components that can be used in high-frequency regions such as microwaves and millimeter waves.

However, when a liquid crystal polyester resin having a high dielectric constant is used as a substrate of an electrical connector, for example, high-frequency signals are attenuated, resulting in a decrease in signal propagation speed. Therefore, liquid crystal polyester resins used in these electronic parts are required to have a low dielectric constant.

In general, it is known that a liquid crystalline polyester resin composition (Patent Document 1) in which glass fibers and glass balloons are blended with a liquid crystalline polyester resin has a low dielectric constant. Further, in order to reduce the dielectric constant of the liquid crystal polyester resin, a liquid crystal polyester resin composition has been proposed in which a fibrous filler having an aspect ratio of 4 or more and an inorganic spherical hollow body having a specific particle size are blended (Patent Document 2). ).

Japanese Patent Application Laid-Open No. 2004-323705 JP-A-2004-143270

However, in the above liquid crystal polyester resin composition, the glass balloons and inorganic spherical hollow bodies in the liquid crystal polyester resin are damaged during molding or are not uniformly dispersed. There were problems such as the occurrence of

Accordingly, there has been a demand for a liquid crystalline polyester resin which does not deteriorate the physical properties of the liquid crystalline polyester resin and which has a low dielectric constant and excellent dielectric properties.

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystalline polyester resin having excellent mechanical strength and excellent dielectric properties in which the resin itself has a low dielectric constant.

As a result of intensive studies, the present inventors have found that a liquid crystalline polyester resin having good mechanical strength such as impact resistance and tensile strength and excellent dielectric properties in a high frequency band can be obtained by using a specific repeating unit as a constituent component. The present inventors have found that it can be obtained, and have completed the present invention.

［式中、
ｐ、ｑおよびｒ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、
０．１≦ｑ／（ｑ＋ｒ）≦０．９、
８≦ｒ≦３４］
で表される繰返し単位を含み、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３．５０以下である、液晶ポリエステル樹脂に関する。 That is, the present invention provides formulas (I) to (III)

[In the formula,
p, q and r are the composition ratios (mol %) of each repeating unit in the liquid crystalline polyester resin, and satisfy the following conditions:
0.01≦p≦7,
0.1≤q/(q+r)≤0.9,
8≦r≦34]
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 3.50 or less. It relates to a liquid crystal polyester resin.

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

The liquid crystalline polyester resin of the present invention is a liquid crystalline polyester resin that forms an anisotropic melt phase, which is called a thermotropic liquid crystalline polyester resin by those skilled in the art.

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、
ｐ、ｑおよびｒ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、
０．１≦ｑ／（ｑ＋ｒ）≦０．９、
８≦ｒ≦３４］
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 (III)

[In the formula,
p, q and r are the composition ratios (mol %) of each repeating unit in the liquid crystalline polyester resin, and satisfy the following conditions:
0.01≦p≦7,
0.1≤q/(q+r)≤0.9,
8≦r≦34]
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 %.

If the repeating unit represented by the formula (I) is less than 0.01 mol %, it is difficult to obtain the effect of improving the dielectric properties, and if it exceeds 7 mol %, the mechanical strength tends to decrease.

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.

The composition ratio q according to formula (II) and the composition ratio r according to formula (III) preferably satisfy 0.3 ≤ q/(q + r) ≤ 0.8, more preferably 0.5 ≤ q/(q + r )≦0.75.

The composition ratio r in formula (III) is preferably 10 to 32 mol %, more preferably 12 to 30 mol %.

Specific examples of monomers that provide the repeating unit represented by formula (II) include 4-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 (III) include 6-hydroxy-2-naphthoic acid, and its acylates, ester derivatives, and ester-forming derivatives such as acid halides. .

A preferred first embodiment of the liquid crystalline polyester resin of the present invention is a liquid crystalline polyester resin composed of repeating units represented by formulas (I) to (III).

［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、ｓおよびｔ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、
０．１≦ｑ／（ｑ＋ｒ）≦０．９、
８≦ｒ≦３４、
１０≦ｓ≦２５、および
１０≦ｔ≦２５］
で表される繰返し単位から構成される液晶ポリエステル樹脂が挙げられる。 Further, as a preferred second embodiment of the liquid crystalline polyester resin of the present invention, formulas (I) to (V)

[In the formula,
Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r, s and t respectively represent the composition ratio of each repeating unit in the liquid crystal polyester resin ( %) and satisfies the following conditions:
0.01≦p≦7,
0.1≤q/(q+r)≤0.9,
8≦r≦34,
10≦s≦25, and 10≦t≦25]
A liquid crystalline polyester resin composed of repeating units represented by is mentioned.

In the second embodiment, the composition ratio p according to formula (I), the composition ratio q according to formula (II), and the composition ratio r according to formula (III) are the same as those described above for the first embodiment. and preferred conditions.

The composition ratio s according to formula (IV) and the composition ratio t according to formula (V) are each preferably 12 to 24 mol %, more preferably 14 to 22 mol %. s and t are preferably 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 (IV) (or (V)) 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 s according to the formula (IV) (or the composition ratio t according to the formula (V)) represents the total composition ratio of two or more repeating units.

Specific examples of monomers that give repeating units represented by formula (IV) 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 (V) 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 (IV) and (V) 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, as Ar ₁ related to the repeating unit represented by formula (IV), the aromatic groups represented by formulas (1) and (4) are the mechanical properties and heat resistance of the obtained liquid crystalline polyester resin. , is more preferable because it is easy to adjust the crystal melting temperature and moldability to appropriate levels.

Monomers that provide these repeating units include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and ester-forming derivatives thereof.

Further, as Ar ₂ related to the repeating unit represented by formula (V), 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 strength, heat resistance, crystalline melting temperature and molding workability of are easy to adjust to appropriate levels.

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

The total composition ratio [p + q + r] of the repeating units in the liquid crystalline polyester resin of the first embodiment and the total composition ratio [p + q + r + s + t] of the repeating units in the liquid crystalline polyester resin of the second embodiment are both 100 mol%. However, other repeating units may be further contained within a range that does not impair the object of the present invention.

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 known polycondensation methods for forming ester bonds by the above monomer components, such as melt acidolysis and slurry polymerization, 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 normal 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 in which an acetylated product of the above monomer component is used 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 case of the melt acidolysis method or the slurry polymerization method, a catalyst may be used as necessary during the reaction.

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 placed in a substantially solid phase under reduced pressure, in a vacuum, or in an atmosphere of an inert gas such as nitrogen or helium for the purpose of increasing the molecular weight and improving the heat resistance. You may heat-process in a 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 liquid crystal polyester resin of the present invention thus obtained has a dielectric constant of 3 when 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. 0.50 or less, and has excellent dielectric properties. The dielectric constant is preferably 3.49 or less, more preferably 3.48 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 strength 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 and electronic components include, but are not limited to, connectors, switches, relays, capacitors, coils, transformers, camera modules, antennas, chip antennas and electronic circuit boards, especially boards such as printed boards. . Among these, it can be used particularly preferably for connectors, antennas or substrates.

Further, the liquid crystal polyester resin or liquid crystal polyester resin composition of the present invention may be made into a film (or sheet) by a known method such as inflation molding or T-die molding. The film may have a single-layer structure or a multi-layer structure with different materials.

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 Examples 1 to 3 and Comparative Example 1 were measured using a melt viscosity measuring device (Capilograph 1D manufactured by Toyo Seiki Co., Ltd.) using a capillary of 0.7 mmφ×10 mm at a shear rate of 1000 sec ⁻¹ . 3 were measured at 320° C., and Examples 4-6 and Comparative Examples 4-6 were measured at 350° C., respectively.

(2) Tensile strength Using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), the cylinder set temperature was 320 ° C. for Examples 1 to 3 and Comparative Examples 1 to 3, Examples 4 to 6 and For Comparative Examples 4 to 6, ASTM No. 4 dumbbell test pieces were molded at 350° C. and a mold temperature of 70° C., and 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. A strip-shaped test piece having a length of 63.5 mm, a width of 12.7 mm, and a thickness of 3.2 mm was obtained by cutting the center of this test piece perpendicularly to the length direction, and the measurement was performed according to ASTM D256.

(4) Dielectric constant Using an injection molding machine (Nissei Plastic Industry Co., Ltd. NEX-15-1E), the cylinder set temperature was 320 ° C. for Examples 1 to 3 and Comparative Examples 1 to 3, and Examples 4 to 6. and Comparative Examples 4 to 6 were molded at 350° C. and a mold temperature of 80° C. into stick-shaped specimens having a length of 85 mm, a width of 1.7 mm and a thickness of 1.7 mm.
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 POB: 4-hydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid TPA: terephthalic acid HQ: hydroquinone

[Example 1] (Reference example)
3HBA: 4.5 g (0.5 mol %), POB: 651.8 g (72.6 mol %) and BON6: 329.0 g (26.6 mol %) were added to a reaction vessel equipped with a torque meter stirrer and a distillation tube. 9 mol %) was charged, and 1.03 times mol of acetic anhydride was charged with respect to the hydroxyl group amount (mol) of all the monomers, and deacetic acid polymerization was carried out under the following conditions.

In a nitrogen gas atmosphere, the temperature was raised from room temperature to 150° C. over 1 hour, and the same temperature was maintained for 30 minutes. Subsequently, the temperature was rapidly raised to 210° C. while distilling off the by-produced acetic acid, and the temperature was maintained for 30 minutes. Then, after raising the temperature to 325° C. over 5 hours, the pressure was reduced to 20 mmHg over 90 minutes. When a predetermined torque was applied, the polymerization reaction was terminated, the contents of the reaction vessel were taken out, 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, evaluation was performed by the above method. Table 1 shows the results.

[Examples 2 and 3, Comparative Examples 1 to 3] (Examples 2 and 3 are reference examples)
Pellets of a liquid crystalline polyester resin were obtained in the same manner as in Example 1, except that 3HBA, POB and BON6 were used in 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.

[Example 4]
3HBA: 4.5 g (0.5 mol %), POB: 393.2 g (43.8 mol %), BON6: 194.5 g (15. 9 mol %), TPA: 214.9 g (19.9 mol %), and HQ: 142.4 g (19.9 mol %), and further 1.03 with respect to the hydroxyl group amount (mol) of all monomers. Two moles of acetic anhydride was charged, and deacetic acid polymerization was carried out under the following conditions.

In a nitrogen gas atmosphere, the temperature was raised from room temperature to 150° C. over 1 hour, and the same temperature was maintained for 30 minutes. Subsequently, the temperature was rapidly raised to 210° C. while distilling off the by-produced acetic acid, and the temperature was maintained for 30 minutes. Then, after raising the temperature to 345° C. over 5 hours, the pressure was reduced to 20 mmHg over 90 minutes. When a predetermined torque was applied, the polymerization reaction was terminated, the contents of the reaction vessel were taken out, 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, evaluation was performed by the above method. Table 2 shows the results.

[Examples 5 and 6, Comparative Examples 4-6]
Liquid crystalline polyester resin pellets were obtained in the same manner as in Example 4, except that 3HBA, POB, BON6, TPA and HQ were used in proportions (mol %) shown in Table 2. Using the obtained pellets, the melt viscosity, tensile strength, Izod impact strength and dielectric constant were measured by the methods described above. Table 2 shows the results.

The liquid crystalline polyester resin in each example (Examples 1 to 6) had a sufficiently low dielectric constant and excellent dielectric properties. On the other hand, the liquid crystal polyester resins (Comparative Examples 1 to 6) in which the content of repeating units given by 3HBA was outside the range of the present invention were inferior in dielectric properties.

本発明の好ましい態様は以下を包含する。
〔１〕式（Ｉ）～（ＩＩＩ）
［化１］

［式中、
ｐ、ｑおよびｒ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、
０．１≦ｑ／（ｑ＋ｒ）≦０．９、
８≦ｒ≦３４］
で表される繰返し単位を含み、
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３．５０以下である、液晶ポリエステル樹脂。
〔２〕液晶ポリエステル樹脂が、式（Ｉ）～（ＩＩＩ）で表される繰返し単位から構成される、〔１〕に記載の液晶ポリエステル樹脂。
〔３〕液晶ポリエステル樹脂が、式（Ｉ）～（Ｖ）
［化２］

［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、ｓおよびｔ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、
０．１≦ｑ／（ｑ＋ｒ）≦０．９、
８≦ｒ≦３４、
１０≦ｓ≦２５、および
１０≦ｔ≦２５］
で表される繰返し単位から構成される、〔１〕に記載の液晶ポリエステル樹脂。
〔４〕Ａｒ _１ およびＡｒ _２ が、互いに独立して、式（１）～（４）
［化３］

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、〔３〕に記載の液晶ポリエステル樹脂。
〔５〕〔１〕～〔４〕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。
〔６〕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、〔５〕に記載の液晶ポリエステル樹脂組成物。
〔７〕〔１〕～〔４〕のいずれかに記載の液晶ポリエステル樹脂または〔５〕～〔６〕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またはフィルム。

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

[In the formula,
p, q and r are the composition ratios (mol %) of each repeating unit in the liquid crystalline polyester resin, and satisfy the following conditions:
0.01≦p≦7,
0.1≤q/(q+r)≤0.9,
8≦r≦34]
containing a repeating unit represented by
A liquid crystalline polyester resin having a dielectric constant of 3.50 or less 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.
[2] The liquid crystalline polyester resin according to [1], wherein the liquid crystalline polyester resin is composed of repeating units represented by formulas (I) to (III).
[3] The liquid crystalline polyester resin is represented by formulas (I) to (V)
[Chemical 2]

[In the formula,
Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r, s and t respectively represent the composition ratio of each repeating unit in the liquid crystal polyester resin ( %) and satisfies the following conditions:
0.01≦p≦7,
0.1≤q/(q+r)≤0.9,
8≦r≦34,
10≦s≦25, and
10≦t≦25]
The liquid crystalline polyester resin according to [1], which is composed of repeating units represented by:
[4] Ar ₁ and Ar ₂ are, independently of each other, the formulas (1) to (4)
[Chemical 3]

The liquid crystalline polyester resin according to [3], which is one or more selected from the group consisting of aromatic groups represented by:
[5] A liquid crystalline polyester resin composition comprising the liquid crystalline polyester resin according to any one of [1] to [4] and an inorganic filler and/or an organic filler.
[6] 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 [5], 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.
[7] A molded article or film composed of the liquid crystalline polyester resin according to any one of [1] to [4] or the liquid crystalline polyester resin composition according to any one of [5] to [6].

Claims (4)

Formulas (I)-(V)

[In the formula,
Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r, s and t respectively represent the composition ratio of each repeating unit in the liquid crystal polyester resin ( %) and satisfies the following conditions:
0.01≦p≦7,
0.1≤q/(q+r)≤0.9,
8≦r≦34,
10≦s≦25, and
10≦t≦25]
Consists of repeating units 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 dielectric constant of 3.50 or less 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. A liquid crystalline polyester resin composition comprising the liquid crystalline polyester resin according to claim 1 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 or film comprising the liquid crystalline polyester resin according to claim 1 or the liquid crystalline polyester resin composition according to any one of claims 2 and 3 .