JP6181587B2 - Liquid crystal polyester blend - Google Patents

Description

  The present invention relates to a liquid crystal polyester blend having excellent fluidity and excellent dielectric properties in a high frequency band.

  In modern society, the use of multimedia in everyday life and the use of ITS (Intelligent Transport Systems) such as ETC devices and GPS on toll roads are rapidly progressing. In order to cope with the explosive increase in information communication traffic accompanying this, the frequency of information transmission is increasing.

  As materials used for information communication devices with higher frequencies, engineering plastic materials with excellent dielectric properties in the high frequency band (especially gigahertz band) and excellent productivity and light weight are considered promising. It is expected to be applied as a casing or package of a device or electronic device, a dielectric device, or the like.

Among the engineering plastics described above, the thermotropic liquid crystal polyester resin (hereinafter abbreviated as liquid crystal polyester resin or LCP)
(1) The dielectric constant (εr) is constant in the frequency band used, and the dielectric property is excellent such as a low dielectric loss tangent (tan δ).
(2) Excellent in various physical properties such as low expansion characteristics (environmental dimensional stability), heat resistance, flame retardancy, mechanical properties such as rigidity,
(3) Excellent fluidity at the time of molding, and can easily process a molded product having a thin part and a fine part.
Therefore, it is a material that is particularly expected in high frequency applications.

  However, along with the rapid growth of information technology (IT), in the information / communication field, electrical and electronic parts are becoming highly integrated, downsized, thinned, and reduced in height. In many cases, a thin wall portion is formed, and even in such a thin wall portion, good fluidity is required so that the resin is completely filled. In general, liquid crystal polyester is excellent in fluidity as compared with other resins, but when such thinning is required, further improvement in fluidity is required.

  Therefore, in order to improve the fluidity of the liquid crystal polyester, a method of blending other resins has been proposed. Patent Document 1 discloses a method of blending two types of liquid crystal polyester resins having different heat distortion temperatures, and Patent Document 2 discloses a method of blending two types of liquid crystal polyester resins having different flow temperatures. .

  However, in the above-mentioned document, neither improvement of fluidity by blending LCPs nor improvement of dielectric properties in a high-frequency band has been studied, and it is still difficult to achieve both dielectric properties and fluidity. .

  Patent Document 3 proposes an aromatic liquid crystal polyester blend which is excellent in dielectric properties in a high frequency band and excellent in impact strength and moldability, but is not yet satisfactory in terms of fluidity during molding. .

  Furthermore, when the molded product is left in a high-temperature air or liquid for a long time or is soldered, a blister called a blister may occur on the surface. The cause of this phenomenon is not clear, but the decomposition gas generated when the liquid crystalline polyester is in a molten state or the air entrained during molding is brought into the molded product, and then the gas is released during high-temperature heat treatment. It is presumed that the surface of the molded product that has been expanded and softened by heating is pushed up and appears as a blister.

  In order to suppress the generation of such blisters, it is conceivable that the material is sufficiently degassed from the vent hole during the melt extrusion of the material, that it does not stay in the molding machine for a long time during the molding, or a back pressure is applied. However, all of these have a narrow operating condition range and are not sufficient to obtain a molded product in which the generation of blisters is suppressed.

Japanese Patent No. 2611376 Japanese Patent Laid-Open No. 10-219085 Japanese Patent No. 5225653

  An object of the present invention is to provide a liquid crystal polyester blend which is excellent in fluidity and excellent in dielectric properties and blister resistance in a high frequency band.

  In view of the above problems, the present inventors have intensively studied the dielectric properties, fluidity and blister resistance of liquid crystal polyester resins. As a result, by blending two liquid crystal polyesters composed of specific repeating units, the dielectric properties can be improved. The inventors have found that a liquid crystal polyester blend excellent in fluidity and blister resistance can be obtained, and has completed the present invention.

  The liquid crystalline polyester resin composition of the present invention is excellent in fluidity during molding, and is excellent in dielectric properties and blister resistance in a high frequency band, so that it can be used in various communication devices, casings and packages of electronic devices, and dielectric devices. It is suitably used for high frequency applications such as.

[式中、
ｐ、ｑ、ｒ、ｓおよびｔは、全繰り返し単位中の各繰返し単位のモル％を示し、以下の条件を満たす：
２５≦ｐ≦４５；
２≦ｑ≦１０；
１０≦ｒ≦２０；
１０≦ｓ≦２０；
２０≦ｔ≦４０；および
ｐ＋ｑ＋ｒ＋ｓ＋ｔ＝１００]
で表される繰返し単位からなる全芳香族液晶ポリエステル、および
（Ｂ）式［ＶＩ］：

で表される繰り返し単位、および
式［ＶＩＩ］：

[式中、
ｕおよびｖは、全繰り返し単位中の各繰返し単位のモル％を示し、以下の条件を満たす：
１０／９０≦ｕ／ｖ≦５０／５０；および
ｕ＋ｖ≧９０]
で表される繰返し単位を含む液晶ポリエステル
を含み、重量比（Ａ）／（Ｂ）は９９／１〜１５／８５である、液晶ポリエステルブレンドを提供するものである。 That is, the present invention
(A) The following formulas [I] to [V]:

[Where
p, q, r, s, and t represent the mol% of each repeating unit in all repeating units, and satisfy the following conditions:
25 ≦ p ≦ 45;
2 ≦ q ≦ 10;
10 ≦ r ≦ 20;
10 ≦ s ≦ 20;
20 ≦ t ≦ 40; and p + q + r + s + t = 100]
A wholly aromatic liquid crystal polyester comprising a repeating unit represented by formula (B):

A repeating unit represented by formula [VII]:

[Where
u and v represent the mole% of each repeating unit in all repeating units and satisfy the following conditions:
10/90 ≦ u / v ≦ 50/50; and u + v ≧ 90]
A liquid crystal polyester blend comprising a liquid crystal polyester containing a repeating unit represented by the formula (1) and having a weight ratio (A) / (B) of 99/1 to 15/85 is provided.

  The wholly aromatic liquid crystal polyester (A) (hereinafter simply referred to as liquid crystal polyester (A)) and liquid crystal polyester (B) used in the liquid crystal polyester blend of the present invention have an anisotropic melt phase called a thermotropic liquid crystal polyester. The liquid crystal polyester to be formed.

  The property of the anisotropic molten phase of the liquid crystal polyester can be confirmed by a normal deflection inspection method using an orthogonal deflector, that is, by observing a sample placed on a hot stage in a nitrogen atmosphere.

Hereinafter, the liquid crystal polyester (A) will be described.
The liquid crystal polyester (A) used in the present invention is a wholly aromatic liquid crystal polyester resin composed of an aromatic oxycarbonyl repeating unit, an aromatic dioxy repeating unit, and an aromatic dicarbonyl repeating unit. The liquid crystalline polyester (A) composed of these repeating units may or may not form an anisotropic molten phase depending on the constituent components, the composition ratio in the polymer, and the sequence distribution. The liquid crystal polyester (A) to be formed is limited to those forming an anisotropic molten phase.

で表されるｐ−オキシベンゾイル繰返し単位、および式［ＩＩ］：

［式中、ｐおよびｑはそれぞれ、液晶ポリエステル（Ａ）における全繰返し単位中の式［Ｉ］および式［ＩＩ］で表される繰返し単位のモル％を示す］
で表される６−オキシ−２−ナフトイル繰返し単位を本質的に含んでなる。 The liquid crystal polyester (A) is represented by the following formula [I] as an aromatic oxycarbonyl repeating unit:

P-oxybenzoyl repeating unit represented by the formula [II]:

[Wherein, p and q represent the mol% of the repeating units represented by the formulas [I] and [II] in all the repeating units in the liquid crystal polyester (A), respectively]
6-oxy-2-naphthoyl repeating unit represented by the formula:

  The liquid crystalline polyester (A) contains 25 to 45 mol%, preferably 30 to 45 mol%, more preferably 30 to 40 mol% of the repeating unit represented by the formula [I], and It comprises 2 to 10 mol%, preferably 3 to 9 mol%, more preferably 3 to 6 mol% of the repeating unit represented by the formula [II] with respect to all repeating units.

  Examples of the monomer that gives the repeating unit represented by the formula [I] include p-hydroxybenzoic acid and ester-forming derivatives such as acylated products, ester derivatives, and acid halides.

  Examples of the monomer that gives the repeating unit represented by the formula [II] include 6-hydroxy-2-naphthoic acid and ester-forming derivatives such as acylated products, ester derivatives, and acid halides.

、および式［ＩＶ］：

［式中、ｒおよびｓはそれぞれ、液晶ポリエステル（Ａ）における全繰返し単位中の式［ＩＩＩ］および式［ＩＶ］で表される繰返し単位のモル％を示す］
で表される繰返し単位を本質的に含んでなる。 Further, the liquid crystal polyester resin (A) is represented by the following formula [III] as an aromatic dioxy repeating unit:

And formula [IV]:

[Wherein, r and s respectively represent mol% of the repeating units represented by the formulas [III] and [IV] in all the repeating units in the liquid crystal polyester (A)].
The repeating unit represented by these is essentially included.

  In the liquid crystal polyester resin (A), the repeating unit represented by the formula [III] is 10 to 20 mol%, preferably 13 to 20 mol%, more preferably 13.5 to 18.5, based on all repeating units. The repeating unit represented by the formula [IV] is contained in an amount of 10 to 20 mol%, preferably 10 to 17 mol%, more preferably 10 to 17 mol%. 11.5 to 15.5 mol%, more preferably 12 to 14 mol%.

  The liquid crystal polyester (A) is a liquid crystal polyester (A) having a repeating unit represented by the formula [IV] in which the composition ratio (mol%) in the liquid crystal polyester (A) of the repeating unit represented by the formula [III] is: More than the composition ratio (mol%) in the case of, i.e., satisfying the relationship of r> s is preferable from the viewpoint of blister resistance.

  Examples of the monomer that gives the repeating unit represented by the formula [III] include hydroquinone and ester-forming derivatives such as acylated products thereof.

  Examples of the monomer that gives the repeating unit represented by the formula [IV] include ester-forming derivatives such as 4,4'-dihydroxybiphenyl and acylated products thereof.

［式中、ｔは、液晶ポリエステル樹脂における全繰返し単位中の式［Ｖ］で表される繰返し単位のモル％を示す］
で表される芳香族ジカルボニル繰返し単位を本質的に含んでなる。 The liquid crystal polyester resin (A) is further represented by the following formula [V]:

[Wherein t represents mol% of the repeating unit represented by the formula [V] in all repeating units in the liquid crystal polyester resin]
Essentially comprising an aromatic dicarbonyl repeat unit represented by:

  The liquid crystal polyester (A) contains 20 to 40 mol%, preferably 25 to 35 mol%, more preferably 28 to 32 mol% of a repeating unit represented by the formula [V] as an aromatic dicarbonyl repeating unit. Become.

  Examples of the monomer that gives the repeating unit represented by the formula [V] include terephthalic acid, ester derivatives thereof, and ester-forming derivatives such as acid halides.

  In the liquid crystal polyester (A), p + q + r + s + t = 100.

  Further, in the liquid crystal polyester (A), the total content of the aromatic dioxy repeating units represented by the formula [III] and the formula [IV] and the content of the aromatic dicarbonyl repeating unit represented by the formula [V] Are preferably substantially equimolar.

で表される繰り返し単位、および式［ＶＩＩ］：

[式中、
ｕおよびｖは、全繰り返し単位中の各繰返し単位のモル％を示し、以下の条件を満たす：
１０／９０≦ｕ／ｖ≦５０／５０；および
ｕ＋ｖ≧９０]
で表される繰り返し単位を含む液晶性ポリエステルである。 Next, the liquid crystal polyester (B) will be described.
The liquid crystal polyester (B) used in the present invention is an aromatic oxycarbonyl repeating unit in all repeating units, and has the formula [VI]:

A repeating unit represented by formula [VII]:

[Where
u and v represent the mole% of each repeating unit in all repeating units and satisfy the following conditions:
10/90 ≦ u / v ≦ 50/50; and u + v ≧ 90]
It is liquid crystalline polyester containing the repeating unit represented by these.

  As for the liquid crystal polyester (B), the liquid crystal polyester (B) may be used as long as it contains a repeating unit represented by the formula [VI] and a repeating unit represented by the formula [VII] in a predetermined amount and ratio. There are no particular restrictions on the type and combination of repeating units to be constructed.

  The liquid crystal polyester (B) used in the present invention comprises two or more liquid crystal polyester resins so as to contain a repeating unit represented by the formula [VI] and a repeating unit represented by the formula [VII] in a predetermined amount and ratio. These may be used separately or by melt kneading to obtain a liquid crystal polyester blend.

  In the liquid crystal polyester (B), the total amount (u + v) of the repeating unit represented by the formula [VI] and the repeating unit represented by the formula [VII] is 90 to 100 mol%, more preferably 95 to 100 mol. %. Particularly preferably, the total amount of the repeating unit represented by the formula [VI] and the repeating unit represented by the formula [VII] is 100 mol%, that is, the repeating unit represented by the formula [VI] and the formula [VII]. This is a case where only the represented repeating unit is included, which is preferable from the viewpoint of ease of polymerization.

  In the liquid crystal polyester (B), the molar ratio (u / v) of the repeating unit represented by the formula [VI] and the repeating unit represented by the formula [VII] is 10/90 to 50/50, more preferably. Is 20/80 to 40/60, particularly preferably 25/75 to 30/70.

  The liquid crystal polyester (B) used in the present invention essentially comprises a repeating unit represented by the formula [VI] and a repeating unit represented by the formula [VII] as aromatic oxycarbonyl repeating units. Examples of the monomer that gives the repeating unit represented by the formula [VI] include 6-hydroxy-2-naphthoic acid and ester-forming derivatives such as acylated products, ester derivatives, and acid halides. Examples of the monomer that gives the repeating unit represented by the formula [VII] include 4-hydroxybenzoic acid and ester-forming derivatives thereof such as acylated products, ester derivatives, and acid halides.

  As the preferred repeating unit excluding the repeating unit represented by the formula [VI] and the repeating unit represented by the formula [VII] constituting the liquid crystal polyester (B) used in the present invention, an aromatic oxycarbonyl repeating unit is used. , Aromatic dicarbonyl repeat unit, aromatic dioxy repeat unit, aromatic aminooxy repeat unit, aromatic aminocarbonyl repeat unit, aromatic diamino repeat unit, aromatic oxydicarbonyl repeat unit, and aliphatic dioxy repeat unit Can be mentioned.

  Specific examples of the monomer giving the aromatic oxycarbonyl repeating unit include, for example, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 5-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4 Aromatic hydroxycarboxylic acids such as' -hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, their alkyl, alkoxy or halogen substituents, and These acylated compounds, ester derivatives, and ester-forming derivatives such as acid halides can be mentioned.

  Specific examples of the monomer that gives the aromatic dioxy repeating unit and the aromatic dicarbonyl repeating unit are the same as those mentioned in the liquid crystal polyester (A).

  Specific examples of the monomer that gives the aromatic aminooxy repeating unit include, for example, p-aminophenol, m-aminophenol, 4-amino-1-naphthol, 5-amino-1-naphthol, and 8-amino-2. -Ester and / or amide-forming derivatives such as aromatic hydroxyamines such as naphthol, 4-amino-4'-hydroxybiphenyl, alkyl, alkoxy or halogen substituents thereof, and acylated products thereof.

  Specific examples of the monomer giving the aromatic aminocarbonyl repeating unit include aromatic aminocarboxylic acids such as p-aminobenzoic acid, m-aminobenzoic acid and 6-amino-2-naphthoic acid, and alkyls thereof. , Alkoxy or halogen substitution products, and acylated products, ester derivatives, ester halides and / or forming derivatives thereof such as acid halides.

  Specific examples of the monomer that gives the aromatic diamino repeating unit include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, and alkyls thereof. , Alkoxy- or halogen-substituted products, and amide-forming derivatives thereof such as acylated products thereof.

  Specific examples of the monomer giving the aromatic oxydicarbonyl repeating unit include hydroxy aromatic dicarboxylic acids such as 3-hydroxy-2,7-naphthalenedicarboxylic acid, 4-hydroxyisophthalic acid, and 5-hydroxyisophthalic acid. Examples include acids, their alkyl, alkoxy or halogen-substituted products, and ester-forming derivatives thereof such as acylated products, ester derivatives, and acid halides.

  Specific examples of the monomer giving the aliphatic dioxy repeating unit include aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and acylated products thereof. In addition, polyesters containing aliphatic dioxy repeating units such as polyethylene terephthalate and polybutylene terephthalate are mixed with the above aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols and acylated products, ester derivatives, acid halides thereof. It is also possible to obtain a liquid crystal polyester containing an aliphatic dioxy repeating unit by reacting with the above.

  Hereinafter, the manufacturing method of liquid crystalline polyester (A) and liquid crystalline polyester (B) is demonstrated.

  There are no particular limitations on the method for producing the liquid crystal polyester (A) and the liquid crystal polyester (B) used in the present invention, and a known polycondensation method for forming an ester bond or an amide bond composed of a combination of the above monomers, for example, melt acidosis Method, slurry polymerization method and the like can be used.

  The melt acidolysis method is a preferable method for use in the production method of the liquid crystalline polyester used in the present invention, and this method first heats the monomer to form a molten liquid of the reactant, and then performs the reaction. Subsequently, a molten polymer is obtained. Note that a vacuum may be applied to facilitate removal of volatiles (for example, acetic acid, water, etc.) by-produced in the final stage of the condensation.

  The slurry polymerization method is a method of reacting in the presence of a heat exchange fluid, and the solid product is obtained in a state suspended in a heat exchange medium.

  In any of the melt acidification method and the slurry polymerization method, the polymerizable monomer component used in producing the liquid crystal polyester is a modified form in which hydroxyl groups and / or amino groups are acylated at room temperature, that is, lower It can also be subjected to the reaction as an acylated product. The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. Particularly preferred is a method using an acetylated product of the monomer in the reaction.

  The acylated product of the monomer may be prepared by separately acylating and synthesized in advance, or it may be generated in the reaction system by adding an acylating agent such as acetic anhydride to the monomer during the production of the liquid crystal polymer. it can.

  In any case of the melt acidification method or the slurry polymerization method, a catalyst may be used as necessary.

  Specific examples of the catalyst include organotin compounds such as dialkyltin oxide (eg dibutyltin oxide) and diaryltin oxide; titanium compounds such as titanium dioxide, antimony trioxide, alkoxy titanium silicate and titanium alkoxide; alkali or alkaline earth of carboxylic acid Metal acid salts (for example, potassium acetate); inorganic acid salts (for example, potassium sulfate); Lewis acid (for example, boron trifluoride); gaseous acid catalysts such as hydrogen halide (for example, hydrogen chloride).

  The ratio of the catalyst used is usually 1 to 1000 ppm, preferably 20 to 200 ppm, based on the monomer.

The liquid crystal polyester (A) and the liquid crystal polyester (B) obtained by the polycondensation reaction in this manner are each extracted from the polymerization reaction tank in a molten state, and then processed into pellets, flakes, or powders. The
The pellet-like, flake-like, or powder-like liquid crystal polyester (A) and liquid crystal polyester (B) are used in vacuum or in an inert gas atmosphere such as nitrogen or helium for the purpose of enhancing heat resistance, if desired. You may heat-process in a solid-phase state.

  The liquid crystal polyester (A) and liquid crystal polyester (B) processed in the form of pellets, flakes, or powders obtained in this manner are obtained using a Banbury mixer, a kneader, a uniaxial or biaxial extruder, etc. It is melt-kneaded to obtain the liquid crystal polyester blend of the present invention.

  The blending ratio (A) / (B) of the liquid crystal polyester (A) and the liquid crystal polyester (B) is 99/1 to 15/85, preferably 98/2 to 20/80, more preferably 97 /. 3-25 / 75.

  When (A) / (B) is larger than 99/1, the fluidity is not sufficiently improved, and when (A) / (B) is smaller than 15/85, the effect of improving blister resistance is obtained. Since it is not possible, it is not preferable.

  Further, the liquid crystal polymer blend of the present invention exhibits a low dielectric loss tangent in the high frequency region of the gigahertz band. Specifically, the dielectric loss tangent measured under the condition of 1 GHz is a very low dielectric loss tangent of 0.0015 or less, preferably 0.0014 or less, more preferably 0.0013 or less.

  The dielectric loss tangent is measured at 1 GHz and 10 GHz using a stick-shaped test piece having a length of 85 mm, a width of 1.75 mm, and a thickness of 1.75 mm in a cavity resonator perturbation method using a vector network analyzer (manufactured by Agilent Technologies). Can be measured.

  A liquid crystal polyester blend composition may be prepared by blending the liquid crystal polyester blend comprising the liquid crystal polyester (A) and the liquid crystal polyester (B) obtained as described above with an inorganic filler and / or an organic filler.

  Examples of the inorganic filler and / or organic filler that may be blended in the liquid crystal polyester blend composition of the present invention include glass fiber, silica alumina fiber, alumina fiber, carbon fiber, potassium titanate fiber, and aluminum borate fiber. And at least one selected from the group consisting of aramid fiber, talc, mica, graphite, wollastonite, dolomite, clay, glass flake, glass beads, glass balloon, calcium carbonate, barium sulfate, and titanium oxide. In these, glass fiber is preferable at the point which the balance of a physical property and cost is excellent.

  The blending amount of the inorganic filler and / or the organic filler in the liquid crystal polyester blend composition of the present invention is 0.1 to 200 with respect to 100 parts by weight of the total amount of the liquid crystal polyester (A) and the liquid crystal polyester (B). Part by weight, preferably 1 to 100 parts by weight.

  When the blending amount of the inorganic filler and / or organic filler exceeds 200 parts by weight, molding processability tends to be reduced, and wear of the cylinder and mold of the molding machine tends to increase.

  In the liquid crystal polyester blend composition of the present invention, higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid metal salts (here, higher fatty acids are those having 10 to 25 carbon atoms) as long as the effects of the present invention are not impaired. 1) selected from among mold release improvers such as polysiloxanes and fluororesins; colorants such as dyes and pigments; antioxidants; thermal stabilizers; ultraviolet absorbers; antistatic agents; You may mix | blend seed | species or 2 or more types in combination.

  For those having an external lubricant effect such as higher fatty acid, higher fatty acid ester, higher fatty acid metal salt, fluorocarbon surfactant, etc., when the liquid crystal polyester blend of the present invention or the composition thereof is molded, the liquid crystal polyester blend or its You may adhere to the surface of the pellet of a composition.

  In addition, the liquid crystal polyester blend of the present invention or a composition thereof is blended with other resin components that can be molded and processed in the same temperature range as the liquid crystal polyester blend of the present invention, as long as the object of the present invention is not impaired. May be. Examples of other resin components include polyamide, polyester, polyacetal, polyphenylene ether and modified products thereof, and thermoplastic resins such as polysulfone, polyethersulfone, polyetherimide, and polyamideimide, phenol resin, epoxy resin, and polyimide resin. These thermosetting resins can be mentioned. Other resin components can be blended alone or in combination of two or more. The blending amount of the other resin components is not particularly limited, and may be appropriately determined according to the use and purpose of the liquid crystal polyester blend composition. Typically, the total blending amount of other resins is 0.1 to 100 with respect to 100 parts by weight of the liquid crystal polyester (A) and the liquid crystal polyester (B) in the liquid crystal polyester blend of the present invention or the composition thereof. It is added in a range of 0.1 to 80 parts by weight, particularly 0.1 to 80 parts by weight.

  The liquid crystal polyester blend of the present invention comprising the liquid crystal polyester (A) and the liquid crystal polyester (B), and an inorganic filler and / or an organic filler may be combined with various additives and other resin components as desired to obtain a predetermined composition. Then, a liquid crystal polyester blend composition can be obtained by melt-kneading using a Banbury mixer, a kneader, a single-screw or twin-screw extruder or the like.

  These inorganic fillers and / or organic fillers, various additives and other resin components may be blended in a liquid crystal polyester blend comprising the liquid crystal polyester (A) and the liquid crystal polyester (B). You may mix | blend simultaneously at the time of melt-kneading A) and liquid crystalline polyester (B).

  The liquid crystal polyester blend or liquid crystal polyester blend composition of the present invention thus obtained is processed into a molded product, a film, a sheet, a nonwoven fabric, and the like by a known molding method using an injection molding machine, an extruder or the like. The

  The liquid crystal polyester blend or liquid crystal polyester blend composition of the present invention is excellent in fluidity and excellent in dielectric properties, blister resistance and mechanical strength in a high frequency band, and therefore used in high frequency applications such as antennas, connectors, and substrates. It is particularly preferably used as the material.

  Hereinafter, the present invention will be described in detail by way of examples.

  In Examples and Comparative Examples, fluidity, blister resistance, dielectric loss tangent (tan δ), and bending strength were measured by the following methods.

1) Fluidity When a cylinder temperature is 350 ° C. and an injection pressure is 20 MPa using an injection molding machine (PS40 manufactured by Nissei Plastic Industry Co., Ltd.) using a bar flow flow length measuring mold having a thickness of 0.3 mm and a width of 12.7 mm. The flow length was evaluated.

2) Blister resistance A test piece of 62.5 × 12.7 × 0.8 mm was heated in a gear oven at 240 ° C. for 10 minutes, and after cooling, a blister exceeding a diameter of 1 mm seen on the surface by visual inspection (blister ) Was counted. The test piece having 0 to 1 blisters was evaluated as “good”, and the test piece having two or more test pieces was evaluated as “poor”.

3) Dissipation factor (tan δ)
A stick-shaped test piece having a length of 85 mm, a width of 1.75 mm, and a thickness of 1.75 mm was prepared using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), and the test piece was used to create a vector network. The dielectric loss tangent at 1 GHz and 10 GHz was measured by a cavity resonator perturbation method with an analyzer (manufactured by Agilent Technologies). When the dielectric loss tangent was 0.0015 or less, it was evaluated as ◯, when it exceeded 0.0015 and 0.0020 or less, Δ when it exceeded 0.0020, and x when it exceeded 0.0020.

4) Bending strength Using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), injection molding was performed at a cylinder temperature of 350 ° C. and a mold temperature of 70 ° C., and a 12.7 × 127 × 3.2 mm strip-shaped bend. A specimen was obtained. The bending test was performed according to ASTM D790.

Hereinafter, the abbreviations in Synthesis Examples and Examples represent the following compounds.
[Liquid crystal polyester resin monomer]
POB: parahydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid BP: 4,4-dihydroxybiphenyl HQ: hydroquinone TPA: terephthalic acid

Synthesis example 1
Synthesis of LCP-I [Liquid Crystalline Polyester (A)]
In a reaction vessel equipped with a stirrer with a torque meter and a distillation pipe, POB, BON6, HQ, BP, and TPA were charged at a composition ratio shown in Table 1 so that the total amount was 6.5 mol. 1.03 times mole of acetic anhydride was charged with respect to the amount of hydroxyl group (mol), and deacetic acid polymerization was performed under the following conditions.

  The temperature was raised from room temperature to 150 ° C. over 1 hour in a nitrogen gas atmosphere, and the temperature was maintained for 30 minutes. Next, the temperature was raised to 350 ° C. over 7 hours while acetic acid produced as a by-product was distilled off, and then the pressure was reduced to 5 mmHg over 80 minutes. When the predetermined torque was exhibited, the polymerization reaction was terminated, the reaction vessel contents were taken out, and liquid crystal polyester resin pellets were obtained using a pulverizer. The amount of acetic acid distilled during the polymerization was almost as theoretical.

Synthesis example 2
Synthesis of LCP-II [Liquid Crystalline Polyester (B)]
In a reaction vessel equipped with a stirrer with a torque meter and a distillation tube, POB and BON6 are charged so that the total amount is 6.5 mol in the composition ratio shown in Table 2 below. 1.03 moles of acetic anhydride was charged and deacetic acid polymerization was carried out under the following conditions.

  The temperature was raised from room temperature to 150 ° C. over 1 hour in a nitrogen gas atmosphere, and the temperature was maintained for 30 minutes. Next, while acetic acid produced as a by-product was distilled off, the temperature was quickly raised to 210 ° C. and held at that temperature for 30 minutes. Then, after heating up to 325 degreeC over 5 hours, it pressure-reduced to 20 mmHg over 90 minutes. When the predetermined torque was exhibited, the polymerization reaction was terminated, the reaction vessel contents were taken out, and liquid crystal polyester resin pellets were obtained using a pulverizer. The amount of acetic acid distilled during the polymerization was almost as theoretical.

Synthesis example 3
Synthesis of LCP-III [Liquid Crystalline Polyester (A)]
POB, BON6, HQ, BP, and TPA were charged into a reaction vessel equipped with a stirring device with a torque meter and a distillation pipe so that the total amount was 6.5 mol at the composition ratio shown in Table 3. Further, 1.03 times mole of acetic anhydride was charged with respect to the hydroxyl amount (mol) of all monomers. Subsequently, deacetic acid polymerization was performed under the same conditions as in Synthesis Example 1 to obtain a liquid crystal polyester resin. The amount of acetic acid distilled during the polymerization was almost as theoretical.

Synthesis example 4
Synthesis of LCP-IV In a reaction vessel equipped with a stirrer with a torque meter and a distillation tube, BON6, HQ, BP and TPA were charged at a composition ratio shown in Table 4 so that the total amount was 6.5 mol. Further, 1.03 times mole of acetic anhydride was charged with respect to the hydroxyl amount (mol) of all monomers. Subsequently, deacetic acid polymerization was performed under the same conditions as in Synthesis Example 1 to obtain a liquid crystal polyester resin. The amount of acetic acid distilled during the polymerization was almost as theoretical.

Examples 1-3
LCP-I and LCP-II were blended so as to have the weight ratios shown in Table 5, and melt kneaded at 350 ° C. using a twin screw extruder TEX-30 (manufactured by Nippon Steel Works). A liquid crystal polyester blend was obtained as pellets. Thereafter, fluidity, blister resistance, dielectric loss tangent (tan δ) and bending strength were measured.

Example 4 and Comparative Example 5
LCP-II and LCPIII were blended so as to have a weight ratio shown in Table 5, and a liquid crystal polyester blend was obtained as pellets in the same manner as in Example 1. Thereafter, fluidity, blister resistance, dielectric loss tangent (tan δ) and bending strength were measured.

Comparative Examples 1-4
With respect to the liquid crystal polyesters LCP-I to LCP-IV obtained in Synthesis Examples 1 to 4, the fluidity, blister resistance, dielectric loss tangent (tan δ), and bending strength were measured independently without blending.

Comparative Example 6
LCP-II and LCP-IV were blended so as to have a weight ratio shown in Table 5, and a liquid crystal polyester blend was obtained as pellets in the same manner as in Example 1. Thereafter, fluidity, blister resistance, dielectric loss tangent (tan δ) and bending strength were measured.

  Table 5 shows the measurement and evaluation results of each example and comparative example.

  All of the liquid crystal polyester blends of the present invention (Examples 1 to 4) exhibited improved blister resistance while maintaining excellent fluidity, and exhibited low dielectric loss tangent and high bending strength.

  In contrast, when the liquid crystal polyester (A) is used alone (Comparative Example 1 and Comparative Example 3), the fluidity and the dielectric loss tangent at 1 GHz are inferior, and when the liquid crystal polyester (B) is used alone (Comparative Example). 2) was inferior in blister resistance and dielectric loss tangent at 10 GHz.

  Moreover, when the compounding ratio of the liquid crystal polyester (A) and the liquid crystal polyester (B) is out of the range of the present invention (Comparative Example 5), sufficient blister resistance cannot be obtained, and the liquid crystal polyester (A) is the present invention. When the above condition was not satisfied (Comparative Example 4 and Comparative Example 6), satisfactory fluidity was not obtained.

Claims (8)

(A) The following formulas [I] to [V]:

[Where
p, q, r, s, and t represent the mol% of each repeating unit in all repeating units, and satisfy the following conditions:
25 ≦ p ≦ 45;
2 ≦ q ≦ 10;
10 ≦ r ≦ 20;
10 ≦ s ≦ 20;
20 ≦ t ≦ 40; and p + q + r + s + t = 100]
A wholly aromatic liquid crystal polyester comprising a repeating unit represented by formula (B):

A repeating unit represented by formula [VII]:

[Where
u and v represent the mole% of each repeating unit in all repeating units and satisfy the following conditions:
10/90 ≦ u / v ≦ 50/50; and u + v ≧ 90]
A liquid crystal polyester blend comprising a liquid crystal polyester containing a repeating unit represented by the formula (1), wherein the weight ratio (A) / (B) is 99/1 to 15/85.   The liquid crystal polyester blend according to claim 1, wherein the liquid crystal polyester (B) includes only a repeating unit represented by the formula [VI] and a repeating unit represented by the formula [VII].   The liquid crystal polyester blend according to claim 1 or 2, wherein a dielectric loss tangent measured at 1 GHz is 0.0015 or less using a stick-shaped test piece having a length of 85 mm, a width of 1.75 mm, and a thickness of 1.75 mm. A liquid crystal polyester blend composition comprising 100 parts by weight of the liquid crystal polyester blend according to any one of claims 1 to 3, and 0.1 to 200 parts by weight of at least one inorganic filler and / or 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 5. The liquid crystal polyester blend composition according to claim 4, which is at least one selected from the group consisting of glass flakes, glass beads, glass balloons, calcium carbonate, barium sulfate, and titanium oxide.   The liquid crystal polyester blend composition according to claim 4, wherein the inorganic filler is glass fiber.   A molded article comprising the liquid crystal polyester blend according to any one of claims 1 to 3 or the liquid crystal polyester blend composition according to any one of claims 4 to 6.   The molded article according to claim 7, wherein the molded article is selected from the group consisting of an antenna, a connector, and a substrate.