JP6177191B2 - 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) Excellent dielectric characteristics such as a constant and low dielectric constant in the operating frequency band and 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.

  On the other hand, along with the rapid growth of information technology (IT), in the information / communication field, high integration, miniaturization, thinning, low profile, etc. of electric and electronic parts are progressing, and it is extremely less than 0.5mm. 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. .

  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

  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 conducted extensive studies on the dielectric properties, fluidity, and blister resistance of liquid crystal polyester resins, and as a result, blended two liquid crystal polyesters composed of specific repeating units at a specific ratio. The inventors have found that a liquid crystal polyester blend having excellent dielectric properties and improved fluidity and blister resistance can be obtained, and the present invention has been completed.

  The liquid crystalline polyester resin composition of the present invention has excellent fluidity during molding, excellent dielectric properties in the high frequency band, particularly low dielectric constant in the high frequency band, and excellent resistance to blistering. It is suitably used for high-frequency applications such as housings and packages of devices and dielectric devices.

It is a schematic diagram of the dumbbell-shaped test piece used for the tensile strength test.

［式中、
ｋ、ｌ、ｍおよびｎは、全繰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：
６０≦ｋ≦８０；
０．１≦ｌ≦１０；
１０≦ｍ≦２０；
１０≦ｎ≦２０；および
ｋ＋ｌ＋ｍ＋ｎ＝１００
式［ＩＩＩ］におけるＡｒ_１は、下記式：

または

で示される構造、またはその両方の構造を含み、そして式［ＩＶ］におけるＡｒ_２は、下記式：

または

で示される構造、またはその両方の構造を含む］
で表される繰返し単位からなる全芳香族ポリエステル、および
（Ｂ）下記式［Ｖ］〜［ＩＸ］：

［式中、
ｐ、ｑ、ｒ、ｓおよびｔは、全繰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
を含み、重量比（Ａ）／（Ｂ）は９７／３〜３／９７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) Formulas [I] to [IV] below:

[Where:
k, l, m and n represent the mole% of each repeating unit in all repeating units and satisfy the following conditions:
60 ≦ k ≦ 80;
0.1 ≦ l ≦ 10;
10 ≦ m ≦ 20;
10 ≦ n ≦ 20; and k + 1 + m + n = 100
Ar ₁ in the formula [III] represents the following formula:

Or

And Ar ₂ in the formula [IV] is a group represented by the following formula:

Or

Including the structure indicated by or both]
And (B) the following formulas [V] to [IX]:

[Where:
p, q, r, s, and t represent the mole% 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 liquid crystal polyester blend comprising a wholly aromatic liquid crystal polyester composed of a repeating unit represented by the formula (1) and having a weight ratio (A) / (B) of 97/3 to 3/97 is provided.

  The wholly aromatic liquid crystal polyester (A) (hereinafter simply referred to as liquid crystal polyester (A)) and wholly aromatic liquid crystal polyester (B) (hereinafter simply referred to as liquid crystal polyester (B)) used in the liquid crystal polyester blend of the present invention are: A liquid crystal polyester that forms an anisotropic melt phase called a thermotropic liquid crystal polyester to those skilled in the art.

  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.

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、ｋおよびｌ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, k and l represent the mol% of the repeating unit represented by the formula [I] and the formula [II] in all 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 60 to 80 mol%, preferably 62 to 78 mol%, more preferably 65 to 75 mol% of the repeating unit represented by the formula [I], and The repeating unit represented by the formula [II] is contained in an amount of 0.1 to 10 mol%, preferably 0.5 to 7 mol%, more preferably 1 to 5 mol%, based on 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.

［式中、ｍは、液晶ポリエステル（Ａ）における全繰返し単位中の式［ＩＩＩ］で表される繰返し単位のモル％を示し、Ａｒ_１は、下記式：

または

で示される構造、またはその両方の構造を含む］
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 (A) has the following as an aromatic dioxy repeating unit:

[Wherein m represents the mol% of the repeating unit represented by the formula [III] in all repeating units in the liquid crystal polyester (A), and Ar ₁ represents the following formula:

Or

Including the structure indicated by or both]
The repeating unit represented by these is essentially included.

  The liquid crystal polyester resin (A) contains 10 to 20 mol%, preferably 10 to 18 mol%, more preferably 12 to 16 mol% of the repeating unit represented by the formula [III] with respect to all repeating units. Become.

  Monomers that give the repeating unit represented by the formula [III] include hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 2,6- Aromatic diols such as dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl ether, alkyl, alkoxy or halogen substituted products thereof, And ester-forming derivatives such as acylated products thereof. Among these, hydroquinone and 4,4′-dihydroxybiphenyl are preferable from the viewpoints of reactivity during polymerization, characteristics of the obtained liquid crystal polyester resin, and the like.

［式中、ｎは、液晶ポリエステル（Ａ）における全繰返し単位中の式［ＩＶ］で表される繰返し単位のモル％を示し、Ａｒ_２は、下記式：

または

で示される構造、またはその両方の構造を含む］
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。 Further, the liquid crystal polyester resin (A) is represented by the following formula [IV]:

[Wherein n represents mol% of the repeating unit represented by the formula [IV] in all repeating units in the liquid crystal polyester (A), and Ar ₂ represents the following formula:

Or

Including the structure indicated by or both]
Essentially comprising an aromatic dicarbonyl repeat unit represented by:

  The liquid crystal polyester resin (A) contains 10 to 20 mol%, preferably 10 to 18 mol%, more preferably 12 to 16 mol% of the repeating unit represented by the formula [IV] with respect to all repeating units. Become.

  Monomers that give the repeating unit represented by the formula [IV] include terephthalic acid, isophthalic acid, 4,4′-dicarboxybiphenyl, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2 , 7-naphthalenedicarboxylic acid, aromatic dicarboxylic acids such as 1,4-naphthalenedicarboxylic acid, and ester-forming derivatives such as ester derivatives and acid halides thereof. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable because the liquid crystal polyester from which terephthalic acid and 2,6-naphthalenedicarboxylic acid are obtained can easily adjust the mechanical properties, heat resistance, crystal melting temperature, and moldability to appropriate levels.

  In the liquid crystal polyester (A), k + l + m + n = 100.

  In the liquid crystal polyester (A), the content of the aromatic dioxy repeating unit represented by the formula [III] and the content of the aromatic dicarbonyl repeating unit represented by the formula [IV] are substantially equal. Mole is preferred.

Next, the liquid crystal polyester (B) will be described.
The liquid crystal polyester (B) 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.

で表されるｐ−オキシベンゾイル繰返し単位、および式［ＶＩ］：

［式中、ｐおよびｑはそれぞれ、液晶ポリエステル（Ｂ）における全繰返し単位中の式［Ｖ］および式［ＶＩ］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 (B) is represented by the following formula [V] as an aromatic oxycarbonyl repeating unit:

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

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

  The liquid crystalline polyester (B) contains 25 to 45 mol%, preferably 30 to 45 mol%, more preferably 30 to 40 mol% of the repeating unit represented by the formula [V], 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 [VI] with respect to all repeating units.

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

  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.

および式［ＶＩＩＩ］

［式中、ｒおよびｓはそれぞれ、液晶ポリエステル（Ｂ）における全繰返し単位中の式［ＶＩＩ］および式［ＶＩＩＩ］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。 In addition, the liquid crystal polyester resin (B) is represented by the following formula [VII]:

And the formula [VIII]

[Wherein, r and s respectively represent mol% of the repeating units represented by the formula [VII] and the formula [VIII] in all repeating units in the liquid crystal polyester (B)].
The repeating unit represented by these is essentially included.

  In the liquid crystal polyester resin (B), the repeating unit represented by the formula [VII] 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 [VIII] 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 (B) is a liquid crystal polyester (B) in which the composition ratio (mol%) in the liquid crystal polyester (B) of the repeating unit represented by the formula [VII] is represented by the formula [VIII]. It is more than the composition ratio (mol%). That is, when satisfying the relationship of r> s, it is preferable from the viewpoint of blister resistance.

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

  Examples of the monomer that gives the repeating unit represented by the formula [VIII] 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（Ｂ）における全繰返し単位中の式［ＩＸ］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。 Furthermore, the liquid crystalline polyester resin (B) has the formula [IX] shown below:

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

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

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

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

  Further, in the liquid crystal polyester (B), the total content of the aromatic dioxy repeating units represented by the formula [VII] and the formula [VIII] and the content of the aromatic dicarbonyl repeating unit represented by the formula [IX] Are preferably substantially equimolar.

  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 97/3 to 3/97, preferably 95/5 to 10/90, more preferably 95 /. 5-20 / 80.

  When (A) / (B) is larger than 97/3 or when (A) / (B) is smaller than 3/97, the fluidity is not sufficiently improved, which is not preferable.

  The liquid crystal polyester (A) and the liquid crystal polyester (B) used in the liquid crystal polyester blend of the present invention preferably have a crystal melting temperature of 300 to 350 ° C. measured by a differential scanning calorimeter. More preferably, it is particularly preferably 315 to 345 ° C.

  If the crystal melting temperature of the liquid crystal polyester (A) and the liquid crystal polyester (B) is lower than 300 ° C, the heat resistance tends to be lowered depending on the blending ratio of both, and if it exceeds 350 ° C, it is molded depending on the blending ratio of both. Since workability tends to decrease, it is not preferable.

  In the present invention, the crystal melting temperature (hereinafter also referred to as Tm) is measured by a differential scanning calorimeter. Specifically, the crystal melting temperature is measured by the following method. Using a differential scanning calorimeter, after measuring the endothermic peak temperature (Tm1) observed when the sample is measured at room temperature to 20 ° C./min, the sample is held at a temperature 50 ° C. higher than Tm1 for 10 minutes. . Next, the sample was cooled to room temperature under a temperature drop condition of 20 ° C./min, and an endothermic peak was measured again when measured under a temperature rise condition of 20 ° C./min. The temperature showing the peak top was the crystal melting temperature (Tm ).

  Since the liquid crystalline polyester blend of the present invention has a low dielectric constant in the high frequency band and excellent dielectric properties, when used as a material for various communication devices and electronic devices, the communication speed is increased and the transmission loss of electrical signals is reduced. It becomes possible.

  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 total of the liquid crystal polyester (A) and the liquid crystal poester (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 dielectric properties in a high frequency band, and is excellent in fluidity, blister resistance and mechanical strength, so that it is an electronic component 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 the synthesis examples, examples and comparative examples, the crystal melting temperature, fluidity, blister resistance, dielectric constant and tensile strength were measured by the following methods.

1) Crystal melting temperature After measuring the endothermic peak temperature (Tm1) observed when the sample was measured at 20 ° C./min from room temperature using Exstar 6000 manufactured by Seiko Instruments Inc. as a differential scanning calorimeter. , And hold at a temperature 50 ° C. higher than Tm1 for 10 minutes. Next, the sample was cooled to room temperature under a temperature drop condition of 20 ° C./min, and an endothermic peak was measured again when measured under a temperature rise condition of 20 ° C./min. The temperature showing the peak top was the crystal melting temperature (Tm ).

2) Fluidity Using an injection molding machine (UH1000-110 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, a cylinder temperature of 350 ° C. and an injection pressure of 40 MPa. The flow length at the time was evaluated.

3) Blister resistance A test piece of 62.5 × 12.7 × 0.8 mm was heat-treated for 10 minutes at 240 ° C. and 270 ° C. in a gear oven, and after cooling, a diameter of 1 mm found on the surface by visual observation. The number of blisters that occurred was observed. The test pieces with 0 to 1 blisters were evaluated as ◯, the test pieces as 2-3 were evaluated as Δ, and the test pieces as four or more were evaluated as X.

4) Dielectric constant 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. The dielectric constant at 1 GHz and 10 GHz was measured by a cavity resonator perturbation method using a vector network analyzer (manufactured by Agilent Technologies).

5) Tensile strength Injection molding was performed at a cylinder temperature of 350 ° C. and a mold temperature of 70 ° C. using an injection molding machine (MINIMAT M26 / 15 manufactured by Sumitomo Heavy Industries, Ltd.) with a clamping pressure of 15 tons. A 0 mm dumbbell-shaped test piece was obtained. The tensile test was performed using INSTRON 5567 (universal testing machine manufactured by Instron Japan Company Limited) at a span distance of 25.4 mm and a tensile speed of 5 mm / min.

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 NDA: 2,6-naphthalenedicarboxylic acid

Synthesis example 1
Synthesis of LCP-I (Liquid Crystalline Polyester (A))
A reaction vessel equipped with a stirrer with a torque meter and a distillation tube was charged with POB, BON6, HQ and NDA so as to give a total amount of 6.5 mol at the composition ratio shown in Table 1, and further the hydroxyl amount of all monomers ( Mole) was charged with 1.03 moles of acetic anhydride, 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, 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. The crystal melting temperature (Tm) of the obtained pellet was 321 ° C.

Synthesis example 2
Synthesis of LCP-II (Liquid Crystalline Polyester (B))
POB, BON6, HQ, BP and TPA are charged into a reaction vessel equipped with a stirrer with a torque meter and a distillation pipe so that the total amount is 6.5 mol at the composition ratio shown in Table 2, and the hydroxyl groups of all monomers are further added. 1.03 moles of acetic anhydride was charged with respect to the amount (mole), 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. The crystal melting temperature (Tm) of the obtained pellet was 335 ° C.

Synthesis example 3
Synthesis of LCP-III A reaction vessel equipped with a stirrer with a torque meter and a distillation tube was charged with POB and BON6 at a composition ratio shown in Table 3 so that the total amount was 6.5 mol, and the hydroxyl groups (moles) of all monomers. ) Was added in an amount of 1.03 moles of acetic anhydride, 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. The crystal melting temperature (Tm) of the obtained pellet was 278 ° C.

Examples 1-5
LCP-I and LCP-II were blended so as to have a weight ratio shown in Table 4, 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 constant and tensile strength were measured.

Comparative Example 1 and Comparative Example 2
For the liquid crystal polyesters LCP-I and LCP-II obtained in Synthesis Example 1 and Synthesis Example 2, the fluidity, blister resistance, dielectric constant and tensile strength were measured independently without blending.

Comparative Example 3
LCP-I and LCP-III were blended so as to have a weight ratio shown in Table 4, and a liquid crystal polyester blend was obtained as pellets in the same manner as in Example 1. Thereafter, fluidity, blister resistance, dielectric constant and tensile strength were measured.

  Table 4 shows the measurement and evaluation results of each example and comparative example.

  All of the liquid crystal polyester blends (Examples 1 to 5) of the present invention have fluidity as compared with Comparative Example 1 (liquid crystal polyester (A) alone, LCP-I) while maintaining dielectric properties and mechanical strength. Excellent, excellent in fluidity and blister resistance as compared with Comparative Example 2 (liquid crystal polyester (B) alone, LCP-II), and very excellent in blister resistance as compared with Comparative Example 3 (LCP-III) It was a thing.

  In Comparative Example 4 which is a liquid crystal polyester blend, the fluidity was improved as compared with LCP-I and LCP-III, but the blister resistance was not sufficient, and the values of dielectric constant were LCP-I and LCP-. It was higher than any of III and inferior in dielectric properties.

Claims (6)

(A) Formulas [I] to [IV] below:

[Where:
k, l, m and n represent the mole% of each repeating unit in all repeating units and satisfy the following conditions:
60 ≦ k ≦ 80;
0.1 ≦ l ≦ 10;
10 ≦ m ≦ 20;
10 ≦ n ≦ 20; and k + 1 + m + n = 100
Ar ₁ in the formula [III] represents the following formula:

Or

And Ar ₂ in the formula [IV] includes a structure represented by the following formula:

Or

Including the structure indicated by or both]
A wholly aromatic liquid crystal polyester comprising a repeating unit represented by formula (B) and the following formulas [V] to [IX]:

[Where
p, q, r, s, and t represent the mole% 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 liquid crystal polyester blend comprising a wholly aromatic liquid crystal polyester composed of a repeating unit represented by the formula (1) and having a weight ratio (A) / (B) of 97/3 to 3/97.   The liquid crystal polyester blend according to claim 1, wherein the crystal melting temperature of the liquid crystal polyester (A) and the liquid crystal polyester (B) measured by a differential scanning calorimeter is 300 to 350 ° C. A liquid crystal polyester blend composition comprising 100 parts by weight of the liquid crystal polyester blend according to any one of claims 1 and 2, 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 The liquid crystal polyester blend composition according to claim 3, 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 3, wherein the inorganic filler is glass fiber.   A molded article comprising the liquid crystal polyester blend according to any one of claims 1 and 2, or the liquid crystal polyester blend composition according to any one of claims 3 to 5.

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