JP6359225B2 - Liquid crystalline resin composition - Google Patents

Description

  The present invention relates to a liquid crystal resin composition.

  Liquid crystalline resins typified by liquid crystalline polyester resins have excellent mechanical strength, heat resistance, chemical resistance, electrical properties, etc. in a well-balanced manner and have excellent dimensional stability. It's being used. On the other hand, in recent years, remarkable technological development has been made in the field of information communication such as mobile phone; wireless LAN; ITS technology such as GPS, VICS (registered trademark) and ETC. Accordingly, there is an increasing need for high-performance high-frequency electronic components that can be applied in high-frequency regions such as microwaves and millimeter waves. A material constituting such an electronic component is required to have an appropriate dielectric property according to the design of the individual electronic component.

  For example, Patent Document 1 discloses an inorganic filler 0 to 90 to 45% by weight of a wholly aromatic liquid crystal polyester having a melting point of 320 ° C. or higher, 10 to 40% by weight of an inorganic spherical hollow body having an aspect ratio of 2 or less, and an aspect ratio of 4 or more. A wholly aromatic liquid crystal polyester resin composition molded article having a relative dielectric constant of 3.0 or less and a dielectric loss tangent of 0.04 or less obtained by injection molding a composition containing ˜15% by weight is solder reflow resistant, etc. And a molded body used for fixing or holding members of transmission / reception parts of information communication equipment used in a high frequency band such as microwaves and millimeter waves.

Japanese Patent Laid-Open No. 2004-27021

  However, according to the study by the present inventors, it has been found that a conventional liquid crystalline resin composition containing a hollow filler such as an inorganic spherical hollow body has extremely high melt viscosity and poor fluidity. Here, the increase in the melt viscosity of the liquid crystalline resin composition does not mean an increase in molecular weight and an improvement in heat resistance of the liquid crystalline resin itself constituting the liquid crystalline resin composition. Therefore, setting the molding temperature high in accordance with the increase in the melt viscosity of the liquid crystalline resin composition causes decomposition of the liquid crystalline resin, which is preferable as a method for improving the moldability of the liquid crystalline resin composition. Absent.

  The present invention has been made to solve the above problems, and an object of the present invention is to provide a low dielectric constant liquid crystalline resin composition having good moldability.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that by using a hollow filler having an aspect ratio of 1.15 or more, an increase in melt viscosity and a deterioration in fluidity are suppressed, and a liquid crystalline resin composition having a good moldability and a low dielectric constant can be obtained. The present invention has been completed. More specifically, the present invention provides the following.

  (1) A liquid crystalline resin composition comprising (A) a liquid crystalline resin and (B) a hollow filler having an aspect ratio of 1.15 or more.

  (2) The composition according to (1), wherein the component (B) is a glass balloon.

  (3) The content of the component (A) is 60% by mass or more and 95% by mass or less, and the content of the component (B) is 5% by mass or more and 20% by mass or less as described in (1) or (2). Composition.

  (4) The composition according to (1) or (2), further comprising (C) a plate-like filler.

  (5) The composition according to (4), wherein the component (C) is mica.

  (6) The content of component (A) is 60% by mass or more and less than 95% by mass, the content of component (B) is 5% by mass or more and 20% by mass or less, and the content of component (C) is 0. The composition according to (4) or (5), which is more than 20% by mass and 20% by mass or less.

  According to the present invention, it is possible to provide a low dielectric constant liquid crystalline resin composition having good moldability.

FIGS. 1A to 1C are ratios L / S calculated for individual particles of glass balloons 1 to 3 to be described later (where L is the length of the longest portion on the particle projection surface, respectively. The maximum length is shown, and S is a histogram showing the frequency distribution and cumulative frequency distribution of the maximum vertical length S which is the length of the longest portion in the direction perpendicular to the maximum length L on the particle projection plane. FIG. 2 is a top view showing the cutout positions of the test pieces for measuring the relative dielectric constant used in the examples and comparative examples.

  Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment.

<Liquid crystal resin composition>
The liquid crystalline resin composition according to the present invention contains (A) a liquid crystalline resin and (B) a hollow filler having an aspect ratio of 1.15 or more.

[(A) Liquid crystalline resin]
The (A) liquid crystalline resin used in the present invention refers to a melt processable polymer having a property capable of forming an optically anisotropic molten phase. The property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. When the liquid crystalline polymer applicable to the present invention is inspected between crossed polarizers, the polarized light is normally transmitted even in the molten stationary state, and optically anisotropic.

  The kind of the above (A) liquid crystalline resin is not particularly limited, and is preferably an aromatic polyester and / or an aromatic polyester amide. Moreover, the polyester which partially contains aromatic polyester and / or aromatic polyester amide in the same molecular chain is also within the range. (A) The liquid crystalline resin is preferably at least about 2.0 dl / g, more preferably 2.0 to 10.0 dl / g when dissolved in pentafluorophenol at 60 ° C. at a concentration of 0.1% by mass. Those having a logarithmic viscosity (IV) of 1 are preferably used.

  The aromatic polyester or aromatic polyester amide as the liquid crystalline resin (A) applicable to the present invention is particularly preferably at least one selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines. An aromatic polyester or an aromatic polyester amide having a structural unit derived from a kind of compound as a structural component.

More specifically,
(1) A polyester mainly composed of structural units derived from one or more aromatic hydroxycarboxylic acids and derivatives thereof;
(2) Mainly (a) a structural unit derived from one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof Or a polyester comprising a structural unit derived from two or more and (c) a structural unit derived from at least one or more of aromatic diol, alicyclic diol, aliphatic diol, and derivatives thereof;
(3) Mainly (a) a structural unit derived from one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or two aromatic hydroxyamines, aromatic diamines, and derivatives thereof A polyesteramide comprising a structural unit derived from at least one species and (c) a structural unit derived from one or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and derivatives thereof;
(4) A structural unit mainly derived from (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or two aromatic hydroxyamines, aromatic diamines, and derivatives thereof Structural units derived from more than one species, (c) structural units derived from one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof, and (d) aromatic diols, alicyclic rings And polyester amides composed of structural units derived from at least one or more of aliphatic diols, aliphatic diols, and derivatives thereof. Furthermore, you may use a molecular weight regulator together with said structural component as needed.

Preferable examples of the specific compound constituting the liquid crystalline resin (A) applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and 2,6-dihydroxy. Aromatic diols such as naphthalene, 1,4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcin, a compound represented by the following general formula (I), and a compound represented by the following general formula (II) Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III); p-aminophenol, p- Aromatic amines such as phenylenediamine and 4-acetoxyaminophenol are exemplified.
(X is a group selected from alkylene (C _{1 to} C ₄ ), alkylidene, —O—, —SO—, —SO ₂ —, —S—, and —CO—)
(Y is a group selected from — (CH ₂ ) _n — (n = 1 to 4) and —O (CH ₂ ) _n O— (n = 1 to 4).

The (A) liquid crystalline resin used in the present invention can be prepared from the above monomer compound (or a mixture of monomers) by a known method using a direct polymerization method or a transesterification method, and usually a melt polymerization method. Or a slurry polymerization method. The above compounds having ester-forming ability may be used for polymerization in the form as they are, or may be modified from a precursor to a derivative having ester-forming ability in the previous stage of polymerization. In the polymerization, various catalysts can be used. Typical examples include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, and alkali of carboxylic acid. And alkaline earth metal salts, Lewis acid salts such as BF _{3 and} the like. The amount of the catalyst used is generally about 0.001 to 1% by weight, particularly about 0.01 to 0.2% by weight, based on the total weight of the monomers. If the polymer produced by these polymerization methods is further necessary, the molecular weight can be increased by solid-phase polymerization by heating in a reduced pressure or an inert gas.

The melt viscosity of the (A) liquid crystalline resin obtained by the above method is not particularly limited. Generally, those having a melt viscosity at a molding temperature of 10 MPa or more and 600 MPa or less at a shear rate of 1000 sec ⁻¹ can be used. However, those having a very high viscosity are not preferable because the fluidity is extremely deteriorated. The (A) liquid crystalline resin may be a mixture of two or more liquid crystalline resins.

  In the liquid crystalline resin composition according to the present invention, the content of the component (A) is preferably 60% by mass to 95% by mass, more preferably 64% by mass to 93% by mass, and still more preferably 69% by mass. It is 90 mass% or less. In particular, when the liquid crystalline resin composition according to the present invention contains (C) a plate-like filler, the content of the component (A) is preferably 60% by mass or more in the liquid crystalline resin composition according to the present invention. It is less than 95% by mass, more preferably 64% by mass to 93% by mass, and even more preferably 69% by mass to 90% by mass. When the content of the component (A) is 60% by mass or more, the fluidity at the time of melting the composition is easily improved. When the content of the component (A) is 95% by mass or less or less than 95% by mass, the content of the component (B) is sufficient, so that the obtained liquid crystalline resin composition tends to have a low dielectric constant.

[(B) Hollow filler having an aspect ratio of 1.15 or more]
(B) The hollow filler is generally called a balloon, and examples of the material of the hollow sphere include inorganic materials such as alumina, silica, and glass; organic materials such as urea resin and phenol resin. It is done. Among these, glass is preferable from the viewpoint of heat resistance and strength. That is, a glass balloon is preferably used as the hollow filler. (B) A component may be used independently or may use 2 or more types together.

  (B) Since the hollow filler has an aspect ratio of 1.15 or more, the anisotropy is larger than that of the hollow filler having an aspect ratio of less than 1.15. Therefore, in the composition containing the (B) hollow filler, since the high molecular orientation that exhibits the good fluidity of the liquid crystalline resin is less likely to be disturbed, an increase in melt viscosity and fluidity deterioration are likely to be suppressed. Guessed.

  (B) The aspect ratio of the hollow filler is 1.15 or more, preferably 1.20 or more and 2.00 or less, more preferably from the viewpoints of increase in melt viscosity, suppression of fluidity deterioration and moldability. It is 1.22 or more and 1.50 or less, and still more preferably 1.25 or more and less than 1.30.

  In this specification, as an aspect ratio, using a dynamic image analysis method / particle state analyzer, the maximum length L which is the length of the longest portion on the particle projection surface and the maximum length L on the particle projection surface The maximum vertical length S, which is the length of the longest part in the vertical direction, is measured for 3000 particles, and the measurement is repeated several times, and the average value of the ratio L / S calculated for each particle is adopted. To do.

  The average particle diameter of the component (B) is preferably 5 μm or more from the viewpoint of moldability, more preferably 10 μm or more, and preferably 200 μm or less from the viewpoint of suppressing the destruction of the component (B) and moldability. More preferably, it is 100 micrometers or less, More preferably, it is 50 micrometers or less. In the present specification, the value (D50) measured by the laser diffraction / scattering particle size distribution measurement method is employed as the average particle size of the component (B).

  In the liquid crystalline resin composition according to the present invention, the content of the component (B) is preferably 5% by mass or more and 20% by mass or less, more preferably 7% by mass or more and 18% by mass or less, and still more preferably 10% by mass. The content is 15% by mass or less. When the content of the component (B) is 5% by mass or more, the obtained liquid crystalline resin composition tends to have a low dielectric constant. When the content of the component (B) is 20% by mass or less, the fluidity at the time of melting of the composition is easily improved.

[(C) Plate-like filler]
The liquid crystalline resin composition according to the present invention may optionally contain (C) a plate-like filler. (C) The plate-like filler acts as a warpage suppressing filler in the molded product of the liquid crystalline resin composition. (C) A component may be used independently or may use 2 or more types together.

  According to the study by the present inventors, a conventional liquid crystalline resin composition containing a hollow filler gives a molded product having a large warpage, and suppresses warpage of a plate-like filler or the like in order to reduce the warpage. It has been found that when the filler is further added to the above conventional liquid crystalline resin composition, the fluidity first deteriorates. However, in the liquid crystalline resin composition according to the present invention, (B) by using a hollow filler having an aspect ratio of 1.15 or more, even when (C) a plate-like filler is added, it is satisfactory. While ensuring the fluidity, the warpage of the molded body can be reduced, and the dimensional stability is excellent.

  (C) The plate-like filler preferably has an average particle size of 15 to 50 μm. When the average particle size is 15 μm or more, necessary mechanical strength is easily secured, and the effect of suppressing warpage of the molded body is likely to increase. When the average particle size is 50 μm or less, the fluidity at the time of melting of the composition is likely to be improved. The average particle size is preferably 20 to 30 μm. In the present specification, the value (MV) measured by the laser diffraction / scattering particle size distribution measurement method is employed as the average particle diameter of the component (C).

  (C) It does not specifically limit as a plate-shaped filler, For example, mica, talc, glass flakes, graphite, various metal foils (for example, aluminum foil, iron foil, copper foil) etc. are mentioned. In the present invention, it is preferable to use mica as the component (C).

  In the liquid crystalline resin composition according to the present invention, the content of the component (C) is preferably more than 0% by mass and 20% by mass or less, more preferably 5% by mass to 18% by mass, and still more preferably 10%. It is at least 16% by mass. When the content of the component (C) is more than 0% by mass, the required mechanical strength is easily ensured, and the effect of suppressing the warpage of the molded body tends to be high. When the content of the component (C) is 20% by mass or less, the fluidity at the time of melting of the composition is easily improved.

[Other ingredients]
The liquid crystalline resin composition according to the present invention includes other polymers, other fillers, and generally known substances that are generally added to synthetic resins, that is, antioxidants and ultraviolet rays, within a range that does not impair the effects of the present invention. Stabilizers such as absorbents, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, mold release agents, crystallization accelerators, crystal nucleating agents, and the like can be appropriately added according to the required performance.

  Examples of other polymers include an epoxy group-containing copolymer. Other fillers refer to fillers other than (B) hollow fillers and (C) plate-like fillers, for example, fibrous fillers such as glass fibers; particulate fillers such as silica; and carbon black. .

[Preparation of liquid crystalline resin composition]
The preparation of the liquid crystalline resin composition according to the present invention is not particularly limited. For example, (A) component, (B) component, optionally (C) component, and optionally other components are blended, and these are melt kneaded using a single screw or twin screw extruder to obtain liquid crystal Preparation of a functional resin composition is performed.

[Liquid Crystalline Resin Composition]

The liquid crystalline resin composition according to the present invention obtained as described above preferably has a melt viscosity of less than 45 Pa · sec, more preferably 42 Pa · sec or less, and even more preferably 40 Pa · sec or less. One of the characteristics of the liquid crystalline resin composition according to the present invention is that the fluidity at the time of melting is high and the moldability is excellent. In this specification, as the melt viscosity, a value obtained by a measurement method based on ISO 11443 under conditions of a cylinder temperature 10 to 30 ° C. higher than the melting point of the liquid crystalline resin and a shear rate of 1000 sec ⁻¹ is adopted.

  The relative dielectric constant of the liquid crystalline resin composition according to the present invention is preferably 3.2 or less, more preferably 3.1 or less, and even more preferably 3.0 or less. The low dielectric constant is also one of the characteristics of the liquid crystalline resin composition according to the present invention.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited only to these examples.

<Liquid crystal resin>
・ Liquid crystalline polyester amide resin (LCP1)
After the following raw materials were charged into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C. and reacted at 140 ° C. for 1 hour. Thereafter, the temperature is further raised to 340 ° C. over 4.5 hours, and then the pressure is reduced to 10 Torr (ie, 1330 Pa) over 15 minutes while acetic acid, excess acetic anhydride, and other low-boiling components are distilled off. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced and the pressure was changed from the reduced pressure state to the normal pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain pellets. The obtained pellets were heat-treated at 300 ° C. for 2 hours under a nitrogen stream to obtain the target polymer. The melting point of the obtained polymer was 334 ° C., and the melt viscosity at 350 ° C. was 19.0 Pa · s. The melt viscosity of the polymer was measured in the same manner as the melt viscosity measurement method described later.
(I) 4-hydroxybenzoic acid (HBA); 188.4 g (60 mol%)
(II) 2-hydroxy-6-naphthoic acid (HNA); 21.4 g (5 mol%)
(III) Terephthalic acid (TA); 66.8 g (17.7 mol%)
(IV) 4,4′-dihydroxybiphenyl (BP); 52.2 g (12.3 mol%)
(V) 4-acetoxyaminophenol (APAP); 17.2 g (5 mol%)
Metal catalyst (potassium acetate catalyst); 15 mg
Acylating agent (acetic anhydride); 226.2 g

・ Liquid crystalline polyester resin (LCP2)
After the following raw materials were charged into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C. and reacted at 140 ° C. for 1 hour. Thereafter, the temperature is further increased to 360 ° C. over 5.5 hours, and then the pressure is reduced to 5 Torr (ie, 667 Pa) over 30 minutes, while acetic acid, excess acetic anhydride, and other low boiling points are distilled off. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced and the pressure was changed from the reduced pressure state to the normal pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain pellets. The obtained pellets were heat-treated at 300 ° C. for 8 hours under a nitrogen stream to obtain the target polymer. The melting point of the obtained polymer was 352 ° C. and the melt viscosity at 380 ° C. was 27.0 Pa · s. The melt viscosity of the polymer was measured in the same manner as the melt viscosity measurement method described later.
(I) 2-hydroxy-6-naphthoic acid (HNA); 166 g (48 mol%)
(II) Terephthalic acid (TA); 76 g (25 mol%)
(III) 4,4′-dihydroxybiphenyl (BP); 86 g (25 mol%)
(IV) 4-hydroxybenzoic acid (HBA); 5 g (2 mol%)
Metal catalyst (potassium acetate catalyst); 22.5 mg
Acylating agent (acetic anhydride); 191 g

<Material other than liquid crystalline resin>
Glass balloon 1: Y12000 (manufactured by Seishin Co., Ltd., aspect ratio (average) 1.264, average particle size (D50) 35 μm)
Glass balloon 2: S60HS (Sumitomo 3M Co., Ltd., aspect ratio (average) 1.091, average particle size (D50) 24 μm)
Glass balloon 3: im30K (Sumitomo 3M Co., Ltd., aspect ratio (average) 1.072, average particle size (D50) 18 μm)
Plate filler: AB-25S (manufactured by Yamaguchi Mica, Mica, average particle size (MV) 24 μm)
-Fibrous filler: ECS03T-786H (manufactured by Nippon Electric Glass Co., Ltd., glass fiber, fiber diameter 10 μm, chopped strand having a length of 3 mm)

<Manufacture of liquid crystalline resin composition>
The above components were melt kneaded at the following cylinder temperature using a twin screw extruder (TEX30α type, manufactured by Nippon Steel Works) at the ratio shown in Table 1 to obtain liquid crystalline resin composition pellets.
[Production conditions]
Cylinder temperature:
350 ° C: In the case of a liquid crystalline resin composition containing a liquid crystalline polyester amide resin (LCP1) 370 ° C: In the case of a liquid crystalline resin composition containing a liquid crystalline polyester resin (LCP2)

<Aspect ratio measurement of glass balloon>
3,000 glass balloon particles were measured using a dynamic image analysis method / particle state analyzer “PITA-3” manufactured by Seishin Co., Ltd., using an optical lens with a magnification of 4 × equipped in the analyzer. The maximum length L that is the length of the longest portion on the particle projection surface and the maximum vertical length S that is the length of the longest portion in the direction perpendicular to the maximum length L on the particle projection surface were measured. This measurement was repeated several times, and the frequency distribution of the ratio L / S calculated for each particle was shown in the histogram, and the average value of the ratio L / S was calculated and adopted as the aspect ratio of the glass balloon. In the measurement, the glass balloon is diluted with an aqueous solution for dilution containing an appropriate amount of a surfactant, the concentration of the glass balloon is adjusted to 3.3 mg / mL, and the glass balloon is dispersed in the aqueous solution by ultrasonic cleaning. A glass balloon dispersion was obtained, and this glass balloon dispersion was used as a measurement sample. 1A to 1C are histograms showing the frequency distribution and cumulative frequency distribution of the ratio L / S calculated for the individual particles of the glass balloons 1 to 3, respectively.

<Melt viscosity>
The melt viscosity of the liquid crystalline resin compositions of Examples and Comparative Examples was measured using the pellets. Specifically, a capillary type rheometer (manufactured by Toyo Seiki Seisakusho Co., Ltd., Capillograph 1D: piston diameter 10 mm) at a temperature 10 to 30 ° C. higher than the melting point of the liquid crystalline resin and a shear rate of 1000 sec ⁻¹ . The apparent melt viscosity was measured according to ISO 11443. For the measurement, an orifice having an inner diameter of 1 mm and a length of 20 mm was used. The specific measurement temperatures are 350 ° C. for the liquid crystalline resin composition containing the liquid crystalline polyester amide resin (LCP1) and 380 ° C. for the liquid crystalline resin composition containing the liquid crystalline polyester resin (LCP2). there were. The results are shown in Table 1.

<Flatness>
The pellets of Examples and Comparative Examples were molded under the following molding conditions using a molding machine (“SE-100DU” manufactured by Sumitomo Heavy Industries, Ltd.), and 5 flat plate test pieces of 80 mm × 80 mm × 1 mm were formed. A sheet was produced. The first flat plate test piece was left on a horizontal plane, and a CNC image measuring machine (model: QVBHU404-PRO1F) manufactured by Mitutoyo Co., Ltd. was used at nine locations on the flat plate test piece from the horizontal plane. The height was measured, and the average height was calculated from the obtained measurement values. The position where the height was measured is that each vertex of this square is placed on a principal plane of a flat specimen when a square with a side of 74 mm is placed so that the distance from each side of the principal plane is 3 mm. , A position corresponding to the midpoint of each side of the square and the intersection of two diagonal lines of the square. The height from the horizontal plane was the same as the average height, and a plane parallel to the horizontal plane was used as a reference plane. The maximum height and the minimum height from the reference plane were selected from the heights measured at the nine locations, and the difference between the two was calculated. Similarly, the above difference was calculated for the other four flat test pieces, and the obtained five values were averaged to obtain the flatness value. The results are shown in Table 1.
〔Molding condition〕
Cylinder temperature:
350 ° C .: In the case of a liquid crystalline resin composition containing a liquid crystalline polyester amide resin (LCP1) 370 ° C .: In the case of a liquid crystalline resin composition containing a liquid crystalline polyester resin (LCP2) Mold temperature: 80 ° C.
Injection speed: 33mm / sec
Holding pressure: 60 MPa

<Relative permittivity>
The pellets of Examples and Comparative Examples were molded under the following molding conditions using a molding machine (“SE-100DU” manufactured by Sumitomo Heavy Industries, Ltd.) to produce a flat test piece of 80 mm × 80 mm × 1 mm. did. As shown in FIG. 2, a test piece of 80 mm × 1 mm × 1 mm was cut out from the center of the flat test piece in the direction perpendicular to the flow, and this was used as a test piece for measuring the relative dielectric constant. About this test piece, the relative dielectric constant in 1 GHz was measured using the cavity resonator perturbation method complex dielectric constant evaluation apparatus of the following structures made from Kanto Electronics Co., Ltd. development.
Scalar Network Analyzer: Agilent Technologies 8757D
Frequency synthesizer: Agilent Technology 83650L sweep CW generator Fixed attenuator: Agilent Technology 85025D detector Cavity resonator: Kanto Electronics Application Development CP431
Measurement program: Kanto Electronics Application Development CPMA-S2 / V2
〔Molding condition〕
Cylinder temperature:
350 ° C .: In the case of a liquid crystalline resin composition containing a liquid crystalline polyester amide resin (LCP1) 370 ° C .: In the case of a liquid crystalline resin composition containing a liquid crystalline polyester resin (LCP2) Mold temperature: 80 ° C.
Injection speed: 33mm / sec
Holding pressure: 60 MPa

  As is clear from the results shown in Table 1, the liquid crystalline resin compositions of the examples had good moldability and a low dielectric constant. In addition, the liquid crystalline resin compositions of the examples maintained good moldability even when mica was added.

Claims (5)

A liquid crystalline resin composition comprising (A) a liquid crystalline resin and (B) a hollow filler having an aspect ratio of 1.15 or more, wherein (B) the component is a glass balloon ,
The aspect ratio is determined by using a dynamic image analysis method / particle state analyzer, and the maximum length L which is the length of the longest portion on the particle projection surface and the direction perpendicular to the maximum length L on the particle projection surface. The maximum vertical length S, which is the length of the long portion, was measured for 3000 particles, and the measurement was repeated several times to obtain an arithmetic average value of the ratio L / S calculated for each particle. Composition .   The composition according to claim 1, wherein the content of the component (A) is 60% by mass or more and 95% by mass or less, and the content of the component (B) is 5% by mass or more and 20% by mass or less.   The composition according to claim 1, further comprising (C) a plate-like filler.   The composition according to claim 3, wherein the component (C) is mica.   The content of the component (A) is 60% by mass or more and less than 95% by mass, the content of the component (B) is 5% by mass or more and 20% by mass or less, and the content of the component (C) is more than 0% by mass. It is 20 mass% or less, The composition of Claim 3 or 4.