WO2017179474A1 - Liquid-crystalline resin composition - Google Patents
Liquid-crystalline resin composition Download PDFInfo
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- WO2017179474A1 WO2017179474A1 PCT/JP2017/014287 JP2017014287W WO2017179474A1 WO 2017179474 A1 WO2017179474 A1 WO 2017179474A1 JP 2017014287 W JP2017014287 W JP 2017014287W WO 2017179474 A1 WO2017179474 A1 WO 2017179474A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
Definitions
- 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.
- 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.
- 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 molded product of wholly aromatic liquid crystal polyester resin composition 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.
- 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.
- a conventional liquid crystalline resin composition containing a hollow filler such as an inorganic spherical hollow body has a remarkably high melt viscosity and poor fluidity.
- 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 liquid crystal resin composition having a low dielectric constant and 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.
- 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.
- composition according to (1) wherein the component (B) is a glass balloon.
- the content of (A) component is 60% by mass or more and 95% by mass or less, and the content of (B) component is 5% by mass or more and 20% by mass or less as described in (1) or (2) Composition.
- composition according to (1) or (2) further comprising (C) a plate-like filler.
- 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.
- liquid crystal resin composition having a low dielectric constant and good moldability.
- FIG. 1 (a) to 1 (c) are ratios L / S calculated for individual particles of glass balloons 1 to 3 described later (where L is the length of the longest portion on the particle projection surface, respectively).
- L is the length of the longest portion on the particle projection surface, respectively.
- 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.
- 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.
- 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.
- 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 type of (A) liquid crystalline resin as described above 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.
- 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 a concentration of 0.1% by mass at 60 ° C. 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.
- Specific 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, compounds represented by the following general formula (I), and compounds 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- And aromatic amines such as phenylenediamine and 4-acetoxyaminophenol.
- X is a group selected from alkylene (C 1 -C 4 ), alkylidene, —O—, —SO—, —SO 2 —, —S—, and —CO—)
- 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.
- 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.
- 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 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. In general, 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.
- 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.
- 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.
- the content of the component (A) is 60% by mass or more, the fluidity at the time of melting the composition is easily improved.
- 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.
- 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.
- a component may be used independently or may use 2 or more types together.
- 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.
- 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.
- 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 ⁇ m or more from the viewpoint of moldability, more preferably 10 ⁇ m or more, and preferably 200 ⁇ m 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.
- 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).
- 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.
- 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.
- 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.
- the liquid crystalline resin composition according to the present invention may optionally contain (C) a plate-like filler.
- the plate-like filler acts as a warpage suppressing filler in the molded product of the liquid crystalline resin composition.
- a component may be used independently or may use 2 or more types together.
- 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.
- (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.
- the plate-like filler preferably has an average particle size of 15 to 50 ⁇ m.
- the average particle size is 15 ⁇ m or more, necessary mechanical strength is easily secured, and the effect of suppressing warpage of the molded body is likely to increase.
- the average particle size is 50 ⁇ m or less, the fluidity at the time of melting of the composition is likely to be improved.
- the average particle diameter is preferably 20 to 30 ⁇ m.
- 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).
- the plate-like filler is not particularly limited, and examples thereof include mica, talc, glass flake, graphite, various metal foils (for example, aluminum foil, iron foil, copper foil) and the like. In the present invention, it is preferable to use mica as the component (C).
- 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.
- 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.
- 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.
- 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 epoxy group-containing copolymers.
- 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. .
- the preparation of the liquid crystalline resin composition according to the present invention is not particularly limited.
- (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.
- 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.
- the melt viscosity is 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 .
- 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.
- Liquid crystal resin > ⁇ Liquid crystalline polyester amide resin (LCP1)
- 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.
- 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.
- 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.
- 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.
- HNA 2-hydroxy-6-naphthoic acid
- TA Terephthalic acid
- BP 4,4′-dihydroxybiphenyl
- HBA 4-hydroxybenzoic acid
- Metal catalyst potassium acetate catalyst
- Acylating agent acetic anhydride
- ⁇ Aspect ratio measurement of glass balloon> 3000 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.
- 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.
- FIGS. 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.
- 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.
- 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.
- Table 1 The results are shown in Table 1.
- the liquid crystalline resin compositions of the examples had good moldability and a low dielectric constant.
- the liquid crystalline resin compositions of the examples maintained good moldability even when mica was added.
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Abstract
Provided is a liquid-crystalline resin composition which has satisfactory moldability and has a low permittivity. The liquid-crystalline resin composition according to the present invention comprises (A) a liquid-crystalline resin and (B) a hollow filler having an aspect ratio of 1.15 or higher. It is preferable that the component (B) be glass balloons. It is preferable that the liquid-crystalline resin composition have a content of component (A) of 60-95 mass% and a content of component (B) of 5-20 mass%. It is preferable that the liquid-crystalline resin composition according to the present invention should further contain (C) a platy filler. It is preferable that the component (C) be mica. It is preferable that the liquid-crystalline resin composition have a content of component (A) of 60 mass% or higher but less than 95 mass%, a content of component (B) of 5-20 mass%, and a content of component (C) higher than 0 mass% but not higher than 20 mass%.
Description
本発明は、液晶性樹脂組成物に関する。
The present invention relates to a liquid crystal resin composition.
液晶性ポリエステル樹脂に代表される液晶性樹脂は、優れた機械的強度、耐熱性、耐薬品性、電気的性質等をバランス良く有し、優れた寸法安定性も有するため高機能エンジニアリングプラスチックとして広く利用されている。一方、近年、携帯電話；無線ＬＡＮ；ＧＰＳ、ＶＩＣＳ（登録商標）、ＥＴＣ等のＩＴＳ技術等の情報通信分野において著しい技術発達がなされている。これに応じて、マイクロ波、ミリ波等の高周波領域において適用できる高性能な高周波対応電子部品のニーズが強くなっている。このような電子部品を構成する材料は、個々の電子部品の設計に応じて、適切な誘電特性を有することが求められている。
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.
例えば、特許文献１には、融点３２０℃以上の全芳香族液晶ポリエステル９０～４５重量％、アスペクト比が２以下の無機球状中空体１０～４０重量％、アスペクト比が４以上の無機充填剤０～１５重量％を配合した組成物を射出成形して得られる、比誘電率が３．０以下、誘電正接が０．０４以下の全芳香族液晶ポリエステル樹脂組成物成形体が、耐ハンダリフロー等の耐熱性を有し、誘電特性に優れ、マイクロ波、ミリ波等の高周波帯域で用いられる情報通信機器の送受信部品の固定あるいは保持部材に用いられる成形体が開示されている。
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 molded product of wholly aromatic liquid crystal polyester resin composition 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.
しかし、本発明者らの検討によれば、無機球状中空体等の中空フィラーを含有する従来の液晶性樹脂組成物は、溶融粘度が著しく高く、流動性が不良であることが判明した。ここで、液晶性樹脂組成物の溶融粘度の上昇は、当該液晶性樹脂組成物を構成する液晶性樹脂そのものの分子量の増加及び耐熱性の向上を意味するものではない。よって、液晶性樹脂組成物の溶融粘度の上昇に合わせて成形温度を高く設定することは、液晶性樹脂の分解を引き起こしてしまい、当該液晶性樹脂組成物の成形性を向上させる方法としては好ましくない。
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 a remarkably 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.
本発明は、上記課題を解決するためになされたものであり、その目的は、成形性の良好な低誘電率の液晶性樹脂組成物を提供することにある。
The present invention has been made to solve the above problems, and an object of the present invention is to provide a liquid crystal resin composition having a low dielectric constant and good moldability.
本発明者らは、上記課題を解決するために鋭意研究を重ねた。その結果、アスペクト比が１．１５以上である中空フィラーを用いることで、溶融粘度上昇及び流動性悪化が抑制され、成形性の良好な低誘電率の液晶性樹脂組成物が得られることを見出し、本発明を完成するに至った。より具体的には本発明は以下のものを提供する。
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）液晶性樹脂と、（Ｂ）アスペクト比が１．１５以上である中空フィラーと、を含有する液晶性樹脂組成物。
(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） （Ｂ）成分がガラスバルーンである（１）に記載の組成物。
(2) The composition according to (1), wherein the component (B) is a glass balloon.
（３） （Ａ）成分の含有量が６０質量％以上９５質量％以下であり、（Ｂ）成分の含有量が５質量％以上２０質量％以下である（１）又は（２）に記載の組成物。
(3) The content of (A) component is 60% by mass or more and 95% by mass or less, and the content of (B) component is 5% by mass or more and 20% by mass or less as described in (1) or (2) Composition.
（４） 更に、（Ｃ）板状充填剤を含有する（１）又は（２）に記載の組成物。
(4) The composition according to (1) or (2), further comprising (C) a plate-like filler.
（５） （Ｃ）成分がマイカである（４）に記載の組成物。
(5) The composition according to (4), wherein the component (C) is mica.
（６） （Ａ）成分の含有量が６０質量％以上９５質量％未満であり、（Ｂ）成分の含有量が５質量％以上２０質量％以下であり、（Ｃ）成分の含有量が０質量％超２０質量％以下である（４）又は（５）に記載の組成物。
(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.
本発明によれば、成形性の良好な低誘電率の液晶性樹脂組成物を提供することができる。
According to the present invention, it is possible to provide a liquid crystal resin composition having a low dielectric constant and good moldability.
以下、本発明の実施形態について説明する。なお、本発明は以下の実施形態に限定されない。
Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment.
＜液晶性樹脂組成物＞
本発明に係る液晶性樹脂組成物は、（Ａ）液晶性樹脂と、（Ｂ）アスペクト比が１．１５以上である中空フィラーと、を含有する。 <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.
本発明に係る液晶性樹脂組成物は、（Ａ）液晶性樹脂と、（Ｂ）アスペクト比が１．１５以上である中空フィラーと、を含有する。 <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）液晶性樹脂］
本発明で使用する（Ａ）液晶性樹脂とは、光学異方性溶融相を形成し得る性質を有する溶融加工性ポリマーを指す。異方性溶融相の性質は、直交偏光子を利用した慣用の偏光検査法により確認することが出来る。より具体的には、異方性溶融相の確認は、Ｌｅｉｔｚ偏光顕微鏡を使用し、Ｌｅｉｔｚホットステージに載せた溶融試料を窒素雰囲気下で４０倍の倍率で観察することにより実施できる。本発明に適用できる液晶性ポリマーは直交偏光子の間で検査したときに、たとえ溶融静止状態であっても偏光は通常透過し、光学的に異方性を示す。 [(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.
本発明で使用する（Ａ）液晶性樹脂とは、光学異方性溶融相を形成し得る性質を有する溶融加工性ポリマーを指す。異方性溶融相の性質は、直交偏光子を利用した慣用の偏光検査法により確認することが出来る。より具体的には、異方性溶融相の確認は、Ｌｅｉｔｚ偏光顕微鏡を使用し、Ｌｅｉｔｚホットステージに載せた溶融試料を窒素雰囲気下で４０倍の倍率で観察することにより実施できる。本発明に適用できる液晶性ポリマーは直交偏光子の間で検査したときに、たとえ溶融静止状態であっても偏光は通常透過し、光学的に異方性を示す。 [(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.
上記のような（Ａ）液晶性樹脂の種類としては特に限定されず、芳香族ポリエステル及び／又は芳香族ポリエステルアミドであることが好ましい。また、芳香族ポリエステル及び／又は芳香族ポリエステルアミドを同一分子鎖中に部分的に含むポリエステルもその範囲にある。（Ａ）液晶性樹脂としては、６０℃でペンタフルオロフェノールに濃度０．１質量％で溶解したときに、好ましくは少なくとも約２．０ｄｌ／ｇ、更に好ましくは２．０～１０．０ｄｌ／ｇの対数粘度（Ｉ．Ｖ．）を有するものが好ましく使用される。
The type of (A) liquid crystalline resin as described above 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 a concentration of 0.1% by mass at 60 ° C. Those having a logarithmic viscosity (IV) of 1 are preferably used.
本発明に適用できる（Ａ）液晶性樹脂としての芳香族ポリエステル又は芳香族ポリエステルアミドは、特に好ましくは、芳香族ヒドロキシカルボン酸、芳香族ヒドロキシアミン、及び芳香族ジアミンからなる群より選ばれる少なくとも１種の化合物に由来する構成単位を構成成分として有する芳香族ポリエステル又は芳香族ポリエステルアミドである。
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.
より具体的には、
（１）主として芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する構成単位からなるポリエステル；
（２）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する構成単位と、（ｂ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上に由来する構成単位と、（ｃ）芳香族ジオール、脂環族ジオール、脂肪族ジオール、及びそれらの誘導体の少なくとも１種又は２種以上に由来する構成単位、とからなるポリエステル；
（３）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する構成単位と、（ｂ）芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体の１種又は２種以上に由来する構成単位と、（ｃ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上に由来する構成単位、とからなるポリエステルアミド；
（４）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する構成単位と、（ｂ）芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体の１種又は２種以上に由来する構成単位と、（ｃ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上に由来する構成単位と、（ｄ）芳香族ジオール、脂環族ジオール、脂肪族ジオール、及びそれらの誘導体の少なくとも１種又は２種以上に由来する構成単位、とからなるポリエステルアミド等が挙げられる。更に上記の構成成分に必要に応じ分子量調整剤を併用してもよい。 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.
（１）主として芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する構成単位からなるポリエステル；
（２）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する構成単位と、（ｂ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上に由来する構成単位と、（ｃ）芳香族ジオール、脂環族ジオール、脂肪族ジオール、及びそれらの誘導体の少なくとも１種又は２種以上に由来する構成単位、とからなるポリエステル；
（３）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する構成単位と、（ｂ）芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体の１種又は２種以上に由来する構成単位と、（ｃ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上に由来する構成単位、とからなるポリエステルアミド；
（４）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する構成単位と、（ｂ）芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体の１種又は２種以上に由来する構成単位と、（ｃ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上に由来する構成単位と、（ｄ）芳香族ジオール、脂環族ジオール、脂肪族ジオール、及びそれらの誘導体の少なくとも１種又は２種以上に由来する構成単位、とからなるポリエステルアミド等が挙げられる。更に上記の構成成分に必要に応じ分子量調整剤を併用してもよい。 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.
本発明に適用できる（Ａ）液晶性樹脂を構成する具体的化合物の好ましい例としては、ｐ－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸等の芳香族ヒドロキシカルボン酸、２，６－ジヒドロキシナフタレン、１，４－ジヒドロキシナフタレン、４，４’－ジヒドロキシビフェニル、ハイドロキノン、レゾルシン、下記一般式（Ｉ）で表される化合物、及び下記一般式（ＩＩ）で表される化合物等の芳香族ジオール；テレフタル酸、イソフタル酸、４，４’－ジフェニルジカルボン酸、２，６－ナフタレンジカルボン酸、及び下記一般式（ＩＩＩ）で表される化合物等の芳香族ジカルボン酸；ｐ－アミノフェノール、ｐ－フェニレンジアミン、４－アセトキシアミノフェノール等の芳香族アミン類が挙げられる。
（Ｘ：アルキレン（Ｃ１～Ｃ４）、アルキリデン、－Ｏ－、－ＳＯ－、－ＳＯ２－、－Ｓ－、及び－ＣＯ－より選ばれる基である）
（Ｙ：－（ＣＨ２）ｎ－（ｎ＝１～４）及び－Ｏ（ＣＨ２）ｎＯ－（ｎ＝１～４）より選ばれる基である。）
Specific 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, compounds represented by the following general formula (I), and compounds 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- And aromatic amines such as phenylenediamine and 4-acetoxyaminophenol.
(X is a group selected from alkylene (C 1 -C 4 ), alkylidene, —O—, —SO—, —SO 2 —, —S—, and —CO—)
(Y: a group selected from — (CH 2 ) n — (n = 1 to 4) and —O (CH 2 ) n O— (n = 1 to 4).
本発明に用いられる（Ａ）液晶性樹脂の調製は、上記のモノマー化合物（又はモノマーの混合物）から直接重合法やエステル交換法を用いて公知の方法で行うことができ、通常は溶融重合法やスラリー重合法等が用いられる。エステル形成能を有する上記化合物類はそのままの形で重合に用いてもよく、また、重合の前段階で前駆体から該エステル形成能を有する誘導体に変性されたものでもよい。これらの重合に際しては種々の触媒の使用が可能であり、代表的なものとしては、ジアルキル錫酸化物、ジアリール錫酸化物、２酸化チタン、アルコキシチタンけい酸塩類、チタンアルコラート類、カルボン酸のアルカリ及びアルカリ土類金属塩類、ＢＦ３の如きルイス酸塩等があげられる。触媒の使用量は一般にはモノマーの全質量に対して約０．００１～１質量％、特に約０．０１～０．２質量％が好ましい。これらの重合方法により製造されたポリマーは更に必要があれば、減圧又は不活性ガス中で加熱する固相重合により分子量の増加を図ることができる。
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 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.
上記のような方法で得られた（Ａ）液晶性樹脂の溶融粘度は特に限定されない。一般には成形温度での溶融粘度が剪断速度１０００ｓｅｃ－１で１０ＭＰａ以上６００ＭＰａ以下のものが使用可能である。しかし、それ自体あまり高粘度のものは流動性が非常に悪化するため好ましくない。なお、上記（Ａ）液晶性樹脂は２種以上の液晶性樹脂の混合物であってもよい。
The melt viscosity of the (A) liquid crystalline resin obtained by the above method is not particularly limited. In general, 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.
（Ａ）成分の含有量は、本発明に係る液晶性樹脂組成物において、好ましくは６０質量％以上９５質量％以下、より好ましくは６４質量％以上９３質量％以下、更により好ましくは６９質量％以上９０質量％以下である。特に、本発明に係る液晶性樹脂組成物が（Ｃ）板状充填剤を含有する場合、（Ａ）成分の含有量は、本発明に係る液晶性樹脂組成物において、好ましくは６０質量％以上９５質量％未満、より好ましくは６４質量％以上９３質量％以下、更により好ましくは６９質量％以上９０質量％以下である。（Ａ）成分の含有量が６０質量％以上であると、組成物の溶融時の流動性が向上しやすい。（Ａ）成分の含有量が９５質量％以下又は９５質量％未満であると、（Ｂ）成分の含有量が十分となるため、得られる液晶性樹脂組成物は低誘電率となりやすい。
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）アスペクト比が１．１５以上である中空フィラー］
（Ｂ）中空フィラーは、一般にバルーンと呼ばれているものであり、中空球体の材料としては、例えば、アルミナ、シリカ、ガラス等の無機材料；尿素樹脂、フェノール樹脂、等の有機材料；が挙げられる。中でも、耐熱性や強度の観点からガラスが好ましい。即ち、中空フィラーとしては、ガラスバルーンが好適に用いられる。（Ｂ）成分は、単独で用いても、２種以上を併用してもよい。 [(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）中空フィラーは、一般にバルーンと呼ばれているものであり、中空球体の材料としては、例えば、アルミナ、シリカ、ガラス等の無機材料；尿素樹脂、フェノール樹脂、等の有機材料；が挙げられる。中でも、耐熱性や強度の観点からガラスが好ましい。即ち、中空フィラーとしては、ガラスバルーンが好適に用いられる。（Ｂ）成分は、単独で用いても、２種以上を併用してもよい。 [(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）中空フィラーは、アスペクト比が１．１５以上であるため、アスペクト比が１．１５未満の中空フィラーと比較して、異方性がより大きい。よって、（Ｂ）中空フィラーを含有する組成物においては、液晶性樹脂の良好な流動性を発揮させている高い分子配向性が乱されにくいため、溶融粘度上昇及び流動性悪化が抑制されやすいと推測される。
(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）中空フィラーのアスペクト比は、溶融粘度上昇及び流動性悪化の抑制並びに成形性等の観点から、１．１５以上であり、好ましくは１．２０以上２．００以下であり、より好ましくは１．２２以上１．５０以下であり、更により好ましくは１．２５以上１．３０未満である。
(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.
本明細書において、アスペクト比としては、動的画像解析法／粒子状態分析計を用いて、粒子投影面において最も長い部分の長さである最大長Ｌと、粒子投影面において最大長Ｌに対し垂直な方向で最も長い部分の長さである最大垂直長Ｓとを３０００個の粒子について測定し、その測定を数回繰り返して、各粒子について計算された比Ｌ／Ｓの平均の値を採用する。
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.
（Ｂ）成分の平均粒子径は、成形性の観点から、５μｍ以上であることが好ましく、より好ましくは１０μｍ以上であり、（Ｂ）成分の破壊抑制や成形性の観点から、好ましくは２００μｍ以下、より好ましくは１００μｍ以下、更により好ましくは５０μｍ以下である。なお、本明細書において、（Ｂ）成分の平均粒子径としては、レーザ回折／散乱式粒度分布測定法で測定した値（Ｄ５０）を採用する。
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).
（Ｂ）成分の含有量は、本発明に係る液晶性樹脂組成物において、好ましくは５質量％以上２０質量％以下、より好ましくは７質量％以上１８質量％以下、更により好ましくは１０質量％以上１５質量％以下である。（Ｂ）成分の含有量が５質量％以上であると、得られる液晶性樹脂組成物は低誘電率となりやすい。（Ｂ）成分の含有量が２０質量％以下であると、組成物の溶融時の流動性が向上しやすい。
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）板状充填剤］
本発明に係る液晶性樹脂組成物は、任意に（Ｃ）板状充填剤を含有してもよい。（Ｃ）板状充填剤は、液晶性樹脂組成物の成形品において、反り抑制充填剤として作用する。（Ｃ）成分は、単独で用いても、２種以上を併用してもよい。 [(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.
本発明に係る液晶性樹脂組成物は、任意に（Ｃ）板状充填剤を含有してもよい。（Ｃ）板状充填剤は、液晶性樹脂組成物の成形品において、反り抑制充填剤として作用する。（Ｃ）成分は、単独で用いても、２種以上を併用してもよい。 [(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.
本発明者らの検討によれば、中空フィラーを含有する従来の液晶性樹脂組成物は、反りの大きい成形品を与えること、及び、反りを小さくするために、板状充填剤等の反り抑制充填剤を更に上記従来の液晶性樹脂組成物に添加すると、まずます流動性が悪化してしまうことが判明した。しかし、本発明に係る液晶性樹脂組成物では、（Ｂ）アスペクト比が１．１５以上である中空フィラーを用いることにより、（Ｃ）板状充填剤を添加した場合であっても、良好な流動性を確保したまま、成形体の反りを小さくすることができ、寸法安定性に優れる。
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）板状充填剤は、平均粒子径が１５～５０μｍであることが好ましい。上記平均粒子径が１５μｍ以上であると、必要な機械強度が確保されやすく、成形体の反り抑制効果が高くなりやすい。上記平均粒子径が５０μｍ以下であると、組成物の溶融時の流動性が向上しやすい。好ましい上記平均粒子径は２０～３０μｍである。なお、本明細書において、（Ｃ）成分の平均粒子径としては、レーザ回折／散乱式粒度分布測定法で測定した値（ＭＶ）を採用する。
(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 diameter 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）板状充填剤としては、特に限定されず、例えば、マイカ、タルク、ガラスフレーク、黒鉛、各種の金属箔（例えば、アルミ箔、鉄箔、銅箔）等が挙げられる。本発明においては（Ｃ）成分として、マイカを使用することが好ましい。
(C) The plate-like filler is not particularly limited, and examples thereof include mica, talc, glass flake, graphite, various metal foils (for example, aluminum foil, iron foil, copper foil) and the like. In the present invention, it is preferable to use mica as the component (C).
（Ｃ）成分の含有量は、本発明に係る液晶性樹脂組成物において、好ましくは０質量％超２０質量％以下であり、より好ましくは５質量％以上１８質量％以下、更により好ましくは１０質量％以上１６質量％以下である。（Ｃ）成分の含有量が０質量％超であると、必要な機械強度が確保されやすく、成形体の反り抑制効果が高くなりやすい。（Ｃ）成分の含有量が２０質量％以下であると、組成物の溶融時の流動性が向上しやすい。
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.
［その他の成分］
本発明に係る液晶性樹脂組成物には、本発明の効果を害さない範囲で、その他の重合体、その他の充填剤、一般に合成樹脂に添加される公知の物質、即ち、酸化防止剤や紫外線吸収剤等の安定剤、帯電防止剤、難燃剤、染料や顔料等の着色剤、潤滑剤、離型剤、結晶化促進剤、結晶核剤等も要求性能に応じ適宜添加することができる。 [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.
本発明に係る液晶性樹脂組成物には、本発明の効果を害さない範囲で、その他の重合体、その他の充填剤、一般に合成樹脂に添加される公知の物質、即ち、酸化防止剤や紫外線吸収剤等の安定剤、帯電防止剤、難燃剤、染料や顔料等の着色剤、潤滑剤、離型剤、結晶化促進剤、結晶核剤等も要求性能に応じ適宜添加することができる。 [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.
その他の重合体としては、例えば、エポキシ基含有共重合体が挙げられる。その他の充填剤とは、（Ｂ）中空フィラー及び（Ｃ）板状充填剤以外の充填剤をいい、例えば、ガラス繊維等の繊維状充填剤；シリカ等の粒状充填剤；カーボンブラックが挙げられる。
Examples of other polymers include epoxy group-containing copolymers. 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. .
［液晶性樹脂組成物の調製］
本発明に係る液晶性樹脂組成物の調製は特に限定されない。例えば、（Ａ）成分、（Ｂ）成分、任意に（Ｃ）成分、及び任意にその他の成分を配合して、これらを１軸又は２軸押出機を用いて溶融混練処理することで、液晶性樹脂組成物の調製が行われる。 [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.
本発明に係る液晶性樹脂組成物の調製は特に限定されない。例えば、（Ａ）成分、（Ｂ）成分、任意に（Ｃ）成分、及び任意にその他の成分を配合して、これらを１軸又は２軸押出機を用いて溶融混練処理することで、液晶性樹脂組成物の調製が行われる。 [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.
［液晶性樹脂組成物］
[Liquid Crystalline Resin Composition]
上記のようにして得られた本発明に係る液晶性樹脂組成物は、溶融粘度が好ましくは４５Ｐａ・ｓｅｃ未満、より好ましくは４２Ｐａ・ｓｅｃ以下、更により好ましくは４０Ｐａ・ｓｅｃ以下である。溶融時の流動性が高く、成形性に優れる点は、本発明に係る液晶性樹脂組成物の特徴の一つである。本明細書において、溶融粘度としては、液晶性樹脂の融点よりも１０～３０℃高いシリンダー温度、せん断速度１０００ｓｅｃ－１の条件で、ＩＳＯ １１４４３に準拠した測定方法で得られた値を採用する。
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, the melt viscosity is 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 .
本発明に係る液晶性樹脂組成物は、比誘電率が好ましくは３．２以下、より好ましくは３．１以下、更により好ましくは３．０以下である。低誘電率である点も、本発明に係る液晶性樹脂組成物の特徴の一つである。
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.
以下に実施例を挙げて、本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
＜液晶性樹脂＞
・液晶性ポリエステルアミド樹脂（ＬＣＰ１）
重合容器に下記の原料を仕込んだ後、反応系の温度を１４０℃に上げ、１４０℃で１時間反応させた。その後、更に３４０℃まで４．５時間かけて昇温し、そこから１５分かけて１０Ｔｏｒｒ（即ち１３３０Ｐａ）まで減圧にして、酢酸、過剰の無水酢酸、及びその他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレットを得た。得られたペレットについて、窒素気流下、３００℃で２時間の熱処理を行って、目的のポリマーを得た。得られたポリマーの融点は３３４℃、３５０℃における溶融粘度は１９．０Ｐａ・ｓであった。なお、上記ポリマーの溶融粘度は、後述する溶融粘度の測定方法と同様にして測定した。
（Ｉ）４－ヒドロキシ安息香酸（ＨＢＡ）；１８８．４ｇ（６０モル％）
（ＩＩ）２－ヒドロキシ－６－ナフトエ酸（ＨＮＡ）；２１．４ｇ（５モル％）
（ＩＩＩ）テレフタル酸（ＴＡ）；６６．８ｇ（１７．７モル％）
（ＩＶ）４，４’－ジヒドロキシビフェニル（ＢＰ）；５２．２ｇ（１２．３モル％）
（Ｖ）４－アセトキシアミノフェノール（ＡＰＡＰ）；１７．２ｇ（５モル％）
金属触媒（酢酸カリウム触媒）；１５ｍｇ
アシル化剤（無水酢酸）；２２６．２ｇ <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
・液晶性ポリエステルアミド樹脂（ＬＣＰ１）
重合容器に下記の原料を仕込んだ後、反応系の温度を１４０℃に上げ、１４０℃で１時間反応させた。その後、更に３４０℃まで４．５時間かけて昇温し、そこから１５分かけて１０Ｔｏｒｒ（即ち１３３０Ｐａ）まで減圧にして、酢酸、過剰の無水酢酸、及びその他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレットを得た。得られたペレットについて、窒素気流下、３００℃で２時間の熱処理を行って、目的のポリマーを得た。得られたポリマーの融点は３３４℃、３５０℃における溶融粘度は１９．０Ｐａ・ｓであった。なお、上記ポリマーの溶融粘度は、後述する溶融粘度の測定方法と同様にして測定した。
（Ｉ）４－ヒドロキシ安息香酸（ＨＢＡ）；１８８．４ｇ（６０モル％）
（ＩＩ）２－ヒドロキシ－６－ナフトエ酸（ＨＮＡ）；２１．４ｇ（５モル％）
（ＩＩＩ）テレフタル酸（ＴＡ）；６６．８ｇ（１７．７モル％）
（ＩＶ）４，４’－ジヒドロキシビフェニル（ＢＰ）；５２．２ｇ（１２．３モル％）
（Ｖ）４－アセトキシアミノフェノール（ＡＰＡＰ）；１７．２ｇ（５モル％）
金属触媒（酢酸カリウム触媒）；１５ｍｇ
アシル化剤（無水酢酸）；２２６．２ｇ <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
・液晶性ポリエステル樹脂（ＬＣＰ２）
重合容器に下記の原料を仕込んだ後、反応系の温度を１４０℃に上げ、１４０℃で１時間反応させた。その後、更に３６０℃まで５．５時間かけて昇温し、そこから３０分かけて５Ｔｏｒｒ（即ち６６７Ｐａ）まで減圧にして、酢酸、過剰の無水酢酸、及びその他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレットを得た。得られたペレットについて、窒素気流下、３００℃で８時間の熱処理を行って、目的のポリマーを得た。得られたポリマーの融点は３５２℃、３８０℃における溶融粘度は２７．０Ｐａ・ｓであった。なお、上記ポリマーの溶融粘度は、後述する溶融粘度の測定方法と同様にして測定した。
（Ｉ）２－ヒドロキシ－６－ナフトエ酸（ＨＮＡ）；１６６ｇ（４８モル％）
（ＩＩ）テレフタル酸（ＴＡ）；７６ｇ（２５モル％）
（ＩＩＩ）４，４’－ジヒドロキシビフェニル（ＢＰ）；８６ｇ（２５モル％）
（ＩＶ）４－ヒドロキシ安息香酸（ＨＢＡ）；５ｇ（２モル％）
金属触媒（酢酸カリウム触媒）；２２．５ｍｇ
アシル化剤（無水酢酸）；１９１ｇ ・ 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
重合容器に下記の原料を仕込んだ後、反応系の温度を１４０℃に上げ、１４０℃で１時間反応させた。その後、更に３６０℃まで５．５時間かけて昇温し、そこから３０分かけて５Ｔｏｒｒ（即ち６６７Ｐａ）まで減圧にして、酢酸、過剰の無水酢酸、及びその他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレットを得た。得られたペレットについて、窒素気流下、３００℃で８時間の熱処理を行って、目的のポリマーを得た。得られたポリマーの融点は３５２℃、３８０℃における溶融粘度は２７．０Ｐａ・ｓであった。なお、上記ポリマーの溶融粘度は、後述する溶融粘度の測定方法と同様にして測定した。
（Ｉ）２－ヒドロキシ－６－ナフトエ酸（ＨＮＡ）；１６６ｇ（４８モル％）
（ＩＩ）テレフタル酸（ＴＡ）；７６ｇ（２５モル％）
（ＩＩＩ）４，４’－ジヒドロキシビフェニル（ＢＰ）；８６ｇ（２５モル％）
（ＩＶ）４－ヒドロキシ安息香酸（ＨＢＡ）；５ｇ（２モル％）
金属触媒（酢酸カリウム触媒）；２２．５ｍｇ
アシル化剤（無水酢酸）；１９１ｇ ・ 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
＜液晶性樹脂以外の材料＞
・ガラスバルーン１：Ｙ１２０００（（株）セイシン企業製、アスペクト比（平均）１．２６４、平均粒子径（Ｄ５０）３５μｍ）
・ガラスバルーン２：Ｓ６０ＨＳ（住友３Ｍ（株）製、アスペクト比（平均）１．０９１、平均粒子径（Ｄ５０）２４μｍ）
・ガラスバルーン３：ｉｍ３０Ｋ（住友３Ｍ（株）製、アスペクト比（平均）１．０７２、平均粒子径（Ｄ５０）１８μｍ）
・板状充填剤：ＡＢ－２５Ｓ（（株）ヤマグチマイカ製、マイカ、平均粒子径（ＭＶ）２４μｍ）
・繊維状充填剤：ＥＣＳ０３Ｔ－７８６Ｈ（日本電気硝子(株)製、ガラス繊維、繊維径１０μｍ、長さ３ｍｍのチョプドストランド） <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, chopped strand having a fiber diameter of 10 μm and a length of 3 mm)
・ガラスバルーン１：Ｙ１２０００（（株）セイシン企業製、アスペクト比（平均）１．２６４、平均粒子径（Ｄ５０）３５μｍ）
・ガラスバルーン２：Ｓ６０ＨＳ（住友３Ｍ（株）製、アスペクト比（平均）１．０９１、平均粒子径（Ｄ５０）２４μｍ）
・ガラスバルーン３：ｉｍ３０Ｋ（住友３Ｍ（株）製、アスペクト比（平均）１．０７２、平均粒子径（Ｄ５０）１８μｍ）
・板状充填剤：ＡＢ－２５Ｓ（（株）ヤマグチマイカ製、マイカ、平均粒子径（ＭＶ）２４μｍ）
・繊維状充填剤：ＥＣＳ０３Ｔ－７８６Ｈ（日本電気硝子(株)製、ガラス繊維、繊維径１０μｍ、長さ３ｍｍのチョプドストランド） <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, chopped strand having a fiber diameter of 10 μm and a length of 3 mm)
＜液晶性樹脂組成物の製造＞
上記成分を、表１に示す割合で二軸押出機（（株）日本製鋼所製ＴＥＸ３０α型）を用いて、下記のシリンダー温度で溶融混練し、液晶性樹脂組成物ペレットを得た。
〔製造条件〕
シリンダー温度：
３５０℃：液晶性ポリエステルアミド樹脂（ＬＣＰ１）を含有する液晶性樹脂組成物の場合
３７０℃：液晶性ポリエステル樹脂（ＬＣＰ２）を含有する液晶性樹脂組成物の場合 <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)
上記成分を、表１に示す割合で二軸押出機（（株）日本製鋼所製ＴＥＸ３０α型）を用いて、下記のシリンダー温度で溶融混練し、液晶性樹脂組成物ペレットを得た。
〔製造条件〕
シリンダー温度：
３５０℃：液晶性ポリエステルアミド樹脂（ＬＣＰ１）を含有する液晶性樹脂組成物の場合
３７０℃：液晶性ポリエステル樹脂（ＬＣＰ２）を含有する液晶性樹脂組成物の場合 <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)
＜ガラスバルーンのアスペクト比測定＞
３０００個のガラスバルーン粒子について、セイシン企業製の動的画像解析法／粒子状態分析計「ＰＩＴＡ－３」を用いて、当該分析計に装備されている倍率４倍の光学レンズを用いて測定した粒子投影面において最も長い部分の長さである最大長Ｌと、粒子投影面において最大長Ｌに対し垂直な方向で最も長い部分の長さである最大垂直長Ｓとを測定した。この測定を数回繰り返して、各粒子について計算された比Ｌ／Ｓの度数分布をヒストグラムに示し、比Ｌ／Ｓの平均の値を算出して、ガラスバルーンのアスペクト比として採用した。測定にあたり、適量の界面活性剤を含む希釈用水溶液にてガラスバルーンを希釈して、ガラスバルーンの濃度を３．３ｍｇ／ｍＬに調整し、超音波洗浄にて上記水溶液中にガラスバルーンを分散させてガラスバルーン分散液を得、このガラスバルーン分散液を測定試料として用いた。なお、図１（ａ）～（ｃ）は、それぞれ、上記ガラスバルーン１～３の個々の粒子について計算した比Ｌ／Ｓの度数分布及び累積度数分布を示すヒストグラムである。 <Aspect ratio measurement of glass balloon>
3000 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. FIGS. 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.
３０００個のガラスバルーン粒子について、セイシン企業製の動的画像解析法／粒子状態分析計「ＰＩＴＡ－３」を用いて、当該分析計に装備されている倍率４倍の光学レンズを用いて測定した粒子投影面において最も長い部分の長さである最大長Ｌと、粒子投影面において最大長Ｌに対し垂直な方向で最も長い部分の長さである最大垂直長Ｓとを測定した。この測定を数回繰り返して、各粒子について計算された比Ｌ／Ｓの度数分布をヒストグラムに示し、比Ｌ／Ｓの平均の値を算出して、ガラスバルーンのアスペクト比として採用した。測定にあたり、適量の界面活性剤を含む希釈用水溶液にてガラスバルーンを希釈して、ガラスバルーンの濃度を３．３ｍｇ／ｍＬに調整し、超音波洗浄にて上記水溶液中にガラスバルーンを分散させてガラスバルーン分散液を得、このガラスバルーン分散液を測定試料として用いた。なお、図１（ａ）～（ｃ）は、それぞれ、上記ガラスバルーン１～３の個々の粒子について計算した比Ｌ／Ｓの度数分布及び累積度数分布を示すヒストグラムである。 <Aspect ratio measurement of glass balloon>
3000 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. FIGS. 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.
＜溶融粘度＞
実施例及び比較例の液晶性樹脂組成物の溶融粘度を、上記ペレットを用いて測定した。具体的には、キャピラリー式レオメーター（（株）東洋精機製作所製、キャピログラフ１Ｄ：ピストン径１０ｍｍ）により、液晶性樹脂の融点よりも１０～３０℃高い温度で、せん断速度１０００ｓｅｃ－１の条件での見かけの溶融粘度をＩＳＯ １１４４３に準拠して測定した。測定には、内径１ｍｍ、長さ２０ｍｍのオリフィスを用いた。なお、具体的な測定温度は、液晶性ポリエステルアミド樹脂（ＬＣＰ１）を含有する液晶性樹脂組成物については３５０℃、液晶性ポリエステル樹脂（ＬＣＰ２）を含有する液晶性樹脂組成物については３８０℃であった。結果を表１に示す。 <Melt viscosity>
The melt viscosity of the liquid crystalline resin compositions of Examples and Comparative Examples was measured using the pellets. Specifically, a capillary rheometer (Capillograph 1D, manufactured by Toyo Seiki Seisakusho Co., Ltd.,piston diameter 10 mm) is used at a temperature 10-30 ° 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.
実施例及び比較例の液晶性樹脂組成物の溶融粘度を、上記ペレットを用いて測定した。具体的には、キャピラリー式レオメーター（（株）東洋精機製作所製、キャピログラフ１Ｄ：ピストン径１０ｍｍ）により、液晶性樹脂の融点よりも１０～３０℃高い温度で、せん断速度１０００ｓｅｃ－１の条件での見かけの溶融粘度をＩＳＯ １１４４３に準拠して測定した。測定には、内径１ｍｍ、長さ２０ｍｍのオリフィスを用いた。なお、具体的な測定温度は、液晶性ポリエステルアミド樹脂（ＬＣＰ１）を含有する液晶性樹脂組成物については３５０℃、液晶性ポリエステル樹脂（ＬＣＰ２）を含有する液晶性樹脂組成物については３８０℃であった。結果を表１に示す。 <Melt viscosity>
The melt viscosity of the liquid crystalline resin compositions of Examples and Comparative Examples was measured using the pellets. Specifically, a capillary rheometer (Capillograph 1D, manufactured by Toyo Seiki Seisakusho Co., Ltd.,
＜平面度＞
実施例及び比較例のペレットを、成形機（住友重機械工業（株）製 「ＳＥ－１００ＤＵ」）を用いて、以下の成形条件で成形し、８０ｍｍ×８０ｍｍ×１ｍｍの平板状試験片を５枚作製した。１枚目の平板状試験片を水平面に静置し、（株）ミツトヨ製のＣＮＣ画像測定機（型式：ＱＶＢＨＵ４０４－ＰＲＯ１Ｆ）を用いて、上記平板状試験片上の９箇所において、上記水平面からの高さを測定し、得られた測定値から平均の高さを算出した。高さを測定した位置は、平板状試験片の主平面上に、この主平面の各辺からの距離が３ｍｍとなるように、一辺が７４ｍｍの正方形を置いたときに、この正方形の各頂点、この正方形の各辺の中点、及びこの正方形の２本の対角線の交点に該当する位置である。上記水平面からの高さが上記平均の高さと同一であり、上記水平面と平行な面を基準面とした。上記９箇所で測定された高さの中から、基準面からの最大高さと最小高さとを選択し、両者の差を算出した。同様にして、他の４枚の平板状試験片についても上記の差を算出し、得られた５個の値を平均して、平面度の値とした。結果を表１に示す。
〔成形条件〕
シリンダー温度：
３５０℃：液晶性ポリエステルアミド樹脂（ＬＣＰ１）を含有する液晶性樹脂組成物の場合
３７０℃：液晶性ポリエステル樹脂（ＬＣＰ２）を含有する液晶性樹脂組成物の場合
金型温度： ８０℃
射出速度： ３３ｍｍ／ｓｅｃ
保圧： ６０ＭＰａ <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-shaped test piece was allowed to stand on a horizontal plane, and the CNC image measuring machine (model: QVBHU404-PRO1F) manufactured by Mitutoyo Co., Ltd. was used at nine locations on the flat plate-shaped 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
実施例及び比較例のペレットを、成形機（住友重機械工業（株）製 「ＳＥ－１００ＤＵ」）を用いて、以下の成形条件で成形し、８０ｍｍ×８０ｍｍ×１ｍｍの平板状試験片を５枚作製した。１枚目の平板状試験片を水平面に静置し、（株）ミツトヨ製のＣＮＣ画像測定機（型式：ＱＶＢＨＵ４０４－ＰＲＯ１Ｆ）を用いて、上記平板状試験片上の９箇所において、上記水平面からの高さを測定し、得られた測定値から平均の高さを算出した。高さを測定した位置は、平板状試験片の主平面上に、この主平面の各辺からの距離が３ｍｍとなるように、一辺が７４ｍｍの正方形を置いたときに、この正方形の各頂点、この正方形の各辺の中点、及びこの正方形の２本の対角線の交点に該当する位置である。上記水平面からの高さが上記平均の高さと同一であり、上記水平面と平行な面を基準面とした。上記９箇所で測定された高さの中から、基準面からの最大高さと最小高さとを選択し、両者の差を算出した。同様にして、他の４枚の平板状試験片についても上記の差を算出し、得られた５個の値を平均して、平面度の値とした。結果を表１に示す。
〔成形条件〕
シリンダー温度：
３５０℃：液晶性ポリエステルアミド樹脂（ＬＣＰ１）を含有する液晶性樹脂組成物の場合
３７０℃：液晶性ポリエステル樹脂（ＬＣＰ２）を含有する液晶性樹脂組成物の場合
金型温度： ８０℃
射出速度： ３３ｍｍ／ｓｅｃ
保圧： ６０ＭＰａ <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-shaped test piece was allowed to stand on a horizontal plane, and the CNC image measuring machine (model: QVBHU404-PRO1F) manufactured by Mitutoyo Co., Ltd. was used at nine locations on the flat plate-shaped 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
＜比誘電率＞
実施例及び比較例のペレットを、成形機（住友重機械工業（株）製 「ＳＥ－１００ＤＵ」）を用いて、以下の成形条件で成形し、８０ｍｍ×８０ｍｍ×１ｍｍの平板状試験片を作製した。図２に示す通り、平板状試験片の中央から流動直角方向に８０ｍｍ×１ｍｍ×１ｍｍの試験片を切り出し、これを比誘電率測定用試験片とした。この試験片について、（株）関東電子応用開発製の以下の構成の空洞共振器摂動法複素誘電率評価装置を用いて、１ＧＨｚでの比誘電率を測定した。
スカラーネットワークアナライザー：アジレントテクノロジー８７５７Ｄ
周波数シンセサイザー：アジレントテクノロジー ８３６５０ＬスイープＣＷジェネレータ
固定減衰器：アジレントテクノロジー８５０２５Ｄディテクター
空洞共振器：関東電子応用開発ＣＰ４３１
測定プログラム：関東電子応用開発ＣＰＭＡ－Ｓ２／Ｖ２
〔成形条件〕
シリンダー温度：
３５０℃：液晶性ポリエステルアミド樹脂（ＬＣＰ１）を含有する液晶性樹脂組成物の場合
３７０℃：液晶性ポリエステル樹脂（ＬＣＰ２）を含有する液晶性樹脂組成物の場合
金型温度： ８０℃
射出速度： ３３ｍｍ／ｓｅｃ
保圧： ６０ＭＰａ <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 flat test pieces 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
実施例及び比較例のペレットを、成形機（住友重機械工業（株）製 「ＳＥ－１００ＤＵ」）を用いて、以下の成形条件で成形し、８０ｍｍ×８０ｍｍ×１ｍｍの平板状試験片を作製した。図２に示す通り、平板状試験片の中央から流動直角方向に８０ｍｍ×１ｍｍ×１ｍｍの試験片を切り出し、これを比誘電率測定用試験片とした。この試験片について、（株）関東電子応用開発製の以下の構成の空洞共振器摂動法複素誘電率評価装置を用いて、１ＧＨｚでの比誘電率を測定した。
スカラーネットワークアナライザー：アジレントテクノロジー８７５７Ｄ
周波数シンセサイザー：アジレントテクノロジー ８３６５０ＬスイープＣＷジェネレータ
固定減衰器：アジレントテクノロジー８５０２５Ｄディテクター
空洞共振器：関東電子応用開発ＣＰ４３１
測定プログラム：関東電子応用開発ＣＰＭＡ－Ｓ２／Ｖ２
〔成形条件〕
シリンダー温度：
３５０℃：液晶性ポリエステルアミド樹脂（ＬＣＰ１）を含有する液晶性樹脂組成物の場合
３７０℃：液晶性ポリエステル樹脂（ＬＣＰ２）を含有する液晶性樹脂組成物の場合
金型温度： ８０℃
射出速度： ３３ｍｍ／ｓｅｃ
保圧： ６０ＭＰａ <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 flat test pieces 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
表１に記載の結果から明らかなように、実施例の液晶性樹脂組成物は、成形性が良好であり、低誘電率であった。また、実施例の液晶性樹脂組成物は、マイカを添加しても、良好な成形性を維持した。
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 (6)
- （Ａ）液晶性樹脂と、（Ｂ）アスペクト比が１．１５以上である中空フィラーと、を含有する液晶性樹脂組成物。 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.
- （Ｂ）成分がガラスバルーンである請求項１に記載の組成物。 The composition according to claim 1, wherein the component (B) is a glass balloon.
- （Ａ）成分の含有量が６０質量％以上９５質量％以下であり、（Ｂ）成分の含有量が５質量％以上２０質量％以下である請求項１又は２に記載の組成物。 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.
- 更に、（Ｃ）板状充填剤を含有する請求項１又は２に記載の組成物。 The composition according to claim 1 or 2, further comprising (C) a plate-like filler.
- （Ｃ）成分がマイカである請求項４に記載の組成物。 The composition according to claim 4, wherein the component (C) is mica.
- （Ａ）成分の含有量が６０質量％以上９５質量％未満であり、（Ｂ）成分の含有量が５質量％以上２０質量％以下であり、（Ｃ）成分の含有量が０質量％超２０質量％以下である請求項４又は５に記載の組成物。 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. The composition according to claim 4 or 5, which is 20% by mass or less.
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| KR1020187028156A KR101945912B1 (en) | 2016-04-15 | 2017-04-05 | Liquid crystalline resin composition |
| JP2018507052A JP6359225B2 (en) | 2016-04-15 | 2017-04-05 | Liquid crystalline resin composition |
| SG11201809000VA SG11201809000VA (en) | 2016-04-15 | 2017-04-05 | Liquid crystal resin composition |
| CN201780019527.0A CN108884329B (en) | 2016-04-15 | 2017-04-05 | Liquid crystalline resin composition |
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| JP2016082296 | 2016-04-15 | ||
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|---|---|---|---|
| PCT/JP2017/014287 WO2017179474A1 (en) | 2016-04-15 | 2017-04-05 | Liquid-crystalline resin composition |
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| JP (1) | JP6359225B2 (en) |
| KR (1) | KR101945912B1 (en) |
| CN (1) | CN108884329B (en) |
| SG (1) | SG11201809000VA (en) |
| TW (1) | TWI707904B (en) |
| WO (1) | WO2017179474A1 (en) |
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| JP2021109891A (en) * | 2020-01-07 | 2021-08-02 | パナソニックＩｐマネジメント株式会社 | Liquid crystalline resin composition and molded article |
| CN113396189A (en) * | 2019-02-05 | 2021-09-14 | 住友化学株式会社 | Resin composition |
| WO2022004630A1 (en) * | 2020-06-30 | 2022-01-06 | Ｅｎｅｏｓ株式会社 | Resin composition and resin molded article comprising said resin composition |
| KR20230019984A (en) | 2020-07-16 | 2023-02-09 | 포리프라스틱 가부시키가이샤 | Resin composition and molded article thereof |
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- 2017-04-05 CN CN201780019527.0A patent/CN108884329B/en active Active
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| WO2021065416A1 (en) * | 2019-10-03 | 2021-04-08 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for ball bearing anti-sliding abrasion member, and ball bearing anti-sliding abrasion member using same |
| JP6906123B1 (en) * | 2019-10-03 | 2021-07-21 | ポリプラスチックス株式会社 | Liquid crystal resin composition for ball bearing sliding wear member and ball bearing sliding wear member using it |
| JP2021109891A (en) * | 2020-01-07 | 2021-08-02 | パナソニックＩｐマネジメント株式会社 | Liquid crystalline resin composition and molded article |
| WO2022004630A1 (en) * | 2020-06-30 | 2022-01-06 | Ｅｎｅｏｓ株式会社 | Resin composition and resin molded article comprising said resin composition |
| KR20230019984A (en) | 2020-07-16 | 2023-02-09 | 포리프라스틱 가부시키가이샤 | Resin composition and molded article thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20180112086A (en) | 2018-10-11 |
| SG11201809000VA (en) | 2018-11-29 |
| KR101945912B1 (en) | 2019-02-08 |
| TWI707904B (en) | 2020-10-21 |
| CN108884329A (en) | 2018-11-23 |
| TW201805354A (en) | 2018-02-16 |
| JP6359225B2 (en) | 2018-07-18 |
| JPWO2017179474A1 (en) | 2018-06-07 |
| CN108884329B (en) | 2019-10-18 |
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