JP6626358B2 - Wholly aromatic liquid crystal polyester resin and method for producing the same - Google Patents

Wholly aromatic liquid crystal polyester resin and method for producing the same Download PDF

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JP6626358B2
JP6626358B2 JP2016020161A JP2016020161A JP6626358B2 JP 6626358 B2 JP6626358 B2 JP 6626358B2 JP 2016020161 A JP2016020161 A JP 2016020161A JP 2016020161 A JP2016020161 A JP 2016020161A JP 6626358 B2 JP6626358 B2 JP 6626358B2
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liquid crystal
mol
crystal polyester
polyester resin
aromatic liquid
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JP2017137438A (en
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山 希 望 秋
山 希 望 秋
村 亮 人 川
村 亮 人 川
藤 正 寿 安
藤 正 寿 安
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Eneos Corp
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JXTG Nippon Oil and Energy Corp
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Priority to PCT/JP2017/003746 priority patent/WO2017135365A1/en
Priority to CN201780006453.7A priority patent/CN108602943B/en
Priority to TW106103627A priority patent/TWI732820B/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/79—Interfacial processes, i.e. processes involving a reaction at the interface of two non-miscible liquids
    • 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
    • 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
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

本発明は、全芳香族液晶ポリエステル樹脂およびその製造方法に関する。さらに、本発明は、該全芳香族液晶ポリエステル樹脂を含む全芳香族液晶ポリエステル樹脂組成物、該組成物を含んでなる成形品および電子部品に関する。   The present invention relates to a wholly aromatic liquid crystal polyester resin and a method for producing the same. Further, the present invention relates to a wholly aromatic liquid crystal polyester resin composition containing the wholly aromatic liquid crystal polyester resin, and a molded article and an electronic component containing the composition.

全芳香族液晶ポリエステル樹脂は、成形性、耐熱性および充填性に優れることから、これを使用して製造した成形品（例えば、射出成形品）は、各種電子部品に用いられている。
近年、パーソナル・コンピューターやスマートフォンなどの小型化から電子部品の高集積化、薄肉化、低背化が進んでおり、非常に薄い肉厚部を有する成形品の需要が高まっている。そのため、全芳香族液晶ポリエステル樹脂には、より優れた充填性を有することが求められている。 Since the wholly aromatic liquid crystal polyester resin is excellent in moldability, heat resistance, and filling property, molded articles (for example, injection molded articles) manufactured using the same are used for various electronic components.
2. Description of the Related Art In recent years, electronic components have been highly integrated, thinned, and reduced in height due to miniaturization of personal computers, smartphones, and the like, and the demand for molded articles having extremely thin thick portions has increased. Therefore, a wholly aromatic liquid crystal polyester resin is required to have more excellent filling properties.

全芳香族液晶ポリエステル樹脂などの液晶ポリマーの充填性、すなわち流動性を改善する方法として、例えば、液晶ポリマーの分子量を下げ、低粘度化させる方法が実施されている。
しかしながら、液晶ポリマーの分子量を下げることにより、成形品の機械的強度などの物性低下が生じるほか、成形品をコネクタなどの電子部品に適用する際に行われるリフロー処理により成形品表面に膨れ（ブリスター）やソリが生じてしまうという問題があった。ここで、特許文献１には、ブリスターの発生を抑制することのできる全芳香族液晶ポリエステル樹脂が提案されている。 As a method of improving the filling property, that is, the fluidity of a liquid crystal polymer such as a wholly aromatic liquid crystal polyester resin, for example, a method of lowering the molecular weight of the liquid crystal polymer and lowering the viscosity has been implemented.
However, by lowering the molecular weight of the liquid crystal polymer, physical properties such as mechanical strength of the molded article are reduced, and the surface of the molded article is swollen (blister) by a reflow treatment performed when the molded article is applied to an electronic component such as a connector. ) And warpage. Here, Patent Document 1 proposes a wholly aromatic liquid crystal polyester resin that can suppress the generation of blisters.

特開２０１２−１２６８４２号公報JP 2012-126842 A

本発明者らは今般、全芳香族液晶ポリエステル樹脂に含まれる構成単位を、特定の構成単位、組成比とし、かつ全芳香族液晶ポリエステル樹脂の融点を３２０℃以上とすることにより、上記問題を解決することができる、との知見を得た。本発明は、かかる知見によるものである。   The present inventors have solved the above problem by setting the constituent units contained in the wholly aromatic liquid crystal polyester resin to a specific constituent unit and composition ratio, and setting the melting point of the wholly aromatic liquid crystal polyester resin to 320 ° C. or higher. It was found that it could be solved. The present invention is based on such findings.

したがって、本発明の目的は、機械的強度などの物性を維持しつつ、優れた充填性および耐ブリスター性ならびに低ソリ性を有する全芳香族液晶ポリエステル樹脂を提供することである。   Accordingly, an object of the present invention is to provide a wholly aromatic liquid crystal polyester resin having excellent filling properties, blister resistance, and low warpage while maintaining physical properties such as mechanical strength.

本発明に係る全芳香族液晶ポリエステル樹脂は、
下記式（Ｉ）〜（Ｖ）で表される構成単位（Ｉ）〜（Ｖ）を含んでなる全芳香族液晶ポリエステル樹脂であって、
芳香族液晶ポリエステル中における構成単位（Ｉ）〜（Ｖ）の組成比（モル％）が、下記の条件を満たし、
１５モル％≦構成単位（Ｉ）≦３５モル％
５モル％≦構成単位（ＩＩ）≦１５モル％
２１モル％≦構成単位（ＩＩＩ）≦２９モル％
１モル％≦構成単位（ＩＶ）≦９モル％
２５モル％≦構成単位（Ｖ）≦４０モル％
構成単位（Ｉ）＋構成単位（ＩＩ）＋構成単位（ＩＩＩ）＋構成単位（ＩＶ）＋構成単位（Ｖ）＝１００モル％、
融点が、３２０℃以上であることを特徴とする。 The wholly aromatic liquid crystal polyester resin according to the present invention,
A wholly aromatic liquid crystal polyester resin comprising the structural units (I) to (V) represented by the following formulas (I) to (V),
The composition ratio (mol%) of the structural units (I) to (V) in the aromatic liquid crystal polyester satisfies the following condition;
15 mol% ≦ structural unit (I) ≦ 35 mol%
5 mol% ≦ structural unit (II) ≦ 15 mol%
21 mol% ≦ structural unit (III) ≦ 29 mol%
1 mol% ≦ structural unit (IV) ≦ 9 mol%
25 mol% ≦ structural unit (V) ≦ 40 mol%
Structural unit (I) + Structural unit (II) + Structural unit (III) + Structural unit (IV) + Structural unit (V) = 100 mol%,
The melting point is 320 ° C. or higher.

上記態様においては、構成単位（ＩＩＩ）の含有量が構成単位（ＩＶ）の含有量の２倍以上であることが好ましい。   In the above embodiment, the content of the structural unit (III) is preferably at least twice the content of the structural unit (IV).

本発明に係る上記全芳香族液晶ポリエステル樹脂の製造方法は、
下記式（１）〜（５）で表されるモノマーを重合する工程を含んでなることを特徴とする。
The method for producing the wholly aromatic liquid crystal polyester resin according to the present invention,
It comprises a step of polymerizing monomers represented by the following formulas (1) to (5).

上記態様においては、モノマーの重合工程が、上記式（１）〜（４）で表されるモノマーが有する全水酸基に対し、１．０５〜１．１５モル当量の無水酢酸の存在下、上記式（１）〜（５）で表されるモノマーを溶融重合することを含んでなることが好ましい。   In the above embodiment, the polymerization step of the monomer is carried out in the presence of 1.05 to 1.15 molar equivalents of acetic anhydride based on the total hydroxyl groups of the monomers represented by the above formulas (1) to (4). Preferably, the method includes melt-polymerizing the monomers represented by (1) to (5).

本発明に係る全芳香族液晶ポリエステル樹脂組成物は、上記全芳香族液晶ポリエステル樹脂および無機充填剤を含んでなることを特徴とする。   A wholly aromatic liquid crystal polyester resin composition according to the present invention is characterized by comprising the above wholly aromatic liquid crystal polyester resin and an inorganic filler.

上記態様においては、無機充填剤が、繊維状充填剤および板状充填剤であることが好ましい。   In the above aspect, the inorganic filler is preferably a fibrous filler and a plate-like filler.

上記態様においては、繊維状充填剤および板状充填剤の含有量が、全芳香族液晶ポリエステル樹脂組成物に含まれる全芳香族液晶ポリエステル樹脂１００重量部に対して、合計１００重量部以下であることが好ましい。   In the above aspect, the content of the fibrous filler and the platy filler is 100 parts by weight or less in total with respect to 100 parts by weight of the wholly aromatic liquid crystal polyester resin contained in the wholly aromatic liquid crystal polyester resin composition. Is preferred.

本発明に係る成形品は、上記全芳香族液晶ポリエステル樹脂組成物を含んでなることを特徴とする。   A molded article according to the present invention is characterized by comprising the above wholly aromatic liquid crystal polyester resin composition.

本発明に係る電子部品は、上記全芳香族液晶ポリエステル樹脂組成物を含んでなることを特徴とする。   An electronic component according to the present invention is characterized by comprising the above-mentioned wholly aromatic liquid crystal polyester resin composition.

本発明によれば、高い機械的強度、充填性および耐ブリスター性を有するため、非常に薄い肉厚部を有する成形品を製造することができ、電子部品の高集積化、薄肉化、低背化を実現することができる。また、本発明によれば、ソリの発生を防止することができる。   ADVANTAGE OF THE INVENTION According to this invention, since it has high mechanical strength, filling property, and blister resistance, it is possible to manufacture a molded article having a very thin wall portion, and to achieve high integration, thinning, and low profile of electronic components. Can be realized. Further, according to the present invention, generation of warpage can be prevented.

実施例の充填性試験で使用された金型の上面図および側面図である。It is the top view and side view of the metal mold | die used by the filling test of the Example. 実施例の箱ソリの測定で作製した箱形成形品の底面図である。It is a bottom view of the box-shaped article manufactured by the measurement of the box warp of an Example. 実施例の箱ソリの測定で作製した箱形成形品の正面図である。It is a front view of the box-shaped article manufactured by the measurement of the box warp of an Example.

（全芳香族液晶ポリエステル樹脂）
本発明による全芳香族液晶ポリエステル樹脂は、下記式（Ｉ）〜（Ｖ）で表される構成単位（Ｉ）〜（Ｖ）を含んでなり、芳香族液晶ポリエステル中における構成単位（Ｉ）〜（Ｖ）の組成比（モル％）は、下記の条件を満たす。このような全芳香族液晶ポリエステル樹脂によれば、該樹脂を使用し作製した成形品に対し、高い機械的強度、充填性および耐ブリスター性ならびに低ソリ性を付与することができる。
１５モル％≦構成単位（Ｉ）≦３５モル％
５モル％≦構成単位（ＩＩ）≦１５モル％
２１モル％≦構成単位（ＩＩＩ）≦２９モル％
１モル％≦構成単位（ＩＶ）≦９モル％
２５モル％≦構成単位（Ｖ）≦４０モル％
構成単位（Ｉ）＋構成単位（ＩＩ）＋構成単位（ＩＩＩ）＋構成単位（ＩＶ）＋構成単位（Ｖ）＝１００モル％、 (Wholly aromatic liquid crystal polyester resin)
The wholly aromatic liquid crystal polyester resin according to the present invention comprises the structural units (I) to (V) represented by the following formulas (I) to (V), and the structural units (I) to The composition ratio (mol%) of (V) satisfies the following condition. According to such a wholly aromatic liquid crystal polyester resin, high mechanical strength, filling property, blister resistance, and low warpage can be imparted to a molded article produced using the resin.
15 mol% ≦ structural unit (I) ≦ 35 mol%
5 mol% ≦ structural unit (II) ≦ 15 mol%
21 mol% ≦ structural unit (III) ≦ 29 mol%
1 mol% ≦ structural unit (IV) ≦ 9 mol%
25 mol% ≦ structural unit (V) ≦ 40 mol%
Structural unit (I) + Structural unit (II) + Structural unit (III) + Structural unit (IV) + Structural unit (V) = 100 mol%,

全芳香族液晶ポリエステル樹脂における構成単位（ＩＩＩ）と、構成単位（ＩＶ）との配合比（モル％）は、構成単位（ＩＩＩ）の含有量が、構成単位（ＩＶ）の含有量の２倍以上であることが好ましく、４倍以上であることがより好ましい。構成単位（ＩＩＩ）と、構成単位（ＩＶ）との配合比（モル％）を上記数値範囲とすることにより、全芳香族液晶ポリエステル樹脂の融点を向上させることができる。   The compounding ratio (mol%) of the structural unit (III) and the structural unit (IV) in the wholly aromatic liquid crystal polyester resin is such that the content of the structural unit (III) is twice the content of the structural unit (IV). It is preferably at least 4 times, more preferably at least 4 times. The melting point of the wholly aromatic liquid crystal polyester resin can be improved by setting the blending ratio (mol%) of the structural unit (III) to the structural unit (IV) within the above numerical range.

また、本発明による全芳香族液晶ポリエステル樹脂の融点は、３２０℃以上である。
本発明に係る全芳香族液晶ポリエステル樹脂は高い融点を有するため、電子部品として要求される耐熱性を満たすことができる。
融点は、ＩＳＯ１１３５７−３、ＡＳＴＭ Ｄ３４１８に準拠するものであり、例えば、セイコー電子工業（株）製の示差走査熱量計（ＤＳＣ）を用いることにより測定することができる。
なお、昇温速度２０℃／分で室温から３８０℃まで昇温し、全芳香族液晶ポリエステル樹脂を完全に融解させたあと、速度１０℃／分で５０℃まで降温し、更に２０℃／分の速度で４２０℃まで昇温するときに得られる吸熱ピークの頂点を融点とする。 The melting point of the wholly aromatic liquid crystal polyester resin according to the present invention is 320 ° C. or higher.
Since the wholly aromatic liquid crystal polyester resin according to the present invention has a high melting point, it can satisfy the heat resistance required as an electronic component.
The melting point complies with ISO11357-3 and ASTM D3418, and can be measured by using, for example, a differential scanning calorimeter (DSC) manufactured by Seiko Denshi Kogyo KK.
The temperature was raised from room temperature to 380 ° C. at a rate of 20 ° C./min to completely melt the wholly aromatic liquid crystal polyester resin, and then the temperature was lowered to 50 ° C. at a rate of 10 ° C./min. The apex of the endothermic peak obtained when the temperature is raised to 420 ° C. at the speed described above is defined as the melting point.

以下、全芳香族液晶ポリエステル樹脂に含まれる各構成単位について説明する。   Hereinafter, each constituent unit contained in the wholly aromatic liquid crystal polyester resin will be described.

（構成単位（Ｉ））
全芳香族液晶ポリエステル樹脂は、上記した構成単位（Ｉ）を含んでなるものであり、芳香族液晶ポリエステル中における構成単位（Ｉ）の組成比（モル％）は、１５モル％〜３５モル％である。より好ましくは２０モル％〜３５モル％であり、さらに好ましくは２５モル％〜３５モル％である。 (Structural unit (I))
The wholly aromatic liquid crystal polyester resin contains the structural unit (I) described above, and the composition ratio (mol%) of the structural unit (I) in the aromatic liquid crystal polyester is from 15 mol% to 35 mol%. It is. More preferably, it is 20 mol% to 35 mol%, and still more preferably, it is 25 mol% to 35 mol%.

構成単位（Ｉ）を与えるモノマーとしては、ｐ−ヒドロキシ安息香酸（ＨＢＡ、下記式（１））、そのアシル化物、エステル誘導体、酸ハロゲン化物などが挙げられる。
Examples of the monomer that provides the structural unit (I) include p-hydroxybenzoic acid (HBA, the following formula (1)), an acylated product thereof, an ester derivative, and an acid halide.

（構成単位（ＩＩ））
全芳香族液晶ポリエステル樹脂は、上記した構成単位（ＩＩ）を含んでなるものであり、芳香族液晶ポリエステル中における構成単位（ＩＩ）の組成比（モル％）は、５モル％〜１５モル％である。より好ましくは８モル％〜１５モル％であり、さらに好ましくは８モル％〜１０モル％である。 (Structural unit (II))
The wholly aromatic liquid crystal polyester resin contains the structural unit (II) described above, and the composition ratio (mol%) of the structural unit (II) in the aromatic liquid crystal polyester is 5 mol% to 15 mol%. It is. It is more preferably from 8 mol% to 15 mol%, and still more preferably from 8 mol% to 10 mol%.

構成単位（ＩＩ）を与えるモノマーとしては、６−ヒドロキシ−２−ナフトエ酸（ＨＮＡ、下記式（２））、そのアシル化物、エステル誘導体、酸ハロゲン化物などが挙げられる。
Examples of the monomer that provides the structural unit (II) include 6-hydroxy-2-naphthoic acid (HNA, the following formula (2)), acylated products thereof, ester derivatives, acid halides, and the like.

（構成単位（ＩＩＩ））
全芳香族液晶ポリエステル樹脂は、上記した構成単位（ＩＩＩ）を含んでなるものであり、芳香族液晶ポリエステル中における構成単位（ＩＩＩ）の組成比（モル％）は、２１モル％〜２９モル％である。より好ましくは２１モル％〜２８モル％であり、さらに好ましくは２２モル％〜２６モル％である。 (Structural unit (III))
The wholly aromatic liquid crystal polyester resin contains the structural unit (III) described above, and the composition ratio (mol%) of the structural unit (III) in the aromatic liquid crystal polyester is from 21 mol% to 29 mol%. It is. More preferably, it is 21 mol% to 28 mol%, and still more preferably, it is 22 mol% to 26 mol%.

構成単位（ＩＩＩ）を与えるモノマーとしては、ハイドロキノン（ＨＱ，下記式（３））、そのアシル化物などが挙げられる。
Examples of the monomer that provides the structural unit (III) include hydroquinone (HQ, the following formula (3)) and acylated products thereof.

（構成単位（ＩＶ））
全芳香族液晶ポリエステル樹脂は、上記した構成単位（ＩＶ）を含んでなるものであり、芳香族液晶ポリエステル中における構成単位（ＩＶ）の組成比（モル％）は、１モル％〜９モル％である。より好ましくは１．５モル％〜９モル％であり、さらに好ましくは１．５モル％〜７モル％である。 (Structural unit (IV))
The wholly aromatic liquid crystal polyester resin contains the structural unit (IV) described above, and the composition ratio (mol%) of the structural unit (IV) in the aromatic liquid crystal polyester is 1 mol% to 9 mol%. It is. More preferably, it is 1.5 mol% to 9 mol%, and still more preferably, 1.5 mol% to 7 mol%.

構成単位（ＩＶ）を与えるモノマーとしては、４，４−ジヒドロキシビフェニル（ＢＰ、下記式（４））、そのアシル化物などが挙げられる。
Examples of the monomer giving the structural unit (IV) include 4,4-dihydroxybiphenyl (BP, the following formula (4)), and acylated products thereof.

（構成単位（Ｖ））
全芳香族液晶ポリエステル樹脂は、上記した構成単位（Ｖ）を含んでなるものであり、芳香族液晶ポリエステル中における構成単位（Ｖ）の組成比（モル％）は、２５モル％〜４０モル％である。より好ましくは２５モル％〜３５モル％であり、さらに好ましくは２７．５モル％〜３２．５モル％である。 (Structural unit (V))
The wholly aromatic liquid crystal polyester resin contains the structural unit (V) described above, and the composition ratio (mol%) of the structural unit (V) in the aromatic liquid crystal polyester is 25 mol% to 40 mol%. It is. More preferably, it is 25 mol% to 35 mol%, and still more preferably, 27.5 mol% to 32.5 mol%.

構成単位（Ｖ）を与えるモノマーとしては、テレフタル酸（ＴＰＡ、下記式（５））、そのエステル誘導体、酸ハロゲン化物などが挙げられる。
Examples of the monomer that provides the structural unit (V) include terephthalic acid (TPA, the following formula (5)), an ester derivative thereof, and an acid halide.

（全芳香族液晶ポリエステル樹脂の製造方法）
本発明に係る全芳香族液晶ポリエステル樹脂は、上記式（１）〜（５）で表されるモノマーを、従来公知の方法で重合することにより製造することができる。
例えば、本発明に係る全芳香族液晶ポリエステル樹脂は、溶融重合のみによって製造することができる。また、溶融重合によりプレポリマーを作製し、これをさらに固相重合することによっても製造することができる。 (Production method of wholly aromatic liquid crystal polyester resin)
The wholly aromatic liquid crystal polyester resin according to the present invention can be produced by polymerizing the monomers represented by the above formulas (1) to (5) by a conventionally known method.
For example, the wholly aromatic liquid crystal polyester resin according to the present invention can be produced only by melt polymerization. Further, it can also be produced by preparing a prepolymer by melt polymerization and further subjecting it to solid phase polymerization.

溶融重合は、本発明に係る全芳香族ポリエステル化合物が効率よく得られる観点から、上記式（１）〜（５）で表されるモノマーを、所定の配合で合わせて１００モル％として、上記式（１）〜（４）で表されるモノマーが有する全水酸基に対し、１．０５〜１．１５モル当量の無水酢酸を存在させて酢酸還流下において行うことが好ましい。   In the melt polymerization, from the viewpoint that the wholly aromatic polyester compound according to the present invention can be efficiently obtained, the monomers represented by the above formulas (1) to (5) are combined in a predetermined mixture to give 100 mol%, and It is preferable to carry out the reaction under reflux of acetic acid in the presence of 1.05 to 1.15 molar equivalents of acetic anhydride with respect to all the hydroxyl groups of the monomers represented by (1) to (4).

溶融重合とこれに続く固相重合の二段階により重合反応を行う場合は、溶融重合により得られたプレポリマーを冷却固化後に粉砕してパウダー状もしくはフレーク状にした後、公知の固相重合方法、例えば、窒素などの不活性雰囲気下、または真空下において２００〜３５０℃の温度範囲で１〜３０時間プレポリマー樹脂を熱処理するなどの方法が好ましくは選択される。固相重合は、攪拌しながら行ってもよく、また攪拌することなく静置した状態で行ってもよい。   When the polymerization reaction is carried out in two stages of melt polymerization and subsequent solid phase polymerization, the prepolymer obtained by melt polymerization is cooled and solidified and then pulverized into a powder or a flake, followed by a known solid state polymerization method. For example, a method in which the prepolymer resin is heat-treated in a temperature range of 200 to 350 ° C. for 1 to 30 hours under an inert atmosphere such as nitrogen or under vacuum is preferably selected. The solid phase polymerization may be performed with stirring, or may be performed in a state of standing without stirring.

重合反応において触媒は使用してもよいし、また使用しなくてもよい。使用する触媒としては、ポリエステルの重合用触媒として従来公知のものを使用することができ、酢酸マグネシウム、酢酸第一錫、テトラブチルチタネート、酢酸鉛、酢酸ナトリウム、酢酸カリウム、三酸化アンチモンなどの金属塩触媒、Ｎ−メチルイミダゾールなどの窒素含有複素環化合物等、有機化合物触媒等が挙げられる。触媒の使用量は、とくに限定されるものではないが、モノマーの総量１００重量部に対して、０．０００１〜０．１重量部であることが好ましい。   In the polymerization reaction, a catalyst may or may not be used. As the catalyst to be used, those conventionally known as catalysts for polyester polymerization can be used, and metals such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide can be used. Organic compound catalysts such as salt catalysts, nitrogen-containing heterocyclic compounds such as N-methylimidazole, and the like can be mentioned. The amount of the catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 part by weight based on 100 parts by weight of the total amount of the monomers.

溶融重合における重合反応装置は特に限定されるものではないが、一般の高粘度流体の反応に用いられる反応装置が好ましく使用される。これらの反応装置の例としては、例えば、錨型、多段型、螺旋帯型、螺旋軸型等、あるいはこれらを変形した各種形状の攪拌翼をもつ攪拌装置を有する攪拌槽型重合反応装置、又は、ニーダー、ロールミル、バンバリーミキサー等の、一般に樹脂の混練に使用される混合装置などが挙げられる。   The polymerization reactor in melt polymerization is not particularly limited, but a reactor used for a reaction of a general high-viscosity fluid is preferably used. Examples of these reactors include, for example, an anchor type, a multi-stage type, a spiral band type, a spiral shaft type, or the like, or a stirred tank type polymerization reactor having a stirrer having a stirring blade having various shapes deformed from these, or , Kneaders, roll mills, Banbury mixers, and other mixing devices generally used for kneading resins.

（全芳香族液晶ポリエステル樹脂組成物）
本発明による全芳香族液晶ポリエステル樹脂組成物は、上記全芳香族液晶ポリエステル樹脂および無機充填剤を含んでなる。
全芳香族液晶ポリエステル樹脂組成物における全芳香族液晶ポリエステル樹脂の含有量は、５０重量％以上であることが好ましく、６０〜９０重量％であることがより好ましい。 (Wholly aromatic liquid crystal polyester resin composition)
The wholly aromatic liquid crystal polyester resin composition according to the present invention comprises the above wholly aromatic liquid crystal polyester resin and an inorganic filler.
The content of the wholly aromatic liquid crystal polyester resin in the wholly aromatic liquid crystal polyester resin composition is preferably 50% by weight or more, and more preferably 60 to 90% by weight.

また、全芳香族液晶ポリエステル樹脂組成物に含まれる無機充填剤としては、例えば、繊維状、板状、粉末状のものを使用することができ、これらを合わせて使用してもよい。中でも、繊維状充填剤および板状充填剤を合わせて使用することが好ましい。
無機充填剤としては、例えば、ガラス繊維、ミルドガラス、シリカアルミナ繊維、アルミナ繊維、炭素繊維、アラミド繊維、チタン酸カリウムウイスカ、ホウ酸アルミニウムウイスカ、ウォラストナイト、タルク、マイカ、グラファイト、炭酸カルシウム、ドロマイト、クレイ、ガラスフレーク、ガラスビーズ、硫酸バリウムおよび酸化チタンなどが挙げられ、全芳香族液晶ポリエステル樹脂組成物は、これらを1種または２種以上含んでいてもよい。 Further, as the inorganic filler contained in the wholly aromatic liquid crystal polyester resin composition, for example, a fibrous, plate-like or powder-like inorganic filler can be used, and these may be used in combination. Especially, it is preferable to use a fibrous filler and a plate-like filler together.
Examples of the inorganic filler include glass fiber, milled glass, silica alumina fiber, alumina fiber, carbon fiber, aramid fiber, potassium titanate whisker, aluminum borate whisker, wollastonite, talc, mica, graphite, calcium carbonate, Examples thereof include dolomite, clay, glass flakes, glass beads, barium sulfate, and titanium oxide, and the wholly aromatic liquid crystal polyester resin composition may include one or more of these.

全芳香族液晶ポリエステル樹脂組成物における無機充填剤の含有量は、全芳香族液晶ポリエステル樹脂組成物に含まれる全芳香族液晶ポリエステル樹脂１００重量部に対して、１００重量部以下であることが好ましく、１０〜６５重量部であることがより好ましい。無機充填剤の含有量を上記数値範囲内とすることにより、成形時の充填性を阻害することなく成形品製造時におけるソリの発生を防止することができる。   The content of the inorganic filler in the wholly aromatic liquid crystal polyester resin composition is preferably 100 parts by weight or less based on 100 parts by weight of the wholly aromatic liquid crystal polyester resin contained in the wholly aromatic liquid crystal polyester resin composition. , 10 to 65 parts by weight. By setting the content of the inorganic filler within the above numerical range, it is possible to prevent warpage during production of a molded article without impairing the filling property at the time of molding.

本発明による全芳香族液晶ポリエステル樹脂組成物は、本発明の効果を損なわない範囲において、全芳香族液晶ポリエステル樹脂以外の樹脂を含んでいてもよい。例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、ポリアリレート、ポリアミド、ポリイミド、ポリエーテルサルホン、ポリエーテルエーテルケトン、ポリフェニレンスルフィド、ポリテトラフルオロエチレンなどが挙げられ、全芳香族液晶ポリエステル樹脂組成物は、これらを1種または２種以上含んでいてもよい。   The wholly aromatic liquid crystal polyester resin composition according to the present invention may contain a resin other than the wholly aromatic liquid crystal polyester resin as long as the effects of the present invention are not impaired. For example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyamide, polyimide, polyether sulfone, polyether ether ketone, polyphenylene sulfide, polytetrafluoroethylene, and the like, and a wholly aromatic liquid crystal polyester resin composition, One or more of these may be included.

本発明による全芳香族液晶ポリエステル樹脂組成物は、本発明の効果を損なわない範囲において、その他の添加剤、例えば、着色剤、分散剤、可塑剤、酸化防止剤、難燃剤、熱安定剤、紫外線吸収剤、帯電防止剤、界面活性剤を含んでいてもよい。   The wholly aromatic liquid crystal polyester resin composition according to the present invention has other additives, for example, a colorant, a dispersant, a plasticizer, an antioxidant, a flame retardant, a heat stabilizer, as long as the effects of the present invention are not impaired. It may contain an ultraviolet absorber, an antistatic agent, and a surfactant.

（全芳香族液晶ポリエステル樹脂組成物の製造方法）
全芳香族液晶ポリエステル樹脂組成物は、全芳香族液晶ポリエステル樹脂に、充填剤などを配合したものを、バンバリーミキサー、ニーダー、一軸または二軸押出機などを用いて、溶融混練することにより得ることができる。 (Production method of wholly aromatic liquid crystal polyester resin composition)
A wholly aromatic liquid crystal polyester resin composition is obtained by melt-kneading a mixture of a wholly aromatic liquid crystal polyester resin with a filler or the like using a Banbury mixer, a kneader, a single-screw or twin-screw extruder, or the like. Can be.

（成形品）
本発明による成形品は、全芳香族液晶ポリエステル樹脂組成物を含んでなるものであり、この組成物を射出成形、押出成形することにより得ることができる。また、同様の方法により、全芳香族液晶ポリエステル樹脂組成物からなるフィルム、シートおよび不織布を得ることができる。
具体的なフィルム化方法としては、インフレーション成形、溶融押出成形、溶液キャスト成形などが挙げられる。このようにして得られたフィルムは、全芳香族ポリエステル樹脂組成物からなる単層フィルムであってもよく、異種材料との多層フィルムであってもよい。
なお、溶融押出成形、溶液キャスト成形したフィルムを寸法安定性、機械特性を改良する目的で、単軸、または二軸にて延伸処理をしてもよい。また、これらフィルムの異方性を除去する目的で熱処理を行ってもよい。 (Molding)
The molded article according to the present invention comprises a wholly aromatic liquid crystal polyester resin composition, and can be obtained by injection molding and extrusion molding this composition. Further, a film, a sheet and a nonwoven fabric made of the wholly aromatic liquid crystal polyester resin composition can be obtained by the same method.
Specific examples of the film forming method include inflation molding, melt extrusion molding, and solution cast molding. The film thus obtained may be a single-layer film made of a wholly aromatic polyester resin composition or a multilayer film made of different materials.
For the purpose of improving dimensional stability and mechanical properties, a film formed by melt extrusion molding or solution casting may be subjected to a uniaxial or biaxial stretching treatment. Further, heat treatment may be performed for the purpose of removing anisotropy of these films.

（電子部品）
本発明による電子部品は、上記全芳香族液晶ポリエステル樹脂組成物を含んでなる。電子部品としては、例えば、高速伝送用コネクタ、ＣＰＵソケット、回路基板、フレキシブル回路基板、積層用回路基板、衝突防止用レーダー、ＲＦＩＤタグ、コンデンサー、インバーター部品、絶縁フィルム、リチウムイオン電池などの二次電池の絶縁材、スピーカー振動板などが挙げられる。具体的には、これら電子部品は、全芳香族液晶ポリエステル樹脂組成物からなる成形品（例えば、射出成形品）やフィルムなどを備えてなる。 (Electronic components)
The electronic component according to the present invention comprises the above wholly aromatic liquid crystal polyester resin composition. Examples of electronic components include high-speed transmission connectors, CPU sockets, circuit boards, flexible circuit boards, circuit boards for lamination, anti-collision radars, RFID tags, capacitors, inverter parts, insulating films, lithium ion batteries, and other secondary components. Examples include a battery insulating material and a speaker diaphragm. Specifically, these electronic components are provided with a molded article (for example, an injection molded article) or a film made of the wholly aromatic liquid crystal polyester resin composition.

以下、実施例により本発明をより具体的に説明するが、本発明は実施例に限定されるものではない。   Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.

＜全芳香族液晶ポリエステル樹脂の製造＞
（実施例１：全芳香族液晶ポリエステル樹脂Ａ）
攪拌翼を有する重合容器にｐ−ヒドロキシ安息香酸（ＨＢＡ）２４．９ｇ（３０モル％）、６−ヒドロキシ−２−ナフトエ酸（ＨＮＡ）１１．３ｇ（１０モル％）、ハイドロキノン（ＨＱ）１５．９ｇ（２４モル％）、４，４−ジヒドロキシビフェニル（ＢＰ）６．７ｇ（６モル％）、テレフタル酸（ＴＰＡ）２９．９（３０モル％）を加え、触媒として酢酸カリウム及び、酢酸マグネシウムを仕込み、重合容器の減圧−窒素注入を３回行って窒素置換を行った後、無水酢酸６６．２ｇ（水酸基に対して１．０８モル当量）を更に添加し、１５０℃まで昇温し、還流状態で２時間アセチル化反応を行った。 <Production of wholly aromatic liquid crystal polyester resin>
(Example 1: wholly aromatic liquid crystal polyester resin A)
In a polymerization vessel having a stirring blade, 24.9 g (30 mol%) of p-hydroxybenzoic acid (HBA), 11.3 g (10 mol%) of 6-hydroxy-2-naphthoic acid (HNA), and hydroquinone (HQ) 15. 9 g (24 mol%), 6.7 g (6 mol%) of 4,4-dihydroxybiphenyl (BP) and 29.9 (30 mol%) of terephthalic acid (TPA) were added, and potassium acetate and magnesium acetate were used as catalysts. After charging and carrying out pressure reduction and nitrogen injection of the polymerization vessel three times to perform nitrogen substitution, 66.2 g of acetic anhydride (1.08 molar equivalent to the hydroxyl group) was further added, and the temperature was raised to 150 ° C. and refluxed. The acetylation reaction was performed for 2 hours in this state.

アセチル化終了後、酢酸留出状態にした重合容器を０．５℃／分で昇温して、槽内の溶融体温度が３１０℃になったところで重合物を抜き出し、冷却固化した。得られた重合物を粉砕し目開き１．０ｍｍの篩を通過する大きさに粉砕してプレポリマーを得た。   After the acetylation was completed, the polymerization vessel in which acetic acid had been distilled was heated at a rate of 0.5 ° C./min, and when the temperature of the melt in the tank reached 310 ° C., the polymer was extracted and cooled and solidified. The obtained polymer was pulverized and pulverized to a size passing through a sieve having an opening of 1.0 mm to obtain a prepolymer.

次に、上記で得られたプレポリマーを柴田科学製ガラスチューブオーブンに充填し、回転させながらヒーター温度を室温から１２時間かけて２９０℃まで昇温した後、２９０℃で温度を１時間保持して固相重合を行った。その後槽を回転させながら室温で自然放熱し、全芳香族液晶ポリエステル樹脂Ａを得た。メトラー製の顕微鏡用ホットステージＦＰ８２ＨＴを備えたオリンパス（株）製の偏光顕微鏡ＢＨ−２を用い、ポリエステル試料を顕微鏡加熱ステージ上にて加熱溶融させ、光学異方性の有無から液晶性を確認した。   Next, the prepolymer obtained above was filled in a glass tube oven manufactured by Shibata Kagaku, and the temperature of the heater was increased from room temperature to 290 ° C. over 12 hours while rotating, and then maintained at 290 ° C. for 1 hour. To perform solid state polymerization. Thereafter, heat was naturally radiated at room temperature while the tank was rotated to obtain a wholly aromatic liquid crystal polyester resin A. Using a polarizing microscope BH-2 manufactured by Olympus Corporation equipped with a hot stage FP82HT for a microscope manufactured by Mettler, the polyester sample was heated and melted on a microscope heating stage, and the liquid crystallinity was confirmed from the presence or absence of optical anisotropy. .

（実施例２：全芳香族液晶ポリエステル樹脂Ｂ）
モノマー仕込みを、ＨＢＡ３０モル％、ＨＮＡ１５モル％、ＨＱ２６モル％、ＢＰ１．５モル％、ＴＰＡ２７．５モル％に変更した以外は実施例１と同様にして、液晶ポリエステル樹脂Ｂを得て、上記と同様にして液晶性を確認した。 (Example 2: wholly aromatic liquid crystal polyester resin B)
A liquid crystal polyester resin B was obtained in the same manner as in Example 1 except that the monomer charge was changed to 30 mol% of HBA, 15 mol% of HNA, 26 mol% of HQ, 1.5 mol% of BP, and 27.5 mol% of TPA. The liquid crystal properties were confirmed in the same manner.

（実施例３：全芳香族液晶ポリエステル樹脂Ｃ）
モノマー仕込みを、ＨＢＡ３０モル％、ＨＮＡ１０モル％、ＨＱ２１モル％、ＢＰ９モル％、ＴＰＡ３０モル％に変更した以外は実施例１と同様にして、液晶ポリエステル樹脂Ｃを得て、上記と同様にして液晶性を確認した。 (Example 3: wholly aromatic liquid crystal polyester resin C)
A liquid crystal polyester resin C was obtained in the same manner as in Example 1 except that the monomer charge was changed to 30 mol% of HBA, 10 mol% of HNA, 21 mol% of HQ, 9 mol% of BP, and 30 mol% of TPA. Was confirmed.

（実施例４：全芳香族液晶ポリエステル樹脂Ｄ）
モノマー仕込みを、ＨＢＡ３０モル％、ＨＮＡ１０モル％、ＨＱ２５モル％、ＢＰ５モル％、ＴＰＡ３０モル％に変更した以外は実施例１と同様にして、液晶ポリエステル樹脂Ｄを得て、上記と同様にして液晶性を確認した。 (Example 4: wholly aromatic liquid crystal polyester resin D)
A liquid crystal polyester resin D was obtained in the same manner as in Example 1 except that the monomer preparation was changed to 30 mol% of HBA, 10 mol% of HNA, 25 mol% of HQ, 5 mol% of BP, and 30 mol% of TPA, and a liquid crystal was obtained in the same manner as above. Was confirmed.

（比較例１：全芳香族液晶ポリエステル樹脂Ｅ）
モノマー仕込みを、ＨＢＡ２０モル％、ＨＮＡ２０モル％、ＨＱ１０モル％、ＢＰ２０モル％、ＴＰＡ３０モル％に変更した以外は実施例１と同様にして、アセチル化終了後、酢酸留出状態にしたプレポリマーを得た。 (Comparative Example 1: wholly aromatic liquid crystal polyester resin E)
After the acetylation was completed, the prepolymer in which acetic acid was distilled off was prepared in the same manner as in Example 1 except that the monomer charge was changed to 20 mol% of HBA, 20 mol% of HNA, 10 mol% of HQ, 20 mol% of BP, and 30 mol% of TPA. Obtained.

次に、上記で得られたプレポリマーを柴田科学製ガラスチューブオーブンに充填し、固相重合にて所望の分子量まで重合させようとしたところ、プレポリマーが溶融してしまい、それ以上固相重合を実施することができなかった。その後、槽を回転させながら室温で自然放熱し、液晶ポリエステル樹脂Ｅを得た。   Next, the prepolymer obtained above was charged into a glass tube oven manufactured by Shibata Kagaku, and when it was tried to polymerize to a desired molecular weight by solid phase polymerization, the prepolymer was melted, and further solid phase polymerization was performed. Could not be implemented. Thereafter, the liquid was naturally radiated at room temperature while rotating the tank, to obtain a liquid crystal polyester resin E.

（比較例２：全芳香族液晶ポリエステル樹脂Ｆ）
モノマー仕込みを、ＨＢＡ３０モル％、ＨＮＡ１０モル％、ＨＱ１６モル％、ＢＰ１４モル％、ＴＰＡ３０モル％に変更した以外は実施例１と同様にしてアセチル化終了後、酢酸留出状態にしたプレポリマーを得た。 (Comparative Example 2: wholly aromatic liquid crystal polyester resin F)
A prepolymer was obtained in the same manner as in Example 1, except that the monomer charge was changed to 30 mol% of HBA, 10 mol% of HNA, 16 mol% of HQ, 14 mol% of BP, and 30 mol% of TPA. Was.

次に、上記で得られたプレポリマーを柴田科学製ガラスチューブオーブンに充填し固相重合にて所望の分子量まで重合させようとしたところプレポリマーが溶融してしまい、それ以上固相重合を実施することができなかった。その後槽を回転させながら室温で自然放熱し、液晶ポリエステル樹脂Ｆを得た。   Next, the prepolymer obtained above was filled into a glass tube oven manufactured by Shibata Kagaku, and solid-state polymerization was attempted to polymerize to a desired molecular weight. I couldn't. Thereafter, the liquid was naturally radiated at room temperature while the tank was rotated to obtain a liquid crystal polyester resin F.

（比較例３：全芳香族液晶ポリエステル樹脂Ｇ）
モノマー仕込みを、ＨＢＡ６モル％、ＨＮＡ１０モル％、ＢＰ４２モル％、ＴＰＡ４２モル％に変更した以外は実施例１と同様にしてアセチル化反応を行った。アセチル化終了後、酢酸留出状態にした重合容器を０．５℃／分で３１０℃まで昇温したところ重合物は固化しやすく、重合容器からの抜き出しができなかった。 (Comparative Example 3: wholly aromatic liquid crystal polyester resin G)
An acetylation reaction was carried out in the same manner as in Example 1, except that the charged monomers were changed to 6 mol% of HBA, 10 mol% of HNA, 42 mol% of BP, and 42 mol% of TPA. After completion of the acetylation, the temperature of the polymerization vessel in which acetic acid was distilled off was raised to 310 ° C. at a rate of 0.5 ° C./min, and the polymer was easily solidified and could not be removed from the polymerization vessel.

（比較例４：全芳香族液晶ポリエステル樹脂Ｈ）
モノマー仕込みを、ＨＢＡ６０モル％、ＢＰ２０モル％、ＴＰＡ１５モル％、イソフタル酸５モル％に変更した以外は実施例１と同様にして、液晶ポリエステル樹脂Ｈを得て、上記と同様にして液晶性を確認した。 (Comparative Example 4: wholly aromatic liquid crystal polyester resin H)
A liquid crystal polyester resin H was obtained in the same manner as in Example 1 except that the monomer preparation was changed to 60 mol% of HBA, 20 mol% of BP, 15 mol% of TPA, and 5 mol% of isophthalic acid. confirmed.

＜＜抜出性＞＞
重合容器の温度が所定の温度に達した後、重合容器から重合物を抜き出す際の挙動を観察し、以下の評価基準に従い、抜出性を評価した。
（評価基準）
○：容易に抜き出し可能であった。
×：抜き出しが困難であり、容器内に樹脂が残存してしまった。 << Extractability >>
After the temperature of the polymerization vessel reached a predetermined temperature, the behavior when the polymer was extracted from the polymerization vessel was observed, and the removability was evaluated according to the following evaluation criteria.
(Evaluation criteria)
：: Extraction was easy.
×: Extraction was difficult, and the resin remained in the container.

＜＜融点の測定＞＞
実施例および比較例において得られた液晶ポリエステル樹脂の融点は、セイコー電子工業（株）製の示差走査熱量計（ＤＳＣ）により測定した。このとき、昇温速度２０℃／分で室温から３８０℃まで昇温してポリマーを完全に融解させた後、速度１０℃／分で５０℃まで降温し、更に２０℃／分の速度で４２０℃まで昇温するときに得られる吸熱ピークの頂点を融点とした。測定結果を表１にまとめた。 << Measurement of melting point >>
The melting points of the liquid crystal polyester resins obtained in the examples and comparative examples were measured by a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc. At this time, the temperature was raised from room temperature to 380 ° C. at a heating rate of 20 ° C./min to completely melt the polymer, and then the temperature was lowered to 50 ° C. at a rate of 10 ° C./min. The peak of the endothermic peak obtained when the temperature was raised to ° C was defined as the melting point. Table 1 summarizes the measurement results.

＜全芳香族液晶ポリエステル樹脂組成物の製造＞
実施例１と同じモノマー組成となるようにｐ−ヒドロキシ安息香酸６６３．０ｇ（３０モル％）、６−ヒドロキシ−２−ナフトエ酸３０１．１ｇ（１０モル％）、ハイドロキノン４２２．８ｇ（２４モル％）、４，４−ジヒドロキシビフェニル１７８．８ｇ（６モル％）、テレフタル酸７９７．４（３０モル％）、触媒として酢酸カリウム０．３０ｇ及び、酢酸マグネシウム０．３０ｇを、ＳＵＳ３１６を材質とし、ダブルヘリカル攪拌翼を有する内容積６Ｌの重合槽へ仕込み、実施例1と同様の条件にてプレポリマーを得た。
次に、上記で得られたプレポリマーを固相重合装置に充填し、窒素を流通しながら、回転速度５ｒｐｍでヒーター温度を室温から１５０℃まで１時間かけて昇温した後、２５０℃まで１０時間かけて昇温し、２５０℃で２時間保持した。
更に２７０℃まで６時間、更に２９０℃まで６時間かけて昇温し、２９０℃で２時間保持した。さらに３１０℃まで６時間かけて昇温し、３１０℃で１時間保持し、固相重合を行った。こうして、全芳香族液晶ポリエステル樹脂Ａを得た。
上記のようにして得られた全芳香族液晶ポリエステル樹脂Ａ１００重量部に対し、繊維状充填剤（セントラルグラスファイバー（株）製、商品名：ＥＦＨ１５０−０１）を７重量部、板状充填剤（マイカ、（株）ヤマグチマイカ製、商品名：ＡＢ−２５Ｓ）を３６重量部、カーボンブラック（キャボット（株）社製、商品名：ＲＥＧＡＬ９９Ｉ）を１重量部配合し、二軸押出機にて溶融混練したものをペレット化し、全芳香族液晶ポリエステル樹脂組成物Ａを得た。
また、全芳香族液晶ポリエステル樹脂Ａを比較例４により得られた全芳香族液晶ポリエステル樹脂Ｈに変更した以外は、同様にして全芳香族液晶ポリエステル樹脂組成物Ｈを得た。 <Production of wholly aromatic liquid crystal polyester resin composition>
663.0 g (30 mol%) of p-hydroxybenzoic acid, 301.1 g (10 mol%) of 6-hydroxy-2-naphthoic acid, 422.8 g (24 mol%) of hydroquinone so as to have the same monomer composition as in Example 1. ), 17,8.8 g (6 mol%) of 4,4-dihydroxybiphenyl, 797.4 (30 mol%) of terephthalic acid, 0.30 g of potassium acetate and 0.30 g of magnesium acetate as catalysts, made of SUS316, A polymerization vessel having an inner volume of 6 L having a helical stirring blade was charged, and a prepolymer was obtained under the same conditions as in Example 1.
Next, the prepolymer obtained above was charged into a solid-state polymerization apparatus, and the temperature of the heater was increased from room temperature to 150 ° C. over 1 hour at a rotation speed of 5 rpm while flowing nitrogen. The temperature was raised over time and kept at 250 ° C. for 2 hours.
The temperature was further raised to 270 ° C. for 6 hours and further to 290 ° C. for 6 hours, and kept at 290 ° C. for 2 hours. The temperature was further raised to 310 ° C. over 6 hours, and the temperature was maintained at 310 ° C. for 1 hour to perform solid-state polymerization. Thus, a wholly aromatic liquid crystal polyester resin A was obtained.
Based on 100 parts by weight of the wholly aromatic liquid crystal polyester resin A obtained as described above, 7 parts by weight of a fibrous filler (trade name: EFH150-01, manufactured by Central Glass Fiber Co., Ltd.) and a plate-like filler ( 36 parts by weight of mica, manufactured by Yamaguchi Mica Co., Ltd., trade name: AB-25S, and 1 part by weight of carbon black (trade name: REGAL99I, manufactured by Cabot Corp.), and melted by a twin screw extruder The kneaded product was pelletized to obtain a wholly aromatic liquid crystal polyester resin composition A.
Also, a wholly aromatic liquid crystal polyester resin composition H was obtained in the same manner except that the wholly aromatic liquid crystal polyester resin A was changed to the wholly aromatic liquid crystal polyester resin H obtained in Comparative Example 4.

＜＜充填性試験（流動長の測定）＞＞
得られた全芳香族液晶ポリエステル樹脂組成物Ａのペレットを、射出成形機（Ｓｏｄｉｃｋ製、商品名：ＬＤ１０ＥＨ２）を用いて、シリンダー温度を見掛け溶融粘度測定（昇温）時、溶融粘度の値が安定し始める温度（３６０℃）に設定し、金型温度を８０℃とし、射出速度１３３ｍｍ／ｓｅｃで金型内へ射出した。
充填性試験において使用した金型は、図１に示す通りのものであり、幅は２．０ｍｍ、長さ４０ｍｍ、厚さ０．１ｍｍの薄肉部を有する金型を使用し、射出された樹脂組成物が、薄肉部へ流入し形成された薄肉部の長さにより樹脂組成物の充填性を評価した。
この試験を２０回繰り返し、形成された薄肉部の長さの平均を表２に記載した。
同様の試験を全芳香族液晶ポリエステル樹脂組成物Ｈに対しても行い、その結果を表２に記載した。 << Fillability test (measurement of flow length) >>
When the obtained pellets of the wholly aromatic liquid crystal polyester resin composition A were measured for melt viscosity (increased temperature) at an apparent cylinder temperature using an injection molding machine (manufactured by Sodick, trade name: LD10EH2), the melt viscosity value was reduced. The temperature was set to be stable (360 ° C.), the mold temperature was set to 80 ° C., and the mold was injected into the mold at an injection speed of 133 mm / sec.
The mold used in the filling test was as shown in FIG. 1. A mold having a thin portion having a width of 2.0 mm, a length of 40 mm, and a thickness of 0.1 mm was used. The filling property of the resin composition was evaluated based on the length of the thin portion formed by the composition flowing into the thin portion.
This test was repeated 20 times, and the average of the lengths of the formed thin portions is shown in Table 2.
The same test was performed on the wholly aromatic liquid crystal polyester resin composition H, and the results are shown in Table 2.

＜＜機械的強度試験（曲げ強度の測定）＞＞
上記のようにして得られた樹脂組成物Ａのペレットを射出成形機（住友重機械工業（株）製、商品名：ＳＧ−２５）を用いて、上記シリンダー温度で、金型温度を８０℃とし、射出速度１００ｍｍ／ｓｅｃで射出成形し、ＡＳＴＭ Ｄ７９０に準じた曲げ試験片（幅１３ｍｍ、長さ１３０ｍｍ、厚さ３ｍｍ）を作成し曲げ強度を測定した。
また、樹脂組成物Ｈを用いて、同様に試験片を作製し、曲げ強度を測定した。測定結果を表２にまとめた。 << Mechanical strength test (measurement of bending strength) >>
Using the injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name: SG-25), the pellets of the resin composition A obtained as described above were subjected to the above-mentioned cylinder temperature and a mold temperature of 80 ° C. Injection molding was performed at an injection speed of 100 mm / sec, and a bending test piece (width: 13 mm, length: 130 mm, thickness: 3 mm) according to ASTM D790 was prepared, and the bending strength was measured.
In addition, a test piece was similarly prepared using the resin composition H, and the bending strength was measured. Table 2 summarizes the measurement results.

＜＜耐ブリスター性試験（耐ブリスター温度の測定）＞＞
（試験片の成形）
上記のようにして得られた樹脂組成物Ａのペレットを、射出成形機（Ｓｏｄｉｃｋ製、商品名：ＬＤ１０ＥＨ２）にて、上記シリンダー温度で、金型温度を８０℃とし、射出速度１５０ｍｍ／ｓｅｃで射出成形し、ＪＩＳ Ｋ７１６０ ２形に準じた試験片（幅１０ｍｍ、長さ６０ｍｍ、厚さ０．４ｍｍ）を作成した。
また、樹脂組成物Ｈを用いて、同様に試験片を作成した。上記のようにして得られた試験片を所定の温度に保持したエアーオーブン中に３０分間放置して、試験片表面にブリスターおよび変形の発生しない最高温度を耐ブリスター温度とした。測定結果を表２にまとめた。 << Blister resistance test (measurement of blister temperature) >>
(Formation of test piece)
The pellets of the resin composition A obtained as described above are subjected to an injection molding machine (manufactured by Sodick, trade name: LD10EH2) at the above-mentioned cylinder temperature, a mold temperature of 80 ° C, and an injection speed of 150 mm / sec. A test piece (width 10 mm, length 60 mm, thickness 0.4 mm) according to JIS K7160 type 2 was prepared by injection molding.
A test piece was prepared in the same manner using the resin composition H. The test piece obtained as described above was allowed to stand in an air oven maintained at a predetermined temperature for 30 minutes, and the maximum temperature at which blisters and deformation did not occur on the test piece surface was defined as the blister resistance temperature. Table 2 summarizes the measurement results.

＜＜箱ソリ量の測定＞＞
上記のようにして得られた樹脂組成物Ａのペレットを、射出成形機（Ｓｏｄｉｃｋ製、商品名：ＬＤ１０ＥＨ２）にて、シリンダー温度を融点＋１０℃、金型温度１００℃とし、射出速度１３３ｍｍ／ｓｅｃで射出成形し、図２（ａ）および（ｂ）に示す箱型成形品を得た。
上記のようにして得られた成形品を２６０℃に保持したエアーオーブン中に１０分間放置し、加熱後の成形品の底面のソリ（ソリ量）をワンショット３Ｄマクロスコープ（（株）キーエンス社製、商品名：ＶＲ−３１００）を用いて測定した。測定結果を表２にまとめた。なお、形状安定性が良いほどソリ量は小さくなる。 << Measurement of box warpage >>
The pellets of the resin composition A obtained as described above were subjected to an injection molding machine (manufactured by Sodick, trade name: LD10EH2) at a cylinder temperature of + 10 ° C., a mold temperature of 100 ° C., and an injection speed of 133 mm / sec. To obtain a box-shaped molded product as shown in FIGS. 2 (a) and 2 (b).
The molded product obtained as described above is left in an air oven maintained at 260 ° C. for 10 minutes, and the warpage (the amount of warpage) on the bottom surface of the molded product after heating is measured by a one-shot 3D macroscope (Keyence Corporation). And trade name: VR-3100). Table 2 summarizes the measurement results. The better the shape stability, the smaller the amount of warpage.

Claims (9)

下記式（Ｉ）〜（Ｖ）で表される構成単位（Ｉ）〜（Ｖ）を含んでなる全芳香族液晶ポリエステル樹脂であって、
前記芳香族液晶ポリエステル中における構成単位（Ｉ）〜（Ｖ）の組成比（モル％）が、下記の条件を満たし、
１５モル％≦構成単位（Ｉ）≦３５モル％
５モル％≦構成単位（ＩＩ）≦１５モル％
２１モル％≦構成単位（ＩＩＩ）≦２９モル％
１モル％≦構成単位（ＩＶ）≦９モル％
２５モル％≦構成単位（Ｖ）≦４０モル％
構成単位（Ｉ）＋構成単位（ＩＩ）＋構成単位（ＩＩＩ）＋構成単位（ＩＶ）＋構成単位（Ｖ）＝１００モル％、
融点が、３２０℃以上であることを特徴とする、全芳香族液晶ポリエステル樹脂。 A wholly aromatic liquid crystal polyester resin comprising the structural units (I) to (V) represented by the following formulas (I) to (V),
The composition ratio (mol%) of the structural units (I) to (V) in the aromatic liquid crystal polyester satisfies the following condition;
15 mol% ≦ structural unit (I) ≦ 35 mol%
5 mol% ≦ structural unit (II) ≦ 15 mol%
21 mol% ≦ structural unit (III) ≦ 29 mol%
1 mol% ≦ structural unit (IV) ≦ 9 mol%
25 mol% ≦ structural unit (V) ≦ 40 mol%
Structural unit (I) + Structural unit (II) + Structural unit (III) + Structural unit (IV) + Structural unit (V) = 100 mol%,
A wholly aromatic liquid crystal polyester resin having a melting point of 320 ° C. or higher. 構成単位（ＩＩＩ）の含有量が構成単位（ＩＶ）の含有量の２倍以上である、請求項１に記載の全芳香族液晶ポリエステル樹脂。   The wholly aromatic liquid crystal polyester resin according to claim 1, wherein the content of the structural unit (III) is at least twice the content of the structural unit (IV). 請求項１または２に記載の全芳香族液晶ポリエステル樹脂の製造方法であって、
下記式（１）〜（５）で表されるモノマーを重合する工程を含んでなる、方法。
A method for producing a wholly aromatic liquid crystal polyester resin according to claim 1 or 2,
A method comprising a step of polymerizing monomers represented by the following formulas (1) to (5).
前記モノマーの重合工程が、前記式（１）〜（４）で表されるモノマーが有する全水酸基に対し、１．０５〜１．１５モル当量の無水酢酸の存在下、前記式（１）〜（５）で表されるモノマーを溶融重合することを含んでなる、請求項３に記載の方法。   The polymerization step of the monomer is carried out in the presence of 1.05 to 1.15 molar equivalents of acetic anhydride based on the total hydroxyl groups of the monomers represented by the formulas (1) to (4). The method according to claim 3, comprising melt-polymerizing the monomer represented by (5). 請求項１または２に記載の全芳香族液晶ポリエステル樹脂および無機充填剤を含んでなる、全芳香族液晶ポリエステル樹脂組成物。   A wholly aromatic liquid crystal polyester resin composition comprising the wholly aromatic liquid crystal polyester resin according to claim 1 and an inorganic filler. 前記無機充填剤が、繊維状充填剤および板状充填剤である、請求項５に記載の全芳香族液晶ポリエステル樹脂組成物。   The wholly aromatic liquid crystal polyester resin composition according to claim 5, wherein the inorganic filler is a fibrous filler and a plate-like filler. 前記繊維状充填剤および前記板状充填剤の含有量が、前記全芳香族液晶ポリエステル樹脂組成物に含まれる全芳香族液晶ポリエステル樹脂１００重量部に対して、合計が１００重量部以下である、請求項６に記載の全芳香族液晶ポリエステル樹脂組成物。 The total content of the fibrous filler and the plate-like filler is 100 parts by weight or less based on 100 parts by weight of the wholly aromatic liquid crystal polyester resin contained in the wholly aromatic liquid crystal polyester resin composition, The wholly aromatic liquid crystal polyester resin composition according to claim 6 . 請求項５〜７のいずれか一項に記載の全芳香族液晶ポリエステル樹脂組成物を含んでなる、成形品。 A molded article comprising the wholly aromatic liquid crystal polyester resin composition according to any one of claims 5 to 7. 請求項５〜７のいずれか一項に記載の全芳香族液晶ポリエステル樹脂組成物を含んでなる、電子部品。 Comprising a wholly aromatic liquid crystal polyester resin composition according to any one of claims 5-7, the electronic component.
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