JP7175834B2 - liquid crystal polyester resin - Google Patents

liquid crystal polyester resin Download PDF

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JP7175834B2
JP7175834B2 JP2019077598A JP2019077598A JP7175834B2 JP 7175834 B2 JP7175834 B2 JP 7175834B2 JP 2019077598 A JP2019077598 A JP 2019077598A JP 2019077598 A JP2019077598 A JP 2019077598A JP 7175834 B2 JP7175834 B2 JP 7175834B2
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polyester resin
liquid crystalline
crystalline polyester
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JP2020176174A (en
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久成 藤原
哲也 山下
明 小畑
哲英 澤田
聖五 高須賀
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Ueno Fine Chemicals Industry Ltd
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Priority to KR1020200042917A priority patent/KR20200121735A/en
Priority to CN202010295250.8A priority patent/CN111825833B/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
    • C08G63/605—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 the hydroxy and carboxylic groups being bound to aromatic rings
    • 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
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • 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
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • 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
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
    • 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
    • C08G2250/00—Compositions for preparing crystalline polymers

Description

本発明は、液晶ポリエステル樹脂に関する。 The present invention relates to a liquid crystalline polyester resin.

サーモトロピック液晶ポリマー（以下、液晶ポリマーまたはＬＣＰと略称する）は、機械特性、成形性、耐薬品性、ガス遮断性、耐湿性、電気特性などに優れるため、多種多様な分野の部品に用いられている。特に、耐熱性、耐溶媒性、薄肉成形性および絶縁性に優れることから、電動機等の絶縁体（インシュレーター）への使用が拡大しつつある。 Thermotropic liquid crystal polymer (hereafter abbreviated as liquid crystal polymer or LCP) has excellent mechanical properties, moldability, chemical resistance, gas barrier properties, moisture resistance, electrical properties, etc., and is used for parts in a wide variety of fields. ing. In particular, due to its excellent heat resistance, solvent resistance, thin moldability, and insulating properties, its use as insulators for electric motors and the like is expanding.

空調機器、冷房機器、冷蔵庫等の密閉型圧縮機の駆動に用いられる電動機は、冷媒に浸漬された状態で駆動される。従って、電動機の内部に搭載されるインシュレーターも冷媒に浸漬され、かつ室温から１００℃前後に亘る、非常に厳しい温度条件下で使用される。 2. Description of the Related Art Electric motors used to drive hermetic compressors in air conditioners, coolers, refrigerators, etc. are driven while immersed in refrigerant. Therefore, the insulator mounted inside the electric motor is also immersed in the coolant and used under extremely severe temperature conditions ranging from room temperature to around 100°C.

そのため、耐熱性、機械物性および耐薬品性に優れる液晶ポリマーの使用が提案されている。 Therefore, it has been proposed to use liquid crystal polymers that are excellent in heat resistance, mechanical properties and chemical resistance.

例えば、特許文献１には、液晶性樹脂に対して充填剤を配合してなる樹脂組成物を溶融成形してなる電動機のインシュレーター成形品が提案されている。また、特許文献２にはパラヒドロキシ安息香酸と２，６－ヒドロキシナフトエ酸を原料とした液晶ポリマーから構成される絶縁体が提案されている。 For example, Patent Literature 1 proposes an insulator molded product for an electric motor, which is obtained by melt-molding a resin composition obtained by blending a filler with a liquid crystalline resin. Further, Patent Document 2 proposes an insulator composed of a liquid crystal polymer made from parahydroxybenzoic acid and 2,6-hydroxynaphthoic acid.

特許文献１および２に記載の絶縁体（インシュレーター）は、液晶ポリマーで構成することによって、耐熱性に優れ、バリの発生が少ないという利点を有する。 The insulators described in Patent Literatures 1 and 2 have the advantage of being excellent in heat resistance and less likely to generate burrs by being composed of a liquid crystal polymer.

特開平０９－１１１１０６号公報JP-A-09-111106 特開２００４―５２７３０号公報JP-A-2004-52730

しかしながら、特許文献１および２に開示された液晶ポリマーは、機械物性、特に曲げ弾性率が不十分であり、過酷な条件での使用に際してはインシュレーターが変形するおそれがあった。また、これらの液晶ポリマーは比較的融点が高いため、高温で反応を行わないと重合が不十分となって樹脂中に低分子量化合物が残存しやすく、これが冷媒中に溶出しやすいという問題があった。 However, the liquid crystal polymers disclosed in Patent Literatures 1 and 2 are insufficient in mechanical properties, particularly in flexural modulus, and there is a risk that the insulator will deform when used under severe conditions. In addition, since these liquid crystal polymers have a relatively high melting point, there is a problem that if the reaction is not carried out at a high temperature, the polymerization will be insufficient and low molecular weight compounds will tend to remain in the resin, which will easily dissolve into the refrigerant. rice field.

このような問題を解消するため、高い耐熱性および機械強度をバランスよく有し、インシュレーターに適した液晶ポリエステル樹脂の開発が要望されている。 In order to solve such problems, there is a demand for the development of a liquid crystalline polyester resin that has a good balance of high heat resistance and mechanical strength and is suitable for insulators.

本発明の目的は、優れた耐熱性および耐溶媒性を維持しつつ、機械特性、とりわけ曲げ弾性率に優れた液晶ポリエステル樹脂を提供することにある。 An object of the present invention is to provide a liquid crystalline polyester resin which is excellent in mechanical properties, especially flexural modulus, while maintaining excellent heat resistance and solvent resistance.

本発明者等は、上記課題に鑑み、鋭意検討した結果、特定の繰返し単位を与える単量体を縮重合することによって、優れた耐熱性および耐溶媒性を維持しつつ、曲げ弾性率に優れた液晶ポリエステル樹脂が得られることを見出し、本発明を完成させるに至った。 In view of the above problems, the present inventors have made intensive studies and found that by condensation polymerization of a monomer that provides a specific repeating unit, excellent flexural modulus is maintained while maintaining excellent heat resistance and solvent resistance. The inventors have found that a liquid crystalline polyester resin can be obtained by the above method, and have completed the present invention.

すなわち、本発明は、以下の好適な態様を包含する。
〔１〕式（Ｉ）～（ＶＩ）

Figure 0007175834000001
［式中、
ｐ、ｑ、ｒ、ｓ、ｔおよびｕは、それぞれ、液晶ポリエステル樹脂中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす：
６０≦ｐ≦７０、
１５≦ｑ＋ｒ≦２０、
１０≦ｓ＋ｔ≦１９、
１≦ｕ≦５］
で表される繰返し単位から構成される液晶ポリエステル樹脂。
〔２〕ｑ／ｒが０．９～１．３である、〔１〕に記載の液晶ポリエステル樹脂。
〔３〕ｓ／ｔが０．９～１．５である、〔１〕または〔２〕に記載の液晶ポリエステル樹脂。
〔４〕曲げ弾性率が１０ＧＰａ以上である、〔１〕～〔３〕のいずれかに記載の液晶ポリエステル樹脂。
〔５〕〔１〕～〔４〕のいずれかに記載の液晶ポリエステル樹脂１００質量部に対し、繊維状、板状または粉状の充填剤０．１～２００質量部を含む、液晶ポリエステル樹脂組成物。
〔６〕〔１〕～〔４〕のいずれかに記載の液晶ポリエステル樹脂あるいは〔５〕に記載の液晶ポリエステル樹脂組成物から構成される成形品。 That is, the present invention includes the following preferred embodiments.
[1] Formulas (I) to (VI)

Figure 0007175834000001
[In the formula,
p, q, r, s, t and u are the composition ratio (mol%) of each repeating unit in the liquid crystalline polyester resin, and satisfy the following conditions:
60≦p≦70,
15≤q+r≤20,
10≤s+t≤19,
1≦u≦5]
Liquid crystalline polyester resin composed of repeating units represented by
[2] The liquid crystalline polyester resin of [1], wherein q/r is 0.9 to 1.3.
[3] The liquid crystalline polyester resin according to [1] or [2], wherein s/t is 0.9 to 1.5.
[4] The liquid crystalline polyester resin according to any one of [1] to [3], which has a flexural modulus of 10 GPa or more.
[5] A liquid crystal polyester resin composition comprising 0.1 to 200 parts by mass of a fibrous, plate-like or powdery filler with respect to 100 parts by mass of the liquid crystal polyester resin according to any one of [1] to [4]. thing.
[6] A molded article composed of the liquid crystalline polyester resin according to any one of [1] to [4] or the liquid crystalline polyester resin composition according to [5].

本発明によれば、優れた耐熱性および耐溶媒性を維持しつつ、曲げ弾性率に優れた液晶ポリエステル樹脂を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the liquid crystalline polyester resin excellent in a bending elastic modulus can be provided, maintaining the heat resistance and solvent resistance which were excellent.

本発明の液晶ポリエステル樹脂は、当業者にサーモトロピック液晶ポリエステル樹脂と呼ばれる、異方性溶融相を形成するポリエステル樹脂である。 The liquid crystalline polyester resin of the present invention is a polyester resin that forms an anisotropic melt phase, which is called a thermotropic liquid crystalline polyester resin by those skilled in the art.

異方性溶融相の性質は、直交偏向子を利用した慣用の偏光検査法により確認することができる。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。本発明の液晶ポリエステル樹脂は光学的に異方性を示すもの、すなわち、直交偏光子の間で検査したときに光を透過させるものである。試料が光学的に異方性であると、たとえ静止状態であっても偏光は透過する。 The nature of the anisotropic melt phase can be confirmed by conventional polarimetry using crossed polarizers. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing the sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. The liquid crystalline polyester resins of the present invention are optically anisotropic, ie, transmit light when examined between crossed polarizers. If the sample is optically anisotropic, polarized light is transmitted even at rest.

本発明の液晶ポリエステル樹脂は、式（Ｉ）～（ＶＩ）

Figure 0007175834000002
［式中、
ｐ、ｑ、ｒ、ｓ、ｔおよびｕは、それぞれ、液晶ポリエステル樹脂中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす：
６０≦ｐ≦７０、
１５≦ｑ＋ｒ≦２０、
１０≦ｓ＋ｔ≦１９、
１≦ｕ≦５］
で表される繰返し単位から構成される。 The liquid crystalline polyester resin of the present invention has formulas (I) to (VI)

Figure 0007175834000002
[In the formula,
p, q, r, s, t and u are respectively the composition ratio (mol%) of each repeating unit in the liquid crystalline polyester resin, satisfying the following conditions:
60≦p≦70,
15≤q+r≤20,
10≤s+t≤19,
1≦u≦5]
Consists of repeating units represented by

式（Ｉ）で表される繰返し単位の組成比ｐは、６２～６８モル％が好ましく、６３～６７モル％がより好ましい。 The composition ratio p of the repeating unit represented by formula (I) is preferably 62 to 68 mol %, more preferably 63 to 67 mol %.

式（ＩＩ）表される繰返し単位の組成比ｑおよび（ＩＩＩ）で表される繰返し単位の組成比ｒの合計（ｑ＋ｒ）は、１６～１９モル％が好ましく、１７～１８モル％がより好ましい。 The sum (q+r) of the composition ratio q of the repeating units represented by formula (II) and the composition ratio r of the repeating units represented by (III) is preferably 16 to 19 mol%, more preferably 17 to 18 mol%. .

式（ＩＶ）で表される繰返し単位の組成比ｓおよび（Ｖ）で表される繰返し単位の組成比ｔの合計（ｓ＋ｔ）は、１２～１７．５モル％が好ましく、１４～１６モル％がより好ましい。 The total (s+t) of the composition ratio s of repeating units represented by formula (IV) and the composition ratio t of repeating units represented by (V) is preferably 12 to 17.5 mol%, and 14 to 16 mol%. is more preferred.

式（ＶＩ）で表される繰返し単位組成比ｕは、１．５～４．０モル％が好ましく、２．０～３．５モル％がより好ましい。 The repeating unit composition ratio u represented by formula (VI) is preferably 1.5 to 4.0 mol %, more preferably 2.0 to 3.5 mol %.

ｑとｒの比（ｑ／ｒ）は０．９～１．３であるのが好ましく、１．０～１．２５であるのがより好ましく、１．０５～１．２５であるのがさらに好ましい。 The ratio of q to r (q/r) is preferably 0.9 to 1.3, more preferably 1.0 to 1.25, and even more preferably 1.05 to 1.25. preferable.

ｓとｔの比（ｓ／ｔ）は０．９～１．５であるのが好ましく、１．０～１．４５であるのがより好ましく、１．０５～１．４であるのがさらに好ましい。 The ratio of s to t (s/t) is preferably 0.9 to 1.5, more preferably 1.0 to 1.45, and further preferably 1.05 to 1.4 preferable.

式（ＩＩ）表される繰返し単位の組成比ｑは、７～１２モル％が好ましく、７．５～１１モル％がより好ましく、８～１０．５モル％がさらに好ましい。
また、式（ＩＩＩ）で表される繰返し単位の組成比ｒは、５～１１モル％が好ましく、６～１０モル％がより好ましく、７～９モル％がさらに好ましい。 The composition ratio q of repeating units represented by formula (II) is preferably 7 to 12 mol %, more preferably 7.5 to 11 mol %, and even more preferably 8 to 10.5 mol %.
Also, the composition ratio r of the repeating units represented by formula (III) is preferably 5 to 11 mol %, more preferably 6 to 10 mol %, and even more preferably 7 to 9 mol %.

式（ＩＶ）で表される繰返し単位の組成比ｓは、５～１１モル％が好ましく、６～１０モル％がより好ましく、７～９モル％がさらに好ましい。
また、式（Ｖ）で表される繰返し単位の組成比ｔは、４～１０モル％が好ましく、４．５～９．５モル％がより好ましく、５～９モル％がさらに好ましい。 The composition ratio s of the repeating units represented by formula (IV) is preferably 5 to 11 mol %, more preferably 6 to 10 mol %, even more preferably 7 to 9 mol %.
Also, the composition ratio t of the repeating unit represented by formula (V) is preferably 4 to 10 mol %, more preferably 4.5 to 9.5 mol %, even more preferably 5 to 9 mol %.

なお、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕ＝１００であることが好ましい。 Note that it is preferable that p+q+r+s+t+u=100.

また、ｑ＋ｒ＝ｓ＋ｔ＋ｕであることが好ましい。 Also, it is preferable that q+r=s+t+u.

式（Ｉ）で表される繰返し単位を与える単量体としては、例えば、４－ヒドロキシ安息香酸、ならびにこのアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性の誘導体が挙げられる。 Examples of monomers that provide the repeating unit represented by formula (I) include 4-hydroxybenzoic acid and ester-forming derivatives such as acylates, ester derivatives and acid halides thereof.

式（ＩＩ）で表される繰返し単位を与える単量体としては、例えば、４，４’－ジヒドロキシビフェニル、およびこのアルキル、アルコキシまたはハロゲン置換体、ならびにこれらのアシル化物などのエステル形成性誘導体が挙げられる。 Examples of monomers that give repeating units represented by formula (II) include 4,4′-dihydroxybiphenyl, alkyl-, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives such as acylated products thereof. mentioned.

式（ＩＩＩ）で表される繰返し単位を与える単量体としては、例えば、ハイドロキノン、およびこのアルキル、アルコキシまたはハロゲン置換体、ならびにこれらのアシル化物などのエステル形成性誘導体が挙げられる。 Monomers that give the repeating unit represented by formula (III) include, for example, hydroquinone and its alkyl, alkoxy or halogen substituted products, and ester-forming derivatives such as acylated products thereof.

式（ＩＶ）で表される繰返し単位を与える単量体としては、例えば、テレフタル酸、およびこのアルキル、アルコキシまたはハロゲン置換体、ならびにこれらのエステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。 Monomers that provide the repeating unit represented by formula (IV) include, for example, terephthalic acid, its alkyl, alkoxy or halogen-substituted products, ester derivatives thereof, and ester-forming derivatives such as acid halides. be done.

式（Ｖ）で表される繰返し単位を与える単量体としては、例えば、イソフタル酸、およびこのアルキル、アルコキシまたはハロゲン置換体、ならびにこれらのエステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。 Monomers that provide the repeating unit represented by formula (V) include, for example, isophthalic acid, its alkyl, alkoxy or halogen-substituted products, ester derivatives thereof, and ester-forming derivatives such as acid halides. be done.

式（ＶＩ）で表される繰返し単位を与える単量体としては、例えば、２，６－ナフタレンジカルボン酸、およびこのアルキル、アルコキシまたはハロゲン置換体、ならびにこれらのエステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。 Examples of monomers that give repeating units represented by formula (VI) include 2,6-naphthalenedicarboxylic acid, alkyl-, alkoxy- or halogen-substituted products thereof, ester derivatives thereof, and esters such as acid halides. Formative derivatives are mentioned.

本発明の液晶ポリエステル樹脂は、上述した通り、式（Ｉ）～（ＶＩ）で表される繰返し単位により構成される液晶ポリエステル樹脂に関し、［ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕ＝１００］であるのが好ましいが、本発明の目的を損なわない範囲において、他の繰返し単位をさらに含有してもよい。 As described above, the liquid crystalline polyester resin of the present invention relates to a liquid crystalline polyester resin composed of repeating units represented by formulas (I) to (VI), and it is preferable that [p + q + r + s + t + u = 100]. Other repeating units may be further contained as long as the purpose is not impaired.

他の繰返し単位を与える単量体としては、他の芳香族ヒドロキシカルボン酸、芳香族ヒドロキシアミン、芳香族ジアミン、芳香族アミノカルボン酸、芳香族ヒドロキシジカルボン酸、脂肪族ジオール、脂肪族ジカルボン酸、芳香族メルカプトカルボン酸、芳香族ジチオール、芳香族メルカプトフェノールおよびこれらの組合せなどが挙げられる。 Examples of monomers that give other repeating units include other aromatic hydroxycarboxylic acids, aromatic hydroxyamines, aromatic diamines, aromatic aminocarboxylic acids, aromatic hydroxydicarboxylic acids, aliphatic diols, aliphatic dicarboxylic acids, Aromatic mercaptocarboxylic acids, aromatic dithiols, aromatic mercaptophenols and combinations thereof, and the like.

これらの他の繰り返し単位を与える単量体は、式（Ｉ）～（ＶＩ）で表される繰返し単位を与える単量体の合計に対し、１０モル％以下であるのが好ましい。 It is preferable that the amount of these other repeating unit-providing monomers is 10 mol % or less relative to the total of the monomers providing the repeating units represented by formulas (I) to (VI).

本発明の液晶ポリエステル樹脂の製造方法には特に限定はなく、上記単量体成分間にエステル結合を形成させる公知のポリエステルの重縮合法、たとえば溶融アシドリシス法、スラリー重合法などを用いることができる。 The method for producing the liquid crystalline polyester resin of the present invention is not particularly limited, and a known polyester polycondensation method for forming an ester bond between the monomer components, such as a melt acidolysis method and a slurry polymerization method, can be used. .

溶融アシドリシス法とは、最初に単量体を加熱して反応物質の溶融溶液を形成し、続いて反応を続けて溶融ポリマーを得るものである。なお、縮合の最終段階で副生する揮発物（たとえば酢酸、水など）の除去を容易にするために真空を適用してもよい。この方法は、本発明において特に好適に用いられる。 The melt acidolysis process involves first heating the monomers to form a molten solution of the reactants, followed by continuing the reaction to obtain a molten polymer. A vacuum may be applied to facilitate removal of volatiles (eg, acetic acid, water, etc.) that are by-produced in the final stages of condensation. This method is particularly suitable for use in the present invention.

スラリー重合法とは、熱交換流体の存在下で反応させる方法であって、固体生成物は熱交換媒質中に懸濁した状態で得られる。 Slurry polymerization is a process in which the reaction is carried out in the presence of a heat exchange fluid and the solid product is obtained in suspension in the heat exchange medium.

溶融アシドリシス法およびスラリー重合法のいずれの場合においても、液晶ポリエステル樹脂を製造する際に使用する重合性単量体成分は、ヒドロキシル基をエステル化した変性形態、すなわち低級アシルエステルとして反応に供することもできる。低級アシル基は炭素原子数２～５のものが好ましく、炭素原子数２または３のものがより好ましい。特に好ましくは前記単量体成分の酢酸エステルを反応に用いる方法が挙げられる。 In both the melt acidolysis method and the slurry polymerization method, the polymerizable monomer component used in producing the liquid crystalline polyester resin should be subjected to the reaction in a modified form obtained by esterifying the hydroxyl group, that is, in the form of a lower acyl ester. can also The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. Particularly preferred is a method of using an acetic acid ester of the monomer component for the reaction.

単量体の低級アシルエステルは、別途アシル化して予め合成したものを用いてもよいし、液晶ポリエステル樹脂の製造時にモノマーに無水酢酸等のアシル化剤を加えて反応系内で生成せしめることもできる。 The lower acyl ester of the monomer may be previously synthesized by acylation separately, or may be generated in the reaction system by adding an acylating agent such as acetic anhydride to the monomer during production of the liquid crystalline polyester resin. can.

溶融アシドリシス法またはスラリー重合法のいずれにおいても、必要に応じて触媒を用いてもよい。 A catalyst may optionally be used in either the melt acidolysis method or the slurry polymerization method.

触媒の具体例としては、ジアルキルスズオキシド（たとえばジブチルスズオキシド）、ジアリールスズオキシドなどの有機スズ化合物；二酸化チタンなどの金属酸化物；三酸化アンチモンなどのアンチモン化合物；アルコキシチタンシリケート、チタンアルコキシドなどの有機チタン化合物；カルボン酸のアルカリおよびアルカリ土類金属塩（たとえば酢酸カリウム）；ルイス酸（たとえば三フッ化硼素）、ハロゲン化水素（たとえば塩化水素）などの気体状酸触媒などが挙げられる。 Specific examples of catalysts include organic tin compounds such as dialkyltin oxide (e.g., dibutyltin oxide) and diaryltin oxide; metal oxides such as titanium dioxide; antimony compounds such as antimony trioxide; titanium compounds; alkali and alkaline earth metal salts of carboxylic acids (eg potassium acetate); gaseous acid catalysts such as Lewis acids (eg boron trifluoride), hydrogen halides (eg hydrogen chloride) and the like.

触媒の使用割合は、通常モノマー全量に対し１０～１０００ｐｐｍ、好ましくは２０～２００ｐｐｍである。 The proportion of the catalyst used is usually 10-1000 ppm, preferably 20-200 ppm, based on the total amount of the monomers.

このようにして得られる本発明の液晶ポリエステル樹脂は、示差走査熱量計（ＤＳＣ）により測定される結晶融解温度が通常３３０℃以下であり、熱分解を抑制できる低温加工性に優れたものである。本発明の液晶ポリエステル樹脂の結晶融解温度は、好ましくは２９０～３３０℃、より好ましくは２９５～３２５℃、さらに好ましくは３００～３２３℃である。 The liquid crystalline polyester resin of the present invention thus obtained has a crystal melting temperature of usually 330° C. or less as measured by a differential scanning calorimeter (DSC), and is excellent in low-temperature workability capable of suppressing thermal decomposition. . The crystal melting temperature of the liquid crystalline polyester resin of the present invention is preferably 290 to 330°C, more preferably 295 to 325°C, still more preferably 300 to 323°C.

本発明の液晶ポリエステル樹脂は、これから構成される成形品について、後述する方法で測定した曲げ強度が、好ましくは１３０ＭＰａ以上、より好ましくは１３０～１７０ＭＰａ、さらに好ましくは１４０～１６０ＭＰａである。 The liquid crystalline polyester resin of the present invention preferably has a bending strength of 130 MPa or more, more preferably 130 to 170 MPa, and still more preferably 140 to 160 MPa, as measured by the method described later, for a molded product formed therefrom.

本発明の液晶ポリエステル樹脂は、これから構成される成形品について、後述する方法で測定した曲げ弾性率が、好ましくは１０ＧＰａ以上、より好ましくは１０～１６ＧＰａ、さらに好ましくは１１～１５ＧＰａである。 The liquid crystalline polyester resin of the present invention preferably has a flexural modulus of 10 GPa or more, more preferably 10 to 16 GPa, and still more preferably 11 to 15 GPa, as measured by the method described below, for a molded product formed therefrom.

本発明の液晶ポリエステル樹脂は、７０℃の温度条件下、クロロホルム７００ｇ中に１６時間浸漬した際の液晶ポリエステル樹脂の溶出率が、好ましくは６００ｐｐｍ以下、より好ましくは５００ｐｐｍ以下、さらに好ましくは４００ｐｐｍ以下である。 The liquid crystalline polyester resin of the present invention has an elution rate of preferably 600 ppm or less, more preferably 500 ppm or less, and still more preferably 400 ppm or less when immersed in 700 g of chloroform for 16 hours under a temperature condition of 70 ° C. be.

本発明はさらに、本発明の液晶ポリエステル樹脂に繊維状、板状、粉状の充填剤の１種または２種以上を配合せしめて得られる液晶ポリエステル樹脂組成物を提供する。充填剤としては、従来から樹脂組成物に用いられることが知られている物質から、液晶ポリエステル樹脂組成物の使用目的、用途等に応じて適宜選択すればよい。 The present invention further provides a liquid crystalline polyester resin composition obtained by blending one or more of fibrous, plate-like and powdery fillers with the liquid crystalline polyester resin of the present invention. The filler may be appropriately selected from substances conventionally known to be used in resin compositions, depending on the intended use, application, etc. of the liquid crystalline polyester resin composition.

繊維状の充填剤としては、例えばガラス繊維、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、などが挙げられる。これらの中では、ガラス繊維が物性とコストのバランスが優れている点から好ましい。 Examples of fibrous fillers include glass fiber, silica-alumina fiber, alumina fiber, carbon fiber, and aramid fiber. Among these, glass fiber is preferable because it has an excellent balance between physical properties and cost.

板状あるいは粉状の充填剤としては、例えばタルク、マイカ、グラファイト、ウォラストナイト、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、酸化チタンなどが挙げられる。これらの中では、タルクが物性とコストのバランスが優れている点から好ましい。 Plate-like or powder-like fillers include, for example, talc, mica, graphite, wollastonite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, and titanium oxide. Among these, talc is preferable because it has an excellent balance between physical properties and cost.

本発明の液晶ポリエステル樹脂組成物において、充填剤はその合計配合量が、液晶ポリエステル樹脂１００質量部に対して、好ましくは０．１～２００質量部、特に１０～１００質量部であるのが好ましい。充填剤の配合量が２００質量部を超える場合、樹脂組成物の成形加工性が低下したり、成形機のシリンダーや金型の磨耗が大きくなる傾向がある。 In the liquid crystal polyester resin composition of the present invention, the total amount of the filler compounded is preferably 0.1 to 200 parts by mass, particularly preferably 10 to 100 parts by mass, per 100 parts by mass of the liquid crystal polyester resin. . When the amount of the filler compounded exceeds 200 parts by mass, there is a tendency that the moldability of the resin composition is lowered and the wear of the cylinder and mold of the molding machine increases.

本発明の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でさらに、高級脂肪酸、高級脂肪酸エステル、高級脂肪酸アミド、高級脂肪酸金属塩、ポリシロキサン、フッ素樹脂などの離型剤；染料、顔料などの着色剤；酸化防止剤；熱安定剤；紫外線吸収剤；帯電防止剤；界面活性剤などの従来から樹脂組成物に用いられることが知られている添加剤を、樹脂組成物の目的及び用途に応じて１種または２種以上を組み合わせて添加してもよい。 The liquid crystalline polyester resin composition of the present invention further contains release agents such as higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid metal salts, polysiloxanes, and fluorine resins, as long as the effects of the present invention are not impaired; Colorants such as pigments; antioxidants; heat stabilizers; ultraviolet absorbers; antistatic agents; and may be added alone or in combination of two or more depending on the application.

高級脂肪酸、高級脂肪酸エステル、高級脂肪酸金属塩、フルオロカーボン系界面活性剤等の外部滑剤効果を有するものについては、成形に際して予めペレットに付着せしめて用いてもよい。 Higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, fluorocarbon-based surfactants, etc., which have an external lubricant effect, may be used by previously adhering them to the pellets during molding.

本発明の液晶ポリエステル樹脂組成物は、充填剤および添加剤などの全ての成分をポリエステル樹脂中へ添加し、バンバリーミキサー、ニーダー、一軸もしくは二軸押出機などを用いて、液晶ポリエステル樹脂の結晶融解温度近傍から結晶融解温度＋１００℃の温度下で溶融混練して調製することができる。 The liquid crystalline polyester resin composition of the present invention is obtained by adding all components such as fillers and additives to the polyester resin, and using a Banbury mixer, a kneader, a single-screw or twin-screw extruder, etc., to melt crystals of the liquid crystalline polyester resin. It can be prepared by melt-kneading at a temperature from the vicinity of the temperature to the crystal melting temperature +100°C.

このようにして得られた本発明の液晶ポリエステル樹脂および液晶ポリエステル樹脂組成物は、従来公知の射出成形、圧縮成形、押出成形、ブローなどの成形法によって、射出成形品、フィルム、シートおよび不織布などの成形品に加工することができる。 The thus obtained liquid crystalline polyester resin and liquid crystalline polyester resin composition of the present invention can be processed into injection molded articles, films, sheets and non-woven fabrics by conventionally known molding methods such as injection molding, compression molding, extrusion molding and blow molding. can be processed into molded products.

本発明の液晶ポリエステル樹脂および液晶ポリエステル樹脂組成物は、耐熱性および機械物性のバランスに優れることから、電気・電子部品、カメラモジュール等の機械機構部品、自動車部品等として好適に使用される。特に本発明の液晶ポリエステル樹脂は、耐溶媒性および曲げ弾性率に優れることから、電動機の絶縁体（インシュレーター）として有用である。 The liquid crystalline polyester resin and the liquid crystalline polyester resin composition of the present invention have an excellent balance of heat resistance and mechanical properties, and are therefore suitably used as electric/electronic parts, mechanical parts such as camera modules, automobile parts, and the like. In particular, the liquid crystalline polyester resin of the present invention is useful as an insulator for electric motors because of its excellent solvent resistance and flexural modulus.

以下、実施例により本発明を詳述するが、本発明はこれに限定されるものではない。 The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these.

実施例中の結晶融解温度、曲げ強度、曲げ弾性率および溶出率は、以下に記載の方法で測定した。 Crystal melting temperature, flexural strength, flexural modulus and elution rate in the examples were measured by the methods described below.

〈結晶融解温度〉
セイコーインスツルメンツ株式会社製Ｅｘｓｔａｒ６０００を用いて測定を行った。液晶ポリエステル樹脂試料を、室温から２０℃／分の昇温条件下で測定し、吸熱ピーク温度（Ｔｍ１）を観測した後、Ｔｍ１より２０～５０℃高い温度で１０分間保持する。次いで２０℃／分の降温条件で室温まで試料を冷却した後に、再度２０℃／分の昇温条件で測定した際の吸熱ピークを観測し、そのピークトップを示す温度を液晶ポリエステル樹脂の結晶融解温度とする。 <Crystal melting temperature>
The measurement was performed using Exstar6000 manufactured by Seiko Instruments Inc. A liquid crystalline polyester resin sample is measured under the condition of increasing the temperature from room temperature by 20° C./min, and after observing the endothermic peak temperature (Tm1), the temperature is maintained at a temperature 20 to 50° C. higher than Tm1 for 10 minutes. Then, after cooling the sample to room temperature under the temperature decreasing condition of 20°C/min, the endothermic peak was measured again under the temperature increasing condition of 20°C/min. Let temperature be

〈曲げ強度および曲げ弾性率〉
型締め圧１５ｔの射出成形機（住友重機械工業（株）製ＭＩＮＩＭＡＴ Ｍ２６／１５）を用いて結晶融解温度＋２０～４０℃のシリンダー温度、金型温度７０℃で射出成形し、短冊状曲げ試験片（長さ６５ｍｍ×幅１２．７ｍｍ×厚さ２．０ｍｍ）を作製した。曲げ試験は、３点曲げ試験をＩＮＳＴＲＯＮ５５６７（インストロンジャパンカンパニイリミティッド社製万能試験機）を用いて、スパン間距離４０．０ｍｍ、圧縮速度１．３ｍｍ／分で行った。 <Bending strength and bending elastic modulus>
Using an injection molding machine (MINIMAT M26/15 manufactured by Sumitomo Heavy Industries, Ltd.) with a mold clamping pressure of 15 tons, injection molding was performed at a cylinder temperature of crystal melting temperature +20 to 40 ° C. and a mold temperature of 70 ° C., and a strip bending test was performed. A piece (65 mm long x 12.7 mm wide x 2.0 mm thick) was made. For the bending test, a three-point bending test was performed using INSTRON5567 (a universal testing machine manufactured by Instron Japan Co., Ltd.) at a span-to-span distance of 40.0 mm and a compression rate of 1.3 mm/min.

〈溶出率〉
曲げ強度および曲げ弾性率の測定に用いた試験片と同様の試験片９本とクロロホルム７００ｇとを１０００ｍＬの四つ口フラスコに入れ、７０℃の水浴に浸けて１６時間還流を行った。試験片と溶液とを濾別し、濾液を減圧乾固し、さらに６０℃で１２時間乾燥した。得られた固形物の質量を、測定に供した試験片の質量で除した値を溶出率として算出した。溶出率が大きいほど、溶出する低分子化合物が多く含まれていることを示す。 <Elution rate>
Nine test pieces similar to the test pieces used for measurement of flexural strength and flexural modulus and 700 g of chloroform were placed in a 1000 mL four-necked flask, immersed in a water bath at 70° C. and refluxed for 16 hours. The test piece and the solution were separated by filtration, and the filtrate was dried under reduced pressure and further dried at 60° C. for 12 hours. The dissolution rate was calculated by dividing the mass of the obtained solid by the mass of the test piece used for measurement. A higher elution rate indicates a higher content of eluted low-molecular-weight compounds.

実施例において、下記の略号は以下の化合物を表す。
ＰＯＢ：４－ヒドロキシ安息香酸
ＢＯＮ６：６－ヒドロキシ－２－ナフトエ酸
ＢＰ：４,４’－ジヒドロキシビフェニル
ＨＱ：ハイドロキノン
ＴＰＡ：テレフタル酸
ＩＰＡ：イソフタル酸
ＮＤＡ：２，６－ナフタレンジカルボン酸 In the examples, the following abbreviations represent the following compounds.
POB: 4-hydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid BP: 4,4'-dihydroxybiphenyl HQ: hydroquinone TPA: terephthalic acid IPA: isophthalic acid NDA: 2,6-naphthalenedicarboxylic acid

（実施例１）
トルクメーター付き攪拌装置および留出管を備えた反応容器にＰＯＢ、ＢＰ、ＨＱ、ＴＰＡ、ＩＰＡおよびＮＤＡを、表１に示す組成比で、総量６．５モルとなるように仕込み、さらに全モノマーの水酸基量（モル）に対して１.０３倍モルの無水酢酸を仕込み、次の条件で脱酢酸重合を行った。 (Example 1)
POB, BP, HQ, TPA, IPA and NDA were charged in a reaction vessel equipped with a stirrer equipped with a torque meter and a distillation tube in a composition ratio shown in Table 1 so that the total amount was 6.5 mol. Acetic anhydride was charged in an amount of 1.03 times the amount (mol) of hydroxyl groups of , and deacetic acid polymerization was carried out under the following conditions.

窒素ガス雰囲気下に室温から１５０℃まで１時間で昇温し、同温度にて３０分間保持した。次いで、副生する酢酸を留去させつつ２１０℃まで速やかに昇温し、同温度にて３０分間保持した。その後、３４０℃まで４時間かけ昇温した後、８０分かけ１０ｍｍＨｇにまで減圧を行なった。所定のトルクを示した時点で重合反応を終了し、反応容器から内容物を取り出し、粉砕機により液晶ポリエステル樹脂のペレットを得た。重合時の留出酢酸量は、ほぼ理論値どおりであった。 In a nitrogen gas atmosphere, the temperature was raised from room temperature to 150° C. over 1 hour, and the same temperature was maintained for 30 minutes. Subsequently, the temperature was rapidly raised to 210° C. while distilling off the by-produced acetic acid, and the temperature was maintained for 30 minutes. Then, after raising the temperature to 340° C. over 4 hours, the pressure was reduced to 10 mmHg over 80 minutes. When a predetermined torque was exhibited, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and pellets of the liquid crystalline polyester resin were obtained with a pulverizer. The amount of acetic acid distilled off during polymerization was almost the same as the theoretical value.

得られた液晶ポリエステル樹脂のペレットを用いて、上記の方法により、結晶融解温度、曲げ強度、曲げ弾性率および溶出率を測定した。結果を表１に示す。 Using the obtained liquid crystalline polyester resin pellets, the crystalline melting temperature, bending strength, bending elastic modulus and elution rate were measured by the methods described above. Table 1 shows the results.

（実施例２～３および比較例１～６）
モノマー組成比を、表１に示す組成比に変えることの他は、実施例１と同様にして、液晶ポリエステル樹脂のペレットを得た。得られたペレットを用いて、結晶融解温度、曲げ強度、曲げ弾性率および溶出率を測定した。結果を表１に示す。 (Examples 2-3 and Comparative Examples 1-6)
Liquid crystalline polyester resin pellets were obtained in the same manner as in Example 1, except that the composition ratio of the monomers was changed to that shown in Table 1. Using the obtained pellets, crystal melting temperature, flexural strength, flexural modulus and elution rate were measured. Table 1 shows the results.

実施例１～３の液晶ポリエステル樹脂は、結晶融解温度が３１８～３２３℃、曲げ強度が１４４～１５５ＭＰａ、曲げ弾性率が１１．６～１２．２ＧＰａであり、耐熱性および機械強度に優れるものであった。また、溶出率は４００ｐｐｍ以下であり、耐溶媒性に優れるものであった。 The liquid crystal polyester resins of Examples 1 to 3 have a crystal melting temperature of 318 to 323° C., a bending strength of 144 to 155 MPa, and a bending elastic modulus of 11.6 to 12.2 GPa, and are excellent in heat resistance and mechanical strength. there were. Moreover, the elution rate was 400 ppm or less, and the solvent resistance was excellent.

一方、比較例１～５の液晶ポリエステル樹脂は、曲げ弾性率が１０ＧＰａを下回るものであり、機械強度に劣るものであった。 On the other hand, the liquid crystal polyester resins of Comparative Examples 1 to 5 had a flexural modulus of less than 10 GPa and were inferior in mechanical strength.

なお、比較例６については、３４０℃まで４時間かけて昇温する際、３０５℃まで昇温した時点で内容物が固化し攪拌が不能になったため反応を中止し、液晶ポリエステル樹脂を得ることができなかった。 In Comparative Example 6, when the temperature was raised to 340°C over 4 hours, the contents were solidified at the time the temperature was raised to 305°C and stirring became impossible, so the reaction was stopped to obtain a liquid crystalline polyester resin. I couldn't do it.

Figure 0007175834000003
Figure 0007175834000003

Claims (5)

式（Ｉ）～（ＶＩ）
Figure 0007175834000004
［式中、
ｐ、ｑ、ｒ、ｓ、ｔおよびｕは、それぞれ、液晶ポリエステル樹脂中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす：
６０≦ｐ≦７０、
１５≦ｑ＋ｒ≦２０、
１０≦ｓ＋ｔ≦１９、ここで、ｓ／ｔは１．０５～１．５である、
１≦ｕ≦５］
で表される繰返し単位から構成される液晶ポリエステル樹脂。 Formulas (I)-(VI)
Figure 0007175834000004
[In the formula,
p, q, r, s, t and u are respectively the composition ratio (mol%) of each repeating unit in the liquid crystalline polyester resin, satisfying the following conditions:
60≦p≦70,
15≤q+r≤20,
10≦s+t≦19, where s/t is between 1.05 and 1.5;
1≦u≦5]
Liquid crystalline polyester resin composed of repeating units represented by ｑ／ｒが０．９～１．３である、請求項１に記載の液晶ポリエステル樹脂。 2. The liquid crystalline polyester resin according to claim 1, wherein q/r is 0.9 to 1.3. 曲げ弾性率が１０ＧＰａ以上である、請求項１または２に記載の液晶ポリエステル樹脂。 3. The liquid crystalline polyester resin according to claim 1, which has a flexural modulus of 10 GPa or more. 請求項１～３のいずれかに記載の液晶ポリエステル樹脂１００質量部に対し、繊維状、板状または粉状の充填剤０．１～２００質量部を含む、液晶ポリエステル樹脂組成物。 A liquid crystal polyester resin composition comprising 0.1 to 200 parts by mass of a fibrous, plate-like or powdery filler with respect to 100 parts by mass of the liquid crystal polyester resin according to any one of claims 1 to 3 . 請求項１～３のいずれかに記載の液晶ポリエステル樹脂あるいは請求項４に記載の液晶ポリエステル樹脂組成物から構成される成形品。 A molded article composed of the liquid crystalline polyester resin according to any one of claims 1 to 3 or the liquid crystalline polyester resin composition according to claim 4 .
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