JP6900151B2 - All-aromatic liquid crystal polyester resins, molded products, and electrical and electronic components - Google Patents
All-aromatic liquid crystal polyester resins, molded products, and electrical and electronic components Download PDFInfo
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- JP6900151B2 JP6900151B2 JP2016069001A JP2016069001A JP6900151B2 JP 6900151 B2 JP6900151 B2 JP 6900151B2 JP 2016069001 A JP2016069001 A JP 2016069001A JP 2016069001 A JP2016069001 A JP 2016069001A JP 6900151 B2 JP6900151 B2 JP 6900151B2
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 108
- 229920001225 polyester resin Polymers 0.000 title claims description 97
- 239000004645 polyester resin Substances 0.000 title claims description 97
- 125000003118 aryl group Chemical group 0.000 claims description 70
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical group OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 19
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 17
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims description 17
- 238000010521 absorption reaction Methods 0.000 claims description 17
- -1 aromatic diol compound Chemical class 0.000 claims description 13
- 239000000470 constituent Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000005259 measurement Methods 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000006267 biphenyl group Chemical group 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000005561 phenanthryl group Chemical group 0.000 claims description 6
- 238000010998 test method Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 description 26
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 22
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 239000000178 monomer Substances 0.000 description 16
- 238000000465 moulding Methods 0.000 description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- 238000004891 communication Methods 0.000 description 10
- 239000007790 solid phase Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- ZYZWCJWINLGQRL-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-diol Chemical group C1=CC(O)(O)CC=C1C1=CC=CC=C1 ZYZWCJWINLGQRL-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 1
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 1
- WUGKVYDVIGOPSI-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenyl)-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C=2C=C(C)C(O)=CC=2)=C1 WUGKVYDVIGOPSI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 208000021302 gastroesophageal reflux disease Diseases 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Description
本発明は、全芳香族液晶ポリエステル樹脂および成形品に関し、より詳細には、とりわけ低い誘電正接および低吸水率を有する全芳香族液晶ポリエステル樹脂ならびにこれを含む成形品および電気電子部品に関する。 The present invention relates to a total aromatic liquid crystal polyester resin and a molded product, and more particularly to a total aromatic liquid crystal polyester resin having a particularly low dielectric loss tangent and a low water absorption rate, and a molded product and an electric / electronic part containing the same.
近年、通信分野における情報通信量の増加に伴い、電子機器や通信機器等において高周波数帯の周波数を有する信号の使用が増加しており、特に、周波数が１０−９以上であるギガヘルツ（ＧＨｚ）帯の周波数を有する信号の使用が盛んに行われている。例えば、自動車分野においてＧＨｚ帯の高周波数帯が使用されている。具体的には、自動車の衝突防止目的で搭載されるミリ波レーダー、準ミリ波レーダーにおいては、それぞれ７６〜７９ＧＨｚ、２４ＧＨｚの高周波数が使用されており、今後更なる普及が進んでいくことが予想される。 In recent years, with the increase in the amount of information communication in the communication field, the use of signals having frequencies in the high frequency band has been increasing in electronic devices and communication devices, and in particular, gigahertz (GHz) having a frequency of 10-9 or higher. The use of signals with band frequencies is widespread. For example, in the field of automobiles, a high frequency band of GHz band is used. Specifically, high frequencies of 76 to 79 GHz and 24 GHz are used in millimeter-wave radars and quasi-millimeter-wave radars installed for the purpose of preventing automobile collisions, respectively, and it is expected that they will become more widespread in the future. is expected.
しかしながら、使用される信号の周波数が高くなるに伴い、情報の誤認識を招きうる出力信号の品質低下、すなわち、伝送損失が大きくなる。この伝送損失は、導体に起因する導体損失と、電子機器や通信機器における基板等の電気電子部品を構成する絶縁用の樹脂に起因する誘電損失とからなるが、導体損失は使用する周波数の０．５乗、誘電損失は周波数の１乗に比例するため、高周波帯、とりわけＧＨｚ帯においては、この誘電損失による影響が非常に大きくなる。また、誘電損失は、樹脂の誘電正接にも比例して増大するため、情報の劣化を防ぐため低誘電正接を有する樹脂が求められている。 However, as the frequency of the signal used increases, the quality of the output signal, which can lead to misrecognition of information, deteriorates, that is, the transmission loss increases. This transmission loss consists of a conductor loss caused by a conductor and a dielectric loss caused by an insulating resin constituting an electric / electronic component such as a substrate in an electronic device or a communication device. The conductor loss is 0 at the frequency used. Since the fifth power and the dielectric loss are proportional to the first power of the frequency, the influence of this dielectric loss becomes very large in the high frequency band, particularly in the GHz band. Further, since the dielectric loss increases in proportion to the dielectric loss tangent of the resin, a resin having a low dielectric loss tangent is required in order to prevent deterioration of information.
上記課題に対し、特許文献１では、高周波数帯において低誘電正接を示す液晶性芳香族ポリエステルとして、ｐ−又はｍ−ヒドロキシ安息香酸に由来する構成単位およびヒドロキシナフトエ酸に由来する構成単位の２種以上を含む液晶性芳香族ポリエステルが提案されている。 In response to the above problems, in Patent Document 1, as a liquid crystal aromatic polyester exhibiting a low dielectric loss tangent in a high frequency band, 2 of a structural unit derived from p- or m-hydroxybenzoic acid and a structural unit derived from hydroxynaphthoic acid. Liquid liquid aromatic polyesters containing more than seeds have been proposed.
ところで、電気電子部品を構成する樹脂には、高温での成形加工性が要求される。このような課題に対し、特許文献２では、耐熱性および成形性に優れる全芳香族ポリエステルとして、ｐ−ヒドロキシ安息香酸に由来する構成単位を１〜６％、６−ヒドロキシ−２−ナフトエ酸に由来する構成単位を４０〜６０％、芳香族ジオール化合物に由来する構成単位を１７．５〜３０％、および芳香族ジカルボン酸に由来する構成単位を１７．５〜３０％含むポリエステル樹脂が提案されている。 By the way, the resin constituting the electric / electronic component is required to have molding processability at a high temperature. In response to such problems, in Patent Document 2, as a total aromatic polyester having excellent heat resistance and moldability, the constituent unit derived from p-hydroxybenzoic acid is 1 to 6%, and 6-hydroxy-2-naphthoic acid is used. A polyester resin containing 40 to 60% of a constituent unit derived from it, 17.5 to 30% of a constituent unit derived from an aromatic diol compound, and 17.5 to 30% of a constituent unit derived from an aromatic dicarboxylic acid has been proposed. ing.
また、水は電気電子部品の誘電特性を悪化させるため、通信の安定性向上のためには、電気電子部品を構成する樹脂は水による影響を受けにくいものである必要がある。したがって、低誘電正接および低吸水率を有する樹脂が求められている。 Further, since water deteriorates the dielectric properties of electrical and electronic components, the resin constituting the electrical and electronic components needs to be less susceptible to the influence of water in order to improve the stability of communication. Therefore, a resin having a low dielectric loss tangent and a low water absorption rate is required.
近年、情報通信量は急速に増加し続け、使用される信号の周波数はさらに高まっており、高周波数帯において更に低い誘電正接を有する樹脂が求められている。本発明者は、特許文献１において提案されるポリエステル樹脂を用いたとしても、高周波数帯において要求される十分な低誘電正接を示さないことを見出した。
また、同様に、特許文献２において提案されるポリエステル樹脂を用いたとしても、高周波数帯において要求される十分な低誘電正接を示さないことを見出した。
In recent years, the amount of information communication has continued to increase rapidly, the frequency of signals used has further increased, and there is a demand for a resin having a lower dielectric loss tangent in the high frequency band. The present inventor has found that even if the polyester resin proposed in Patent Document 1 is used, it does not exhibit a sufficiently low dielectric loss tangent required in a high frequency band.
Similarly, it has been found that even if the polyester resin proposed in Patent Document 2 is used, it does not exhibit sufficient low dielectric loss tangent required in the high frequency band.
そして、本発明者は、上記課題を解決するために鋭意検討した結果、全芳香族液晶ポリエステル樹脂において、特定の構成単位およびそれらを特定の組成比に調節することにより、低誘電正接および低吸水率を有する全芳香族液晶ポリエステル樹脂を得られることを見出した。 Then, as a result of diligent studies to solve the above problems, the present inventor has made a low dielectric loss tangent and low water absorption by adjusting a specific structural unit and a specific composition ratio in the total aromatic liquid crystal polyester resin. It has been found that a total aromatic liquid crystal polyester resin having a ratio can be obtained.
本発明の目的は、とりわけ低い誘電正接および低吸水率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。また、本発明の他の目的は、この全芳香族液晶ポリエステル樹脂を含む成形品および電気電子部品を提供することである。 An object of the present invention is to provide a totally aromatic liquid crystal polyester resin having a particularly low dielectric loss tangent and low water absorption. Another object of the present invention is to provide a molded product and an electric / electronic component containing the all-aromatic liquid crystal polyester resin.
本発明による全芳香族液晶ポリエステル樹脂は、ｐ−ヒドロキシ安息香酸に由来する構成単位（Ｉ）、６−ヒドロキシ−２−ナフトエ酸に由来する構成単位（ＩＩ）、芳香族ジオール化合物に由来する構成単位（ＩＩＩ）および芳香族ジカルボン酸に由来する構成単位（ＩＶ）を含んでなり、構成単位（Ｉ）〜（ＩＶ）の組成比（モル％）が、下記の条件を満たすことを特徴とする。
１０モル％≦構成単位（Ｉ）≦４０モル％
５０モル％≦構成単位（ＩＩ）≦８５モル％
１モル％≦構成単位（ＩＩＩ）≦２０モル％
１モル％≦構成単位（ＩＶ）≦２０モル％
The all-aromatic liquid crystal polyester resin according to the present invention has a structural unit (I) derived from p-hydroxybenzoic acid, a structural unit (II) derived from 6-hydroxy-2-naphthoic acid, and a constitution derived from an aromatic diol compound. It comprises the unit (III) and the structural unit (IV) derived from the aromatic dicarboxylic acid, and the composition ratio (mol%) of the structural units (I) to (IV) satisfies the following conditions. ..
10 mol% ≤ structural unit (I) ≤ 40 mol%
50 mol% ≤ structural unit (II) ≤ 85 mol%
1 mol% ≤ structural unit (III) ≤ 20 mol%
1 mol% ≤ structural unit (IV) ≤ 20 mol%
本発明の態様においては、構成単位（Ｉ）〜（ＩＶ）の組成比（モル％）が、下記の条件を満たすことが好ましい。
１５モル％≦構成単位（Ｉ）≦３５モル％
６０モル％≦構成単位（ＩＩ）≦８０モル％
１モル％≦構成単位（ＩＩＩ）≦１５モル％
１モル％≦構成単位（ＩＶ）≦１５モル％
In the aspect of the present invention, it is preferable that the composition ratio (mol%) of the constituent units (I) to (IV) satisfies the following conditions.
15 mol% ≤ structural unit (I) ≤ 35 mol%
60 mol% ≤ structural unit (II) ≤ 80 mol%
1 mol% ≤ structural unit (III) ≤ 15 mol%
1 mol% ≤ structural unit (IV) ≤ 15 mol%
本発明の態様においては、構成単位（ＩＩＩ）が、下記式で表されることが好ましい。
本発明の態様においては、構成単位（ＩＶ）が、下記式で表されることが好ましい。
本発明の態様においては、全芳香族液晶ポリエステル樹脂の融点が、２９０℃以上であることが好ましい。 In the aspect of the present invention, the melting point of the total aromatic liquid crystal polyester resin is preferably 290 ° C. or higher.
本発明の態様においては、全芳香族液晶ポリエステル樹脂の測定周波数１０ＧＨｚにおける誘電正接が、０．７５×１０−３以下であることが好ましい。 In the embodiment of the present invention, the dielectric loss tangent of the all-aromatic liquid crystal polyester resin at a measurement frequency of 10 GHz is preferably 0.75 × 10 -3 or less.
本発明の態様においては、ＡＳＴＭ Ｄ５７０の試験方法に準拠して測定した吸水率が、０．０３％以下であることが好ましい。 In the aspect of the present invention, the water absorption rate measured according to the test method of ASTM D570 is preferably 0.03% or less.
本発明による成形品は、上記全芳香族液晶ポリエステル樹脂を含んでなることを特徴とする。 The molded product according to the present invention is characterized by containing the above-mentioned all-aromatic liquid crystal polyester resin.
本発明の態様においては、成形品は、フィルム形状を有することが好ましい。 In the aspect of the present invention, the molded product preferably has a film shape.
本発明の態様においては、成形品は、射出成形品であることが好ましい。 In the aspect of the present invention, the molded product is preferably an injection molded product.
本発明による電気電子部品は、上記全芳香族液晶ポリエステル樹脂を含んでなることを特徴とする。 The electrical and electronic components according to the present invention are characterized by containing the above-mentioned all-aromatic liquid crystal polyester resin.
本発明によれば、全芳香族液晶ポリエステル樹脂を構成する単位を、特定の構成単位およびそれらを特定の組成比とすることにより、とりわけ低い誘電正接および低吸水率を有する全芳香族液晶ポリエステル樹脂を実現することができる。
したがって、周波数の高い信号を使用する電気電子機器や通信機器における出力信号の品質の低下を防止することができ、これらを構成する材料として好適に使用することができる。
According to the present invention, by setting the unit constituting the total aromatic liquid crystal polyester resin to a specific constituent unit and a specific composition ratio thereof, the total aromatic liquid crystal polyester resin has a particularly low dielectric loss tangent and low water absorption. Can be realized.
Therefore, it is possible to prevent deterioration of the quality of the output signal in electrical and electronic equipment and communication equipment that use high frequency signals, and it can be suitably used as a material constituting these.
（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、ｐ−ヒドロキシ安息香酸に由来する構成単位（Ｉ）、６−ヒドロキシ−２−ナフトエ酸に由来する構成単位（ＩＩ）、芳香族ジオール化合物に由来する構成単位（ＩＩＩ）および芳香族ジカルボン酸に由来する構成単位（ＩＶ）を含んでなり、全芳香族液晶ポリエステル樹脂中における構成単位（Ｉ）〜（ＩＶ）の組成比（モル％）は、下記の条件を満たす。
１０モル％≦構成単位（Ｉ）≦４０モル％
５０モル％≦構成単位（ＩＩ）≦８５モル％
１モル％≦構成単位（ＩＩＩ）≦２０モル％
１モル％≦構成単位（ＩＶ）≦２０モル％
(All aromatic liquid crystal polyester resin)
The all-aromatic liquid crystal polyester resin according to the present invention has a structural unit (I) derived from p-hydroxybenzoic acid, a structural unit (II) derived from 6-hydroxy-2-naphthoic acid, and a configuration derived from an aromatic diol compound. The composition ratio (mol%) of the structural units (I) to (IV) in the total aromatic liquid crystal polyester resin, which comprises the unit (III) and the structural unit (IV) derived from the aromatic dicarboxylic acid, is as follows. Satisfy the conditions.
10 mol% ≤ structural unit (I) ≤ 40 mol%
50 mol% ≤ structural unit (II) ≤ 85 mol%
1 mol% ≤ structural unit (III) ≤ 20 mol%
1 mol% ≤ structural unit (IV) ≤ 20 mol%
このような構成を有する全芳香族液晶ポリエステル樹脂によれば、とりわけ低い誘電正接および低吸水率を有する全芳香族液晶ポリエステル樹脂を実現することができる。
また、高い融点およびガラス転移温度の全芳香族液晶ポリエステル樹脂とすることもできるため、耐熱性の高い成形品を得ることができる。
さらに、体積膨張率を低下させることができ、成形時および加工時の寸法安定性が高い全芳香族液晶ポリエステル樹脂を実現することができる。
According to the total aromatic liquid crystal polyester resin having such a structure, it is possible to realize a total aromatic liquid crystal polyester resin having a particularly low dielectric loss tangent and a low water absorption rate.
Further, since a fully aromatic liquid crystal polyester resin having a high melting point and a glass transition temperature can be used, a molded product having high heat resistance can be obtained.
Further, the coefficient of thermal expansion can be reduced, and a total aromatic liquid crystal polyester resin having high dimensional stability during molding and processing can be realized.
本発明による全芳香族液晶ポリエステル樹脂の誘電正接（測定周波数：１０ＧＨｚ）は、０．７５×１０−３以下であることが好ましく、０．７０以下×１０−３であることがより好ましい。
なお、本明細書において、全芳香族液晶ポリエステル樹脂の誘電正接は、キーサイト・テクノロジー社のネットワークアナライザーＮ５２４７Ａ等を用いて、スプリットポスト誘電体共振器法（ＳＰＤＲ法）により測定することができる。
The dielectric loss tangent (measurement frequency: 10 GHz) of the total aromatic liquid crystal polyester resin according to the present invention is preferably 0.75 × 10 -3 or less, and more preferably 0.70 or less × 10 -3.
In the present specification, the dielectric loss tangent of the all-aromatic liquid crystal polyester resin can be measured by the split post dielectric resonator method (SPDR method) using a network analyzer N5247A manufactured by Keysight Technology Co., Ltd.
また、本発明による全芳香族液晶ポリエステル樹脂の吸水率は、０．０３％以下が好ましく、０．０２％以下がより好ましい。
なお、本明細書において、全芳香族液晶ポリエステル樹脂の吸水率は、本発明による全芳香族液晶ポリエステル樹脂を加熱溶融した後、射出成形、プレス成形、フィルム成形して得られた成形品を、ＡＳＴＭ Ｄ５７０の試験方法に準拠して、室温（２３℃）、２４時間水中に浸漬し、浸漬前の試験片の重量および２４時間浸漬後の試験片の重量を測定し、以下式に従い算出することができる。
吸水率（％）＝（２４時間浸漬後の試験片の重量−浸漬前の試験片の重量）／浸漬前の試験片の重量×１００
The water absorption rate of the total aromatic liquid crystal polyester resin according to the present invention is preferably 0.03% or less, more preferably 0.02% or less.
In the present specification, the water absorption rate of the total aromatic liquid crystal polyester resin is a molded product obtained by heat-melting the total aromatic liquid crystal polyester resin according to the present invention, and then injection molding, press molding, or film molding. According to the test method of ASTM D570, soak in water at room temperature (23 ° C.) for 24 hours, measure the weight of the test piece before immersion and the weight of the test piece after immersion for 24 hours, and calculate according to the following formula. Can be done.
Water absorption rate (%) = (weight of test piece after immersion for 24 hours-weight of test piece before immersion) / weight of test piece before immersion × 100
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、２９０℃以上であることが好ましく、３００℃〜３５０℃であることがより好ましく、３００℃〜３３０℃であることがさらに好ましい。
本発明による全芳香族液晶ポリエステル樹脂の融点を上記数値範囲とすることにより、電気電子機器や通信機器等に使用される成形品の耐熱性を向上させることができる。
なお、本明細書において、全芳香族液晶ポリエステル樹脂の融点は、ＩＳＯ１１３５７、ＡＳＴＭ Ｄ３４１８の試験方法に準拠するものであり、日立ハイテクサイエンス（株）製の示差走査熱量計（ＤＳＣ）等を用いて、測定することができる。
The melting point of the all-aromatic liquid crystal polyester resin according to the present invention is preferably 290 ° C. or higher, more preferably 300 ° C. to 350 ° C., and even more preferably 300 ° C. to 330 ° C.
By setting the melting point of the all-aromatic liquid crystal polyester resin according to the present invention within the above numerical range, the heat resistance of the molded product used for electrical and electronic equipment, communication equipment and the like can be improved.
In this specification, the melting point of the total aromatic liquid crystal polyester resin conforms to the test methods of ISO11357 and ASTM D3418, and a differential scanning calorimetry (DSC) manufactured by Hitachi High-Tech Science Co., Ltd. is used. , Can be measured.
また、本発明による全芳香族液晶ポリエステル樹脂のガラス転移温度は、１２０℃以上であることが好ましく、１２５℃〜１５０℃であることがより好ましい。
本発明による全芳香族液晶ポリエステル樹脂のガラス転移温度を上記数値範囲とすることにより、電子機器や通信機器等に使用される成形品の耐熱性を向上させることができる。
なお、本明細書において、全芳香族液晶ポリエステル樹脂のガラス転移温度は、ＪＩＳＫ７２４４に準拠し、動的粘弾性測定装置（日立ハイテクサイエンス(株)、商品名：ＤＭＡ７１００）等を用い、動的粘弾性測定により得られるｔａｎＤのピークトップ温度から求めることができる。
The glass transition temperature of the all-aromatic liquid crystal polyester resin according to the present invention is preferably 120 ° C. or higher, more preferably 125 ° C. to 150 ° C.
By setting the glass transition temperature of the all-aromatic liquid crystal polyester resin according to the present invention within the above numerical range, the heat resistance of the molded product used for electronic devices, communication devices and the like can be improved.
In this specification, the glass transition temperature of the total aromatic liquid crystal polyester resin conforms to JIS K7244, and uses a dynamic viscoelasticity measuring device (Hitachi High-Tech Science Co., Ltd., trade name: DMA7100) or the like to obtain dynamic viscoelasticity. It can be obtained from the peak top temperature of tanD obtained by viscoelasticity measurement.
また、本発明による全芳香族液晶ポリエステル樹脂の体積膨張率は、成形時の寸法安定性の観点から、２３０ｐｐｍ／℃以下であることが好ましく、１８０ｐｐｍ／℃〜２２５ｐｐｍ／℃であることがより好ましい。
なお、本明細書において、全芳香族液晶ポリエステル樹脂の体積膨張率は、この樹脂を加熱溶融し、射出成形やプレス成形、フィルム成形して得られた成形品から熱機械的分析装置（日立ハイテクサイエンス（株）製、商品名：ＴＭＡ７０００）を用いて測定することができる。
The volume expansion coefficient of the total aromatic liquid crystal polyester resin according to the present invention is preferably 230 ppm / ° C. or lower, more preferably 180 ppm / ° C. to 225 ppm / ° C. from the viewpoint of dimensional stability during molding. ..
In the present specification, the volume expansion rate of the total aromatic liquid crystal polyester resin is determined by a thermomechanical analyzer (Hitachi High-Tech) from a molded product obtained by heating and melting this resin, injection molding, press molding, and film molding. It can be measured using a product manufactured by Science Co., Ltd., trade name: TMA7000).
また、成形性という観点からは、本発明による液晶ポリエステル樹脂の粘度は、液晶ポリエステル樹脂の融点＋２０℃、せん断速度１０００ｓ−１における粘度は、１０Ｐａ・ｓ〜１０００Ｐａ・ｓであることが好ましく、１０Ｐａ・ｓ〜５００Ｐａ・ｓであることがより好ましい。
なお、本明細書において、全芳香族液晶ポリエステル樹脂の粘度は、ＪＩＳ Ｋ７１９９に準拠し、キャピラリーレオメーター粘度計を用いて測定することができる。
From the viewpoint of moldability, the viscosity of the liquid crystal polyester resin according to the present invention is preferably 10 Pa · s to 1000 Pa · s at a melting point of the liquid crystal polyester resin of + 20 ° C. and a shear rate of 1000 s-1. -S to 500 Pa · s is more preferable.
In this specification, the viscosity of the total aromatic liquid crystal polyester resin conforms to JIS K7199 and can be measured using a capillary rheometer viscometer.
本発明による全芳香族液晶ポリエステル樹脂の液晶性は、メトラー製の顕微鏡用ホットステージ（商品名：ＦＰ８２ＨＴ）を備えたオリンパス（株）製の偏光顕微鏡（商品名：ＢＨ−２）等を用い、全芳香族液晶ポリエステル樹脂を顕微鏡加熱ステージ上にて加熱溶融させた後、光学異方性の有無を観察することにより確認することができる。 For the liquid crystal property of the total aromatic liquid crystal polyester resin according to the present invention, a polarizing microscope (trade name: BH-2) manufactured by Olympus Corporation equipped with a hot stage for a microscope (trade name: FP82HT) manufactured by METTLER is used. The total aromatic liquid crystal polyester resin can be confirmed by heating and melting it on a microscope heating stage and then observing the presence or absence of optical anisotropy.
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 structural unit contained in the total aromatic liquid crystal polyester resin will be described.
（ｐ−ヒドロキシ安息香酸に由来する構成単位（Ｉ））
全芳香族液晶ポリエステル樹脂は、下記式で表されるｐ−ヒドロキシ安息香酸に由来する構成単位（Ｉ）を含み、全芳香族液晶ポリエステル樹脂中における構成単位（Ｉ）の組成比（モル％）は、１０モル％〜４０モル％である。全芳香族液晶ポリエステル樹脂の低誘電正接化および低吸水率化という観点からは、より好ましくは１５モル％〜３５モル％であり、さらに好ましくは２０モル％〜３０モル％である。
The total aromatic liquid crystal polyester resin contains a structural unit (I) derived from p-hydroxybenzoic acid represented by the following formula, and the composition ratio (mol%) of the structural unit (I) in the total aromatic liquid crystal polyester resin. Is 10 mol% to 40 mol%. From the viewpoint of low dielectric loss tangent and low water absorption of the total aromatic liquid crystal polyester resin, it is more preferably 15 mol% to 35 mol%, and further preferably 20 mol% to 30 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））、そのアセチル化物、エステル誘導体、酸ハロゲン化物等が挙げられる。
（６−ヒドロキシ−２−ナフトエ酸に由来する構成単位（ＩＩ））
全芳香族液晶ポリエステル樹脂は、下記式で表される６−ヒドロキシ−２−ナフトエ酸に由来する構成単位（ＩＩ）を含み、全芳香族液晶ポリエステル樹脂中における構成単位（ＩＩ）の組成比（モル％）は、５０モル％〜８５モル％である。全芳香族液晶ポリエステル樹脂の低誘電正接化および低吸水率化という観点からは、より好ましくは６０モル％〜８０モル％であり、さらに好ましくは６０モル％〜７５モル％である。
The total aromatic liquid crystal polyester resin contains a structural unit (II) derived from 6-hydroxy-2-naphthoic acid represented by the following formula, and the composition ratio of the structural unit (II) in the total aromatic liquid crystal polyester resin ( Mol%) is 50 mol% to 85 mol%. From the viewpoint of low dielectric loss tangent and low water absorption of the total aromatic liquid crystal polyester resin, it is more preferably 60 mol% to 80 mol%, and further preferably 60 mol% to 75 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））、そのアセチル化物、エステル誘導体、酸ハロゲン化物等が挙げられる。
（芳香族ジオール化合物に由来する構成単位（ＩＩＩ））
全芳香族液晶ポリエステル樹脂は、芳香族ジオール化合物に由来する構成単位（ＩＩＩ）を含んでなるものであり、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、１モル％〜２０モル％である。全芳香族液晶ポリエステル樹脂の低誘電正接化および低吸水率化という観点からは、より好ましくは１モル％〜１５モル％であり、さらに好ましくは２モル％〜１０モル％である。全芳香族液晶ポリエステル樹脂は、２種以上の構成単位（ＩＩＩ）を含むものであってもよい。
(Constituent unit derived from aromatic diol compound (III))
The total aromatic liquid crystal polyester resin contains a structural unit (III) derived from an aromatic diol compound, and the composition ratio (mol%) of the structural unit (III) in the liquid crystal polyester is from 1 mol% to 1 mol%. It is 20 mol%. From the viewpoint of low dielectric loss tangent and low water absorption of the total aromatic liquid crystal polyester resin, it is more preferably 1 mol% to 15 mol%, and further preferably 2 mol% to 10 mol%. The total aromatic liquid crystal polyester resin may contain two or more kinds of structural units (III).
一実施態様において、構成単位（ＩＩＩ）は下記式で表される。
構成単位（ＩＩＩ）を与えるモノマーとしては、例えば、ハイドロキノン（ＨＱ，下記式（３））、４，４−ジヒドロキシビフェニル（ＢＰ、下記式（４））、３，３’−ジメチル−１，１’−ビフェニル−４，４’−ジオール（ＯＣＢＰ、下記式（５））およびこれらのアシル化物等が挙げられる。
（芳香族ジカルボン酸に由来する構成単位（ＩＶ））
全芳香族液晶ポリエステル樹脂は、芳香族ジカルボン酸に由来する構成単位（ＩＶ）を含んでなるものであり、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％〜２０モル％である。全芳香族液晶ポリエステル樹脂の低誘電正接化および低吸水率化という観点からは、より好ましくは１モル％〜１５モル％であり、さらに好ましくは２モル％〜１０モル％である。全芳香族液晶ポリエステル樹脂は、２種以上の構成単位（ＩＶ）を含むものであってもよい。
(Constituent unit derived from aromatic dicarboxylic acid (IV))
The total aromatic liquid crystal polyester resin contains a structural unit (IV) derived from an aromatic dicarboxylic acid, and the composition ratio (mol%) of the structural unit (IV) in the liquid crystal polyester is from 1 mol% to 1 mol%. It is 20 mol%. From the viewpoint of low dielectric loss tangent and low water absorption of the total aromatic liquid crystal polyester resin, it is more preferably 1 mol% to 15 mol%, and further preferably 2 mol% to 10 mol%. The total aromatic liquid crystal polyester resin may contain two or more kinds of structural units (IV).
一実施態様において、構成単位（ＩＶ）は下記式で表される。
構成単位（ＩＶ）を与えるモノマーとしては、テレフタル酸（ＴＰＡ、下記式（６））、イソフタル酸（ＩＰＡ、下記式（７））およびこれらのエステル誘導体、酸ハロゲン化物等が挙げられる。
（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、構成単位（Ｉ）〜（ＩＶ）を与えるモノマーを、溶融重合、固相重合、溶液重合およびスラリー重合等、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。
一実施態様において、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２段階重合によっても製造することができる。
(Manufacturing method of all aromatic liquid crystal polyester resin)
The total aromatic liquid crystal polyester resin according to the present invention is produced by polymerizing the monomers giving the constituent units (I) to (IV) by a conventionally known method such as melt polymerization, solid phase polymerization, solution polymerization and slurry polymerization. can do.
In one embodiment, the all-aromatic liquid crystal polyester resin according to the present invention can be produced only by melt polymerization. It can also be produced by two-step polymerization in which a prepolymer is produced by melt polymerization and then solid-phase polymerized.
溶融重合は、本発明に係るポリエステル化合物が効率よく得られる観点から、上記構成単位（Ｉ）〜（ＩＶ）を与えるモノマーを、所定の配合で合わせて１００モル％として、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 of efficiently obtaining the polyester compound according to the present invention, the monomers giving the above-mentioned structural units (I) to (IV) are combined in a predetermined formulation to be 100 mol%, and the total hydroxyl groups of the monomers are combined. On the other hand, it is preferable to carry out the process under acetic acid reflux in the presence of 1.05 to 1.15 molar equivalents of acetic anhydride.
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、窒素等の不活性雰囲気下、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等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 steps of melt polymerization and subsequent solid phase polymerization, the prepolymer obtained by melt polymerization is cooled and solidified, pulverized into powder or flakes, and then a known solid phase polymerization method. For example, a method of heat-treating the prepolymer resin in an inert atmosphere such as nitrogen or in a vacuum in a temperature range of 200 to 350 ° C. for 1 to 30 hours is preferably selected. Solid-phase polymerization may be carried out with stirring, or may be carried out in a stationary state 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、三酸化アンチモン等の金属塩触媒、Ｎ−メチルイミダゾール等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、特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。 The catalyst may or may not be used in the polymerization reaction. As the catalyst to be used, conventionally known catalysts for polymerizing polyester 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. Examples thereof include salt catalysts, nitrogen-containing heterocyclic compounds such as N-methylimidazole, and organic compound catalysts. The amount of the catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 parts by weight with respect to 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等が挙げられる。 The polymerization reaction device in the melt polymerization is not particularly limited, but a reaction device used for the 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, etc., or a stirring tank type polymerization reaction device having a stirring device having various shapes of stirring blades obtained by modifying these, or a stirring tank type polymerization reaction device. , Kneader, roll mill, Banbury mixer and the like, which are generally used for kneading resins.
（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を含んでなるものであり、その形状は用途に応じ適宜変更されるものであり、特に限定されず、例えば、フィルム状、板状、繊維状等とすることができる。
(Molding)
The molded product according to the present invention contains a totally aromatic liquid crystal polyester resin, and its shape is appropriately changed according to the intended use, and is not particularly limited, and is, for example, a film shape, a plate shape, or a fibrous shape. And so on.
また、本発明による成形品は、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、ポリアリレートおよびポリブチレンテレフタレート等のポリエステル樹脂、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂、シクロオレフィンポリマー、ポリ塩化ビニル等のビニル樹脂、ポリアクリレート、ポリメタアクリレートおよびポリメチルメタアクリレート等の（メタ）アクリル樹脂、ポリフェニレンエーテル樹脂、ポリアセタール樹脂、ポリアミド樹脂、ポリイミドおよびポリエーテルイミド等のイミド樹脂、ポリスチレン、高衝撃ポリスチレン、ＡＳ樹脂およびＡＢＳ樹脂等のポリスチレン樹脂、エポキシ樹脂等の熱硬化樹脂、セルロース樹脂、ポリエーテルエーテルケトン樹脂、フッ素樹脂ならびにポリカーボネート樹脂等が挙げられ、成形品は、これらを1種または２種以上含んでいてもよい。 Further, the molded product according to the present invention may contain a resin other than the all-aromatic liquid crystal polyester resin as long as the effects of the present invention are not impaired. For example, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polyarylate and polybutylene terephthalate, polyolefin resins such as polyethylene and polypropylene, cycloolefin polymers, vinyl resins such as polyvinyl chloride, polyacrylates, polymethacrylates and polymethylmethas. Heat of (meth) acrylic resin such as acrylate, polyphenylene ether resin, polyacetal resin, polyamide resin, imide resin such as polyimide and polyetherimide, polystyrene resin such as polystyrene, high impact polystyrene, AS resin and ABS resin, and epoxy resin. Examples thereof include a cured resin, a cellulose resin, a polyether ether ketone resin, a fluororesin, and a polycarbonate resin, and the molded product may contain one or more of these.
本発明による成形品は、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、硬化剤、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 molded product according to the present invention has other additives such as a colorant, a dispersant, a plasticizer, an antioxidant, a curing agent, a flame retardant, a heat stabilizer, and an ultraviolet absorber as long as the effects of the present invention are not impaired. , Antistatic agent, surfactant may be contained.
本発明による成形品は、全芳香族液晶ポリエステル樹脂および所望によりその他の樹脂や添加剤等を含む混合物をプレス成形、発泡成形、射出成形、押出成形、打ち抜き成形することにより得ることができる。
なお、混合物は、全芳香族液晶ポリエステル樹脂等をバンバリーミキサー、ニーダー、一軸または二軸押出機等を用いて、溶融混練することにより得ることができる。
The molded product according to the present invention can be obtained by press molding, foam molding, injection molding, extrusion molding, or punch molding of a mixture containing a total aromatic liquid crystal polyester resin and, if desired, other resins and additives.
The mixture can be obtained by melt-kneading a fully aromatic liquid crystal polyester resin or the like using a Banbury mixer, a kneader, a single-screw or twin-screw extruder or the like.
一実施態様において、成形品のフィルムは、インフレーション成形、溶融押出成形等の押出成形、および溶液キャスト法により得ることができる。このようにして得られるフィルムは、全芳香族液晶ポリエステル樹脂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、または耐熱性向上目的で熱処理を行ってもよい。
In one embodiment, the film of the molded product can be obtained by extrusion molding such as inflation molding, melt extrusion molding, and a solution casting method. The film thus obtained may be a single-layer film made of a fully aromatic liquid crystal polyester resin, or may be a multilayer film with different materials.
The film melt-extruded or solution-cast may be stretched on a single shaft or a double shaft for the purpose of improving dimensional stability and mechanical properties. Further, heat treatment may be performed for the purpose of removing the anisotropy of these films or improving the heat resistance.
（電気電子部品）
本発明による電気電子部品は、上記全芳香族液晶ポリエステル樹脂を含んでなる。
電気電子部品としては、例えば、ＥＴＣ、ＧＰＳ、無線ＬＡＮおよび携帯電話等の電子機器や通信機器に使用されるアンテナ、高速伝送用コネクタ、ＣＰＵソケット、回路基板、フレキシブルプリント基板（ＦＰＣ）、積層用回路基板、衝突防止用レーダーなどのミリ波および準ミリ波レーダー、ＲＦＩＤタグ、コンデンサー、インバーター部品、絶縁フィルム、ケーブルの被覆材、リチウムイオン電池等の二次電池の絶縁材、スピーカー振動板等が挙げられる。
一実施態様において、電気電子部品は、全芳香族液晶ポリエステル樹脂を含む成形品（例えば、射出成形品やフィルム等）を備えてなる。
(Electrical and electronic parts)
The electrical and electronic components according to the present invention include the above-mentioned all-aromatic liquid crystal polyester resin.
Examples of electrical and electronic components include antennas used in electronic devices and communication devices such as ETC, GPS, wireless LAN and mobile phones, high-speed transmission connectors, CPU sockets, circuit boards, flexible printed circuit boards (FPC), and stacking. Circuit boards, millimeter-wave and quasi-millimeter-wave radars such as collision prevention radars, RFID tags, capacitors, inverter parts, insulating films, cable coverings, secondary battery insulating materials such as lithium-ion batteries, speaker diaphragms, etc. Can be mentioned.
In one embodiment, the electrical and electronic component comprises a molded article (eg, an injection molded article, a film, etc.) containing a fully aromatic liquid crystal polyester resin.
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 in more detail 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の合成）
攪拌翼を有する重合容器にｐ−ヒドロキシ安息香酸（ＨＢＡ）１１３．９５ｇ（２５モル％）、６−ヒドロキシ−２−ナフトエ酸（ＨＮＡ）４０３．６５ｇ（６５モル％）、４，４−ジヒドロキシビフェニル（ＢＰ）３０．７２ｇ（５モル％）、テレフタル酸（ＴＰＡ）２７．４１ｇ（５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３６３．８５ｇ（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。
<Manufacturing of all-aromatic liquid crystal polyester resin>
(Example 1: Synthesis of total aromatic liquid crystal polyester resin A)
113.95 g (25 mol%) of p-hydroxybenzoic acid (HBA), 403.65 g (65 mol%) of 6-hydroxy-2-naphthoic acid (HNA), 4,4-dihydroxybiphenyl in a polymerization vessel with a stirring blade. Add 30.72 g (5 mol%) of (BP) and 27.41 g (5 mol%) of terephthalic acid (TPA), add potassium acetate and magnesium acetate as catalysts, and perform vacuum-nitrogen injection of the polymerization vessel three times. After the nitrogen substitution, 363.85 g of acetic anhydride (1.08 molar equivalent with respect to the hydroxyl group) was further added, the temperature was raised to 150 ° C., and the acetylation reaction was carried out in a refluxed state for 2 hours.
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 completion of acetylation, the temperature of the polymerization vessel in the acetic acid distillate state was raised at 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 a mesh size of 1.0 mm to obtain a prepolymer.
次に、上記で得られたプレポリマーを、ヤマト科学（株）製のオーブンでヒーターにより、温度を室温から１１時間かけて２８０℃まで昇温した後、２８０℃で温度を２時間保持して固相重合を行った。その後室温で自然放熱し、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（商品名：ＦＰ８２ＨＴ）を備えたオリンパス（株）製の偏光顕微鏡（商品名：ＢＨ−２）を用い、全芳香族液晶ポリエステル樹脂Ａ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 temperature of the prepolymer obtained above was raised from room temperature to 280 ° C. over 11 hours by a heater in an oven manufactured by Yamato Scientific Co., Ltd., and then the temperature was maintained at 280 ° C. for 2 hours. Solid phase polymerization was performed. Then, the heat was naturally dissipated at room temperature to obtain a totally aromatic liquid crystal polyester resin A. Using a polarizing microscope (trade name: BH-2) manufactured by Olympus Corporation equipped with a hot stage for a microscope (trade name: FP82HT) manufactured by METTLER, a sample of all aromatic liquid crystal polyester resin A is placed on a microscope heating stage. It was melted by heating, and the liquid crystal property 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の合成）
モノマー仕込みを、ＨＢＡ２５モル％、ＨＮＡ７０モル％、３，３’−ジメチル−１，１’−ビフェニル−４，４’−ジオール（ＯＣＢＰ）２．５モル％、ＴＰＡ２．５モル％に変更し、固相重合の最終温度を２９５℃にした以外は実施例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: Synthesis of total aromatic liquid crystal polyester resin B)
The monomer charge was changed to 25 mol% of HBA, 70 mol% of HNA, 2.5 mol% of 3,3'-dimethyl-1,1'-biphenyl-4,4'-diol (OCBP), and 2.5 mol% of TPA. A liquid crystal polyester resin B was obtained in the same manner as in Example 1 except that the final temperature of the solid phase polymerization was set to 295 ° C., and the liquid crystal property was confirmed in the same manner as above.
（実施例３：全芳香族液晶ポリエステル樹脂Ｃの合成）
モノマー仕込みを、ＨＢＡ２０モル％、ＨＮＡ７５モル％、ＢＰ２．５モル％、ＴＰＡ２．５モル％に変更し、固相重合の最終温度を２９５℃にした以外は実施例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: Synthesis of total aromatic liquid crystal polyester resin C)
The liquid crystal polyester was charged in the same manner as in Example 1 except that the monomer charge was changed to HBA 20 mol%, HNA 75 mol%, BP 2.5 mol%, and TPA 2.5 mol%, and the final temperature of solid phase polymerization was 295 ° C. Resin C was obtained, and the liquid crystal property was confirmed in the same manner as described above.
（実施例４：全芳香族液晶ポリエステル樹脂Ｄの合成）
モノマー仕込みを、ＨＢＡ２５モル％、ＨＮＡ６５モル％、ハイドロキノン（ＨＱ）５モル％、ＴＰＡ５モル％に変更し、固相重合の最終温度を２９５℃にした以外は実施例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: Synthesis of total aromatic liquid crystal polyester resin D)
The liquid crystal polyester was charged in the same manner as in Example 1 except that the monomer charge was changed to HBA 25 mol%, HNA 65 mol%, hydroquinone (HQ) 5 mol%, and TPA 5 mol%, and the final temperature of solid phase polymerization was 295 ° C. Resin D was obtained, and the liquid crystal property was confirmed in the same manner as described above.
（実施例５：全芳香族液晶ポリエステル樹脂Ｅの合成）
モノマー仕込みを、ＨＢＡ２５モル％、ＨＮＡ７０モル％、ＢＰ２．５モル％、ＴＰＡ２．５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Ｅを得て、上記と同様にして液晶性を確認した。
(Example 5: Synthesis of total aromatic liquid crystal polyester resin E)
A liquid crystal polyester resin E was obtained in the same manner as in Example 1 except that the monomer charge was changed to HBA 25 mol%, HNA 70 mol%, BP 2.5 mol%, and TPA 2.5 mol%, and the liquid crystal was obtained in the same manner as above. I confirmed the sex.
（比較例１：全芳香族液晶ポリエステル樹脂Ｆの合成）
モノマー仕込みを、ＨＢＡ６０モル％、ＢＰ２０モル％、ＴＰＡ１５モル％、イソフタル酸（ＩＰＡ）５モル％に変更し、固相重合の最終温度を３１０℃にした以外は実施例１と同様にして、液晶ポリエステル樹脂Ｆを得て、上記と同様にして液晶性を確認した。
(Comparative Example 1: Synthesis of Total Aromatic Liquid Crystal Polyester Resin F)
The liquid crystal was charged in the same manner as in Example 1 except that the monomer charge was changed to HBA 60 mol%, BP 20 mol%, TPA 15 mol%, and isophthalic acid (IPA) 5 mol%, and the final temperature of solid phase polymerization was 310 ° C. A polyester resin F was obtained, and the liquid crystal property was confirmed in the same manner as described above.
（比較例２：全芳香族液晶ポリエステル樹脂Ｇの合成）
モノマー仕込みを、ＨＢＡ２モル％、ＨＮＡ４８モル％、ＢＰ２５モル％、ＴＰＡ２５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Ｇを得て、上記と同様にして液晶性を確認した。
(Comparative Example 2: Synthesis of Total Aromatic Liquid Crystal Polyester Resin G)
A liquid crystal polyester resin G was obtained in the same manner as in Example 1 except that the monomer charge was changed to 2 mol% HBA, 48 mol% HNA, 25 mol% BP, and 25 mol% TPA, and the liquid crystal property was confirmed in the same manner as above. ..
（比較例３：全芳香族液晶ポリエステル樹脂Ｈの合成）
モノマー仕込みを、ＨＢＡ２７モル％、ＨＮＡ７３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 3: Synthesis of Total 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 charge was changed to 27 mol% HBA and 73 mol% HNA, and the liquid crystal property was confirmed in the same manner as above.
（比較例４：全芳香族液晶ポリエステル樹脂Ｉの合成）
モノマー仕込みを、ＨＮＡ７０モル％、ＨＱ１５モル％、ＴＰＡ１５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Ｉを得て、上記と同様にして液晶性を確認した。
(Comparative Example 4: Synthesis of Total Aromatic Liquid Crystal Polyester Resin I)
A liquid crystal polyester resin I was obtained in the same manner as in Example 1 except that the monomer charge was changed to 70 mol% HNA, 15 mol% HQ, and 15 mol% TPA, and the liquid crystal property was confirmed in the same manner as above.
＜＜性能評価＞＞
＜誘電正接測定＞
実施例および比較例により得られた全芳香族液晶ポリエステル樹脂を融点〜融点＋３０℃条件で加熱溶融、射出成形し、３０ｍｍ×３０ｍｍ×０．４ｍｍの平板状試験片を作製した。この試験片の誘電正接を、キーサイト・テクノロジー社のネットワークアナライザーＮ５２４７Ａを用いて、スプリットポスト誘電体共振器法（ＳＰＤＲ法）により、周波数１０ＧＨｚの誘電正接を測定した。
<< Performance Evaluation >>
<Dissipation factor measurement>
The all-aromatic liquid crystal polyester resin obtained in Examples and Comparative Examples was heated and melted under the conditions of melting point to melting point + 30 ° C. and injection molded to prepare a flat plate-shaped test piece having a size of 30 mm × 30 mm × 0.4 mm. The dielectric loss tangent of this test piece was measured by the split post dielectric resonator method (SPDR method) using a network analyzer N5247A manufactured by Keysight Technology Co., Ltd. at a frequency of 10 GHz.
＜吸水率＞
上記のようにして作製した試験片を、ＡＳＴＭ Ｄ５７０の試験方法を用い、室温（２３℃）、２４時間水中に浸漬し、浸漬前の試験片の重量および２４時間浸漬後の試験片の重量を測定し、吸水率を算出した、表１にまとめた。
<Water absorption rate>
The test piece prepared as described above was immersed in water at room temperature (23 ° C.) for 24 hours using the test method of ASTM D570, and the weight of the test piece before immersion and the weight of the test piece after immersion for 24 hours were determined. It was measured and the water absorption rate was calculated, which is summarized in Table 1.
＜融点の測定＞
実施例および比較例において得られた全芳香族液晶ポリエステル樹脂の融点を、日立ハイテクサイエンス（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１０℃／分で室温から３６０〜３８０℃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３０℃まで降温し、更に１０℃／分の速度で３８０℃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 total aromatic liquid crystal polyester resins obtained in Examples and Comparative Examples were measured by a differential scanning calorimetry (DSC) manufactured by Hitachi High-Tech Science Co., Ltd. At this time, the temperature is raised from room temperature to 360 to 380 ° C. at a heating rate of 10 ° C./min to completely melt the polymer, then the temperature is lowered to 30 ° C. at a rate of 10 ° C./min, and further at a rate of 10 ° C./min. The apex of the endothermic peak obtained when the temperature was raised to 380 ° C. was taken as the melting point. The measurement results are summarized in Table 1.
＜ガラス転移温度の測定＞
実施例および比較例において得られた全芳香族液晶ポリエステル樹脂を融点〜融点＋３０℃条件で加熱溶融、射出成形し、３０ｍｍ×３０ｍｍ×０．４ｍｍの平板状試験片を作成した。この平板状試験片を幅８ｍｍに切削し、３０×８×０．４ｍｍの短冊状試験片を準備した。動的粘弾性測定装置（日立ハイテクサイエンス(株)製、商品名：ＤＭＡ７１００）を用い、引張モードの動的粘弾性測定により得られるｔａｎＤのピークトップ温度から、全芳香族液晶ポリエステル樹脂のガラス転移点を求めた。測定結果を表１にまとめた。
<Measurement of glass transition temperature>
The all-aromatic liquid crystal polyester resin obtained in Examples and Comparative Examples was heated and melted under the conditions of melting point to melting point + 30 ° C. and injection molded to prepare a flat plate-shaped test piece of 30 mm × 30 mm × 0.4 mm. This flat plate-shaped test piece was cut to a width of 8 mm to prepare a strip-shaped test piece having a width of 30 × 8 × 0.4 mm. Glass transition of all aromatic liquid crystal polyester resin from the peak top temperature of tanD obtained by dynamic viscoelasticity measurement in tensile mode using a dynamic viscoelasticity measuring device (manufactured by Hitachi High-Tech Science Co., Ltd., trade name: DMA7100) I asked for a point. The measurement results are summarized in Table 1.
＜体積膨張率の測定＞
実施例および比較例により得られた全芳香族液晶ポリエステル樹脂を、融点〜融点＋３０℃で加熱溶融、射出成形し、３０ｍｍ×３０ｍｍ×０．４ｍｍの平板状試験片を作成した。この平板状試験片を引張モード用に幅５ｍｍに切削し、３０×５×０．４ｍｍの短冊状試験片を準備した。また圧縮モード用に平板状試験片中央部を７×７ｍｍに切削し、７×７×０．４ｍｍの板状試験片を準備した。
これらの試験片の３０〜１５０℃の体積膨張率（ＭＤ線膨張率＋ＴＤ線膨張率＋厚み線膨張率）を、熱機械的分析装置（日立ハイテクサイエンス（株）製、商品名：ＴＭＡ７０００）を用いて測定した、なお、ＭＤ方向およびＴＤ方向は引張モード、厚み方向は圧縮モードで評価した。測定結果を表１にまとめた。
<Measurement of coefficient of thermal expansion>
The all-aromatic liquid crystal polyester resin obtained in Examples and Comparative Examples was heated and melted at a melting point to a melting point of + 30 ° C. and injection molded to prepare a flat plate-shaped test piece having a size of 30 mm × 30 mm × 0.4 mm. This flat plate-shaped test piece was cut to a width of 5 mm for the tension mode, and a strip-shaped test piece having a width of 30 × 5 × 0.4 mm was prepared. Further, the central portion of the flat plate-shaped test piece was cut to 7 × 7 mm for the compression mode, and a plate-shaped test piece having a size of 7 × 7 × 0.4 mm was prepared.
The coefficient of thermal expansion (MD line expansion rate + TD line expansion rate + thickness line expansion rate) of these test pieces at 30 to 150 ° C. is measured by a thermomechanical analyzer (manufactured by Hitachi High-Tech Science Co., Ltd., trade name: TMA7000). The MD direction and the TD direction were evaluated in the tension mode, and the thickness direction was evaluated in the compression mode. The measurement results are summarized in Table 1.
Claims (10)
６−ヒドロキシ−２−ナフトエ酸に由来する構成単位（II）、
芳香族ジオール化合物に由来する構成単位（III）および
芳香族ジカルボン酸に由来する構成単位（IV）を含んでなり、
前記構成単位（I）〜（IV）の組成比（モル％）が、下記の条件を満たし、
融点が、２９０℃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。
１５モル％≦構成単位（I）≦３５モル％
６０モル％≦構成単位（II）≦８０モル％
１モル％≦構成単位（III）≦１０モル％
１モル％≦構成単位（IV）≦１０モル％ Constituent unit (I) derived from p-hydroxybenzoic acid,
Constituent unit (II) derived from 6-hydroxy-2-naphthoic acid,
It comprises a structural unit (III) derived from an aromatic diol compound and a structural unit (IV) derived from an aromatic dicarboxylic acid.
The composition ratio (mol%) of the structural units (I) to (IV) satisfies the following conditions.
A totally aromatic liquid crystal polyester resin having a melting point of 290 ° C. or higher.
15 mol% ≤ structural unit (I) ≤ 35 mol%
60 mol% ≤ structural unit (II) ≤ 80 mol%
1 mol% ≤ structural unit (III) ≤ 10 mol%
1 mol% ≤ structural unit (IV) ≤ 10 mol%
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