TWI732820B - Fully aromatic liquid crystal polyester resin and its manufacturing method - Google Patents

Fully aromatic liquid crystal polyester resin and its manufacturing method Download PDF

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TWI732820B
TWI732820B TW106103627A TW106103627A TWI732820B TW I732820 B TWI732820 B TW I732820B TW 106103627 A TW106103627 A TW 106103627A TW 106103627 A TW106103627 A TW 106103627A TW I732820 B TWI732820 B TW I732820B
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liquid crystal
crystal polyester
polyester resin
aromatic liquid
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TW201739786A (en
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秋山希望
川村亮人
安藤正寿
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日商捷客斯能源股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/79—Interfacial processes, i.e. processes involving a reaction at the interface of two non-miscible liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Abstract

本發明之課題在於提供一種具有較高之機械強度及優異之填充性及耐起泡性以及低翹曲性之全芳香族液晶聚酯樹脂。 本發明之全芳香族液晶聚酯樹脂之特徵在於：其係包含下述式(I)～(V)所表示之結構單元(I)～(V)而成者，

Figure 106103627-A0305-004-001
上述芳香族液晶聚酯中之結構單元(I)～(V)之組成比(莫耳%)滿足下述條件： 15莫耳%≦結構單元(I)≦35莫耳% 5莫耳%≦結構單元(II)≦15莫耳% 21莫耳%≦結構單元(III)≦29莫耳% 1莫耳%≦結構單元(IV)≦9莫耳% 25莫耳%≦結構單元(V)≦40莫耳% 結構單元(I)＋結構單元(II)＋結構單元(III)＋結構單元(IV)＋結構單元(V)＝100莫耳%，且 上述全芳香族液晶聚酯樹脂之熔點為320℃以上。The subject of the present invention is to provide a wholly aromatic liquid crystal polyester resin with high mechanical strength, excellent filling properties, blistering resistance, and low warpage. The wholly aromatic liquid crystal polyester resin of the present invention is characterized in that it contains structural units (I) to (V) represented by the following formulas (I) to (V),
Figure 106103627-A0305-004-001
The composition ratio (mol%) of the structural units (I) to (V) in the above aromatic liquid crystal polyester satisfies the following conditions: 15 mol%≦structural unit (I)≦35 mol% 5 mol%≦ Structural unit (II) ≦ 15 mol% 21 mol% ≦ structural unit (III) ≦ 29 mol% 1 mol% ≦ structural unit (IV) ≦ 9 mol% 25 mol% ≦ structural unit (V) ≦40 mol% structural unit (I) + structural unit (II) + structural unit (III) + structural unit (IV) + structural unit (V) = 100 mol%, and the above-mentioned wholly aromatic liquid crystal polyester resin The melting point is above 320°C.

Description

全芳香族液晶聚酯樹脂以及其製造方法Fully aromatic liquid crystal polyester resin and its manufacturing method

本發明係關於一種全芳香族液晶聚酯樹脂以及其製造方法。進而，本發明係關於一種包含該全芳香族液晶聚酯樹脂之全芳香族液晶聚酯樹脂組合物、包含該組合物而成之成形品及電子零件。The present invention relates to a wholly aromatic liquid crystal polyester resin and its manufacturing method. Furthermore, the present invention relates to a wholly aromatic liquid crystal polyester resin composition containing the wholly aromatic liquid crystal polyester resin, molded articles and electronic parts containing the composition.

由於全芳香族液晶聚酯樹脂之成形性、耐熱性及填充性優異，因而使用其所製造之成形品(例如射出成形品)被用於各種電子零件。 近年來，由於個人電腦或智慧型手機等之小型化，故而電子零件之高積體化、薄壁化、低背化不斷發展，對具有非常薄之厚壁部之成形品之需求增長。因此，對於全芳香族液晶聚酯樹脂要求具有更優異之填充性。 作為改善全芳香族液晶聚酯樹脂等液晶聚合物之填充性即流動性之方法，例如，實施降低液晶聚合物之分子量而使之低黏度化之方法。 然而，因降低液晶聚合物之分子量而存在如下之問題：產生成形品之機械強度等物性之降低，此外，因將成形品應用於連接器等電子零件時所進行之回焊處理而於成形品表面產生鼓出(起泡)或翹曲。於是，於專利文獻1中提出一種能夠抑制起泡之發生之全芳香族液晶聚酯樹脂。 先前技術文獻 專利文獻 專利文獻1：日本專利特開2012-126842號公報Since the wholly aromatic liquid crystal polyester resin has excellent moldability, heat resistance, and filling properties, molded products (for example, injection molded products) manufactured using it are used in various electronic parts. In recent years, due to the miniaturization of personal computers, smart phones, etc., the high integration, thinning, and low profile of electronic parts have continued to develop, and the demand for molded products with very thin thick-walled parts has increased. Therefore, the wholly aromatic liquid crystal polyester resin is required to have more excellent filling properties. As a method of improving the filling property, that is, the fluidity of liquid crystal polymers such as wholly aromatic liquid crystal polyester resins, for example, a method of reducing the molecular weight of the liquid crystal polymer to lower the viscosity is implemented. However, the lowering of the molecular weight of the liquid crystal polymer has the following problems: the physical properties such as the mechanical strength of the molded product are reduced, and the molded product is reflowed when the molded product is applied to electronic parts such as connectors. The surface is bulged (bubbled) or warped. Therefore, Patent Document 1 proposes a wholly aromatic liquid crystal polyester resin capable of suppressing the occurrence of blistering. Prior Art Documents Patent Documents Patent Document 1: Japanese Patent Laid-Open No. 2012-126842

[發明所欲解決之問題] 本發明者等人此次得出如下之見解：藉由將全芳香族液晶聚酯樹脂所包含之結構單元設為特定之結構單元、組成比，且將全芳香族液晶聚酯樹脂之熔點設為320℃以上，能夠解決上述問題。本發明係基於該見解者。 因而，本發明之目的在於提供一種維持機械強度等物性並且具有優異之填充性及耐起泡性以及低翹曲性之全芳香族液晶聚酯樹脂。 [解決問題之技術手段] 本發明之全芳香族液晶聚酯樹脂之特徵在於：其係包含下述式(I)～(V)所表示之結構單元(I)～(V)而成者， [化1]

Figure 02_image003
[化2]
Figure 02_image005
[化3]
Figure 02_image007
[化4]
Figure 02_image009
[化5]
Figure 02_image011
芳香族液晶聚酯中之結構單元(I)～(V)之組成比(莫耳%)滿足下述條件： 15莫耳%≦結構單元(I)≦35莫耳% 5莫耳%≦結構單元(II)≦15莫耳% 21莫耳%≦結構單元(III)≦29莫耳% 1莫耳%≦結構單元(IV)≦9莫耳% 25莫耳%≦結構單元(V)≦40莫耳% 結構單元(I)＋結構單元(II)＋結構單元(III)＋結構單元(IV)＋結構單元(V)＝100莫耳%，且 上述全芳香族液晶聚酯樹脂之熔點為320℃以上。 於上述態樣中，較佳為結構單元(III)之含量為結構單元(IV)之含量之2倍以上。 本發明之上述全芳香族液晶聚酯樹脂之製造方法之特徵在於包括使下述式(1)～(5)所表示之單體聚合之步驟。 [化6]
Figure 02_image013
[化7]
Figure 02_image015
[化8]
Figure 02_image017
[化9]
Figure 02_image019
[化10]
Figure 02_image021
於上述態樣中，較佳為單體之聚合步驟包括使相對於上述式(1)～(4)所表示之單體所具有之所有羥基為1.05～1.15莫耳當量之乙酸酐之存在下，使上述式(1)～(5)所表示之單體熔融聚合。 本發明之全芳香族液晶聚酯樹脂組合物之特徵在於包含上述全芳香族液晶聚酯樹脂及無機填充劑而成。 於上述態樣中，較佳為無機填充劑係纖維狀填充劑及板狀填充劑。 於上述態樣中，較佳為相對於全芳香族液晶聚酯樹脂組合物所包含之全芳香族液晶聚酯樹脂100重量份，纖維狀填充劑及板狀填充劑之含量合計為100重量份以下。 本發明之成形品之特徵在於包含上述全芳香族液晶聚酯樹脂組合物而成。 本發明之電子零件之特徵在於包含上述全芳香族液晶聚酯樹脂組合物而成。 [發明之效果] 根據本發明，由於具有較高之機械強度、填充性及耐起泡性，因而能夠製造具有非常薄之厚壁部之成形品，能夠實現電子零件之高積體化、薄壁化、低背化。又，根據本發明，能夠防止翹曲之發生。[Problem to be Solved by the Invention] The inventors of the present invention came to the following insights this time: by setting the structural unit contained in the wholly aromatic liquid crystal polyester resin to a specific structural unit and composition ratio, and setting the wholly aromatic The melting point of the group liquid crystal polyester resin is set to 320°C or higher, which can solve the above-mentioned problems. The present invention is based on this knowledge. Therefore, the object of the present invention is to provide a wholly aromatic liquid crystal polyester resin that maintains physical properties such as mechanical strength and has excellent filling properties, blistering resistance, and low warpage. [Technical Means to Solve the Problem] The wholly aromatic liquid crystal polyester resin of the present invention is characterized in that it contains structural units (I) to (V) represented by the following formulas (I) to (V), [化1]
Figure 02_image003
[化2]
Figure 02_image005
[化3]
Figure 02_image007
[化4]
Figure 02_image009
[化5]
Figure 02_image011
The composition ratio (mol%) of the structural units (I)～(V) in the aromatic liquid crystal polyester satisfies the following conditions: 15mol%≦structural unit (I)≦35mol% 5mol%≦structure Unit (II)≦15 mol% 21 mol%≦structural unit (III)≦29 mol% 1 mol%≦structural unit (IV)≦9 mol% 25 mol%≦structural unit (V)≦ 40 mol% structural unit (I) + structural unit (II) + structural unit (III) + structural unit (IV) + structural unit (V) = 100 mol%, and the melting point of the above-mentioned wholly aromatic liquid crystal polyester resin Above 320°C. In the above aspect, it is preferable that the content of the structural unit (III) is more than twice the content of the structural unit (IV). The method for producing the above-mentioned wholly aromatic liquid crystal polyester resin of the present invention is characterized by including the step of polymerizing the monomers represented by the following formulas (1) to (5). [化6]
Figure 02_image013
[化7]
Figure 02_image015
[化8]
Figure 02_image017
[化9]
Figure 02_image019
[化10]
Figure 02_image021
In the above aspect, it is preferable that the polymerization step of the monomer includes the presence of 1.05-1.15 molar equivalent of acetic anhydride with respect to all the hydroxyl groups of the monomer represented by the above formulas (1) to (4). , The monomers represented by the above formulas (1) to (5) are melt-polymerized. The wholly aromatic liquid crystal polyester resin composition of the present invention is characterized by comprising the above-mentioned wholly aromatic liquid crystal polyester resin and an inorganic filler. Among the above aspects, inorganic filler-based fibrous fillers and plate-shaped fillers are preferred. In the above aspect, it is preferable that the total content of the fibrous filler and the plate-shaped filler is 100 parts by weight relative to 100 parts by weight of the wholly aromatic liquid crystal polyester resin contained in the wholly aromatic liquid crystal polyester resin composition the following. The molded article of the present invention is characterized by containing the above-mentioned wholly aromatic liquid crystal polyester resin composition. The electronic component of the present invention is characterized by comprising the above-mentioned wholly aromatic liquid crystal polyester resin composition. [Effects of the Invention] According to the present invention, due to its high mechanical strength, filling properties, and blistering resistance, it is possible to manufacture molded products with very thin thick-walled parts, and it is possible to achieve high integration and thinness of electronic parts. Wall, low profile. Furthermore, according to the present invention, the occurrence of warpage can be prevented.

(全芳香族液晶聚酯樹脂) 本發明之全芳香族液晶聚酯樹脂係包含下述式(I)～(V)所表示之結構單元(I)～(V)而成，芳香族液晶聚酯中之結構單元(I)～(V)之組成比(莫耳%)滿足下述條件。根據此種全芳香族液晶聚酯樹脂，能夠對使用該樹脂而製作之成形品賦予較高之機械強度、填充性及耐起泡性以及低翹曲性。 [化11]

Figure 02_image023
[化12]
Figure 02_image025
[化13]
Figure 02_image027
[化14]
Figure 02_image029
[化15]
Figure 02_image031
15莫耳%≦結構單元(I)≦35莫耳% 5莫耳%≦結構單元(II)≦15莫耳% 21莫耳%≦結構單元(III)≦29莫耳% 1莫耳%≦結構單元(IV)≦9莫耳% 25莫耳%≦結構單元(V)≦40莫耳% 結構單元(I)＋結構單元(II)＋結構單元(III)＋結構單元(IV)＋結構單元(V)＝100莫耳%。 關於全芳香族液晶聚酯樹脂中之結構單元(III)與結構單元(IV)之調配比(莫耳%)，較佳為結構單元(III)之含量為結構單元(IV)之含量之2倍以上，更佳為4倍以上。藉由將結構單元(III)與結構單元(IV)之調配比(莫耳%)設為上述數值範圍，能夠提高全芳香族液晶聚酯樹脂之熔點。 又，本發明之全芳香族液晶聚酯樹脂之熔點為320℃以上。 由於本發明之全芳香族液晶聚酯樹脂具有較高之熔點，因而能夠滿足作為電子零件所要求之耐熱性。 熔點係依據ISO11357-3、ASTM D3418者，例如能夠藉由使用精工電子工業(股)製造之示差掃描熱量計(DSC)而測定。 再者，以升溫速度20℃/分鐘自室溫升溫至380℃，使全芳香族液晶聚酯樹脂完全熔解後，以速度10℃/分鐘降溫至50℃，進而以20℃/分鐘之速度升溫至420℃，將此時所得之吸熱波峰之頂點設為熔點。 以下，對於全芳香族液晶聚酯樹脂所包含之各結構單元進行說明。 (結構單元(I)) 全芳香族液晶聚酯樹脂係包含上述結構單元(I)而成者，芳香族液晶聚酯中之結構單元(I)之組成比(莫耳%)為15莫耳%～35莫耳%。更佳為20莫耳%～35莫耳%，進而較佳為25莫耳%～35莫耳%。 作為提供結構單元(I)之單體，可列舉對羥基苯甲酸(HBA，下述式(1))、其醯化物、酯衍生物、醯鹵化物等。 [化16]
Figure 02_image033
(結構單元(II)) 全芳香族液晶聚酯樹脂係包含上述結構單元(II)而成者，芳香族液晶聚酯中之結構單元(II)之組成比(莫耳%)為5莫耳%～15莫耳%。更佳為8莫耳%～15莫耳%，進而較佳為8莫耳%～10莫耳%。 作為提供結構單元(II)之單體，可列舉6-羥基-2-萘甲酸(HNA，下述式(2))、其醯化物、酯衍生物、醯鹵化物等。 [化17]
Figure 02_image035
(結構單元(III)) 全芳香族液晶聚酯樹脂係包含上述結構單元(III)而成者，芳香族液晶聚酯中之結構單元(III)之組成比(莫耳%)為21莫耳%～29莫耳%。更佳為21莫耳%～28莫耳%，進而較佳為22莫耳%～26莫耳%。 作為提供結構單元(III)之單體，可列舉對苯二酚(HQ，下述式(3))、其醯化物等。 [化18]
Figure 02_image037
(結構單元(IV)) 全芳香族液晶聚酯樹脂係包含上述結構單元(IV)而成者，芳香族液晶聚酯中之結構單元(IV)之組成比(莫耳%)為1莫耳%～9莫耳%。更佳為1.5莫耳%～9莫耳%，進而較佳為1.5莫耳%～7莫耳%。 作為提供結構單元(IV)之單體，可列舉4,4-二羥基聯苯(BP，下述式(4))、其醯化物等。 [化19]
Figure 02_image039
(結構單元(V)) 全芳香族液晶聚酯樹脂係包含上述結構單元(V)而成者，芳香族液晶聚酯中之結構單元(V)之組成比(莫耳%)為25莫耳%～40莫耳%。更佳為25莫耳%～35莫耳%，進而較佳為27.5莫耳%～32.5莫耳%。 作為提供結構單元(V)之單體，可列舉對苯二甲酸(TPA，下述式(5))、其酯衍生物、醯鹵化物等。 [化20]
Figure 02_image041
(全芳香族液晶聚酯樹脂之製造方法) 本發明之全芳香族液晶聚酯樹脂能夠藉由使上述式(1)～(5)所表示之單體以先前公知之方法聚合而製造。 例如，本發明之全芳香族液晶聚酯樹脂能夠僅藉由熔融聚合而製造。又，亦能夠藉由利用熔融聚合製作預聚物並將其進而進行固相聚合而製造。 關於熔融聚合，自效率良好地獲得本發明之全芳香族聚酯化合物之觀點而言，較佳為將上述式(1)～(5)所表示之單體以特定之組合總計設為100莫耳%，使相對於上述式(1)～(4)所表示之單體所具有之所有羥基為1.05～1.15莫耳當量之乙酸酐存在而於乙酸回流下進行。 於藉由熔融聚合及隨後之固相聚合之二階段而進行聚合反應之情形時，將藉由熔融聚合所得之預聚物冷卻固化後粉碎而使之成為粉末狀或薄片狀，然後較佳為選擇公知之固相聚合方法，例如於氮氣等惰性氣體氛圍下或真空下在200～350℃之溫度範圍內將預聚物樹脂熱處理1～30小時等方法。固相聚合可一面攪拌一面進行，又，亦可不攪拌而於靜置之狀態下進行。 於聚合反應中可使用觸媒，又，亦可不使用。作為使用之觸媒，能夠使用作為聚酯之聚合用觸媒而於先前公知者，可列舉乙酸鎂、乙酸亞錫、鈦酸四丁酯、乙酸鉛、乙酸鈉、乙酸鉀、三氧化二銻等金屬鹽觸媒、N-甲基咪唑等含氮之雜環化合物等、有機化合物觸媒等。觸媒之使用量並無特別限定，相對於單體之總量100重量份，較佳為0.0001～0.1重量份。 熔融聚合中之聚合反應裝置並無特別限定，較佳為使用一般之高黏度流體之反應所使用之反應裝置。作為該等反應裝置之例，例如可列舉具有具備錨型、多段型、螺旋帶型、螺旋軸型等、或將該等變形而成之各種形狀之攪拌葉之攪拌裝置的攪拌槽型聚合反應裝置，或捏合機、輥磨機、班布里混合機等一般用於樹脂之混練之混合裝置等。 (全芳香族液晶聚酯樹脂組合物) 本發明之全芳香族液晶聚酯樹脂組合物係包含上述全芳香族液晶聚酯樹脂及無機填充劑而成。 全芳香族液晶聚酯樹脂組合物中之全芳香族液晶聚酯樹脂之含量較佳為50重量%以上，更佳為60～90重量%。 又，作為全芳香族液晶聚酯樹脂組合物所包含之無機填充劑，例如，能夠使用纖維狀、板狀、粉末狀者，亦可將該等一併使用。其中，較佳為將纖維狀填充劑及板狀填充劑一併使用。 作為無機填充劑，例如可列舉玻璃纖維、磨碎玻璃、矽鋁纖維、氧化鋁纖維、碳纖維、芳香族聚醯胺纖維、鈦酸鉀晶鬚、硼酸鋁晶鬚、矽灰石、滑石、雲母、石墨、碳酸鈣、白雲石、黏土、玻璃薄片、玻璃珠、硫酸鋇及氧化鈦等，全芳香族液晶聚酯樹脂組合物可包含該等之1種或2種以上。 相對於全芳香族液晶聚酯樹脂組合物所包含之全芳香族液晶聚酯樹脂100重量份，全芳香族液晶聚酯樹脂組合物中之無機填充劑之含量較佳為100重量份以下，更佳為10～65重量份。藉由將無機填充劑之含量設為上述數值範圍內，能夠不阻礙成形時之填充性而防止成形品製造時之翹曲之發生。 本發明之全芳香族液晶聚酯樹脂組合物於不損害本發明之效果之範圍內，亦可包含全芳香族液晶聚酯樹脂以外之樹脂。例如可列舉聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚碳酸酯、聚芳酯、聚醯胺、聚醯亞胺、聚醚碸、聚醚醚酮、聚苯硫醚、聚四氟乙烯等，全芳香族液晶聚酯樹脂組合物可包含該等之1種或2種以上。 本發明之全芳香族液晶聚酯樹脂組合物於不損害本發明之效果之範圍內，亦可包含其他添加劑，例如著色劑、分散劑、塑化劑、抗氧化劑、阻燃劑、熱穩定劑、紫外線吸收劑、抗靜電劑、界面活性劑。 (全芳香族液晶聚酯樹脂組合物之製造方法) 全芳香族液晶聚酯樹脂組合物能夠藉由使用班布里混合機、捏合機、單軸或雙軸擠出機等，將向全芳香族液晶聚酯樹脂調配填充劑等而成者熔融混練而獲得。 (成形品) 本發明之成形品係包含全芳香族液晶聚酯樹脂組合物而成者，能夠藉由將該組合物射出成形、擠出成形而獲得。又，能夠藉由相同之方法獲得包含全芳香族液晶聚酯樹脂組合物之膜、片材及不織布。 作為具體之膜化方法，可列舉吹脹成形、熔融擠出成形、溶液澆鑄成形等。如此獲得之膜可為包含全芳香族聚酯樹脂組合物之單層膜，亦可為與異種材料組成之多層膜。 再者，為了改良熔融擠出成形、溶液澆鑄成形而成之膜之尺寸穩定性、機械特性，亦可於單軸或雙軸進行延伸處理。又，亦可為了去除該等膜之各向異性而進行熱處理。 (電子零件) 本發明之電子零件係包含上述全芳香族液晶聚酯樹脂組合物而成。作為電子零件，例如，可列舉高速傳輸用連接器、CPU(central processing unit，中央處理器)插口、電路基板、可撓性電路基板、積層用電路基板、防碰撞用雷達、RFID(radio frequency identification，射頻識別)標籤、電容器、換流器零件、絕緣膜、鋰離子電池等二次電池之絕緣材料、揚聲器振動板等。具體而言，該等電子零件係具備包含全芳香族液晶聚酯樹脂組合物之成形品(例如，射出成形品)或膜等而成。 實施例 以下，藉由實施例更具體地說明本發明，但本發明不限定於實施例。 ＜全芳香族液晶聚酯樹脂之製造＞ (實施例1：全芳香族液晶聚酯樹脂A) 向具有攪拌葉之聚合容器加入對羥基苯甲酸(HBA)24.9 g(30莫耳%)、6-羥基-2-萘甲酸(HNA)11.3 g(10莫耳%)、對苯二酚(HQ)15.9 g(24莫耳%)、4,4-二羥基聯苯(BP)6.7 g(6莫耳%)、對苯二甲酸(TPA)29.9(30莫耳%)，並添加乙酸鉀及乙酸鎂作為觸媒，將聚合容器之減壓-氮氣注入進行3次而進行氮氣置換後，進而添加乙酸酐66.2 g(相對於羥基為1.08莫耳當量)，升溫至150℃，並於回流狀態下進行2小時乙醯化反應。 乙醯化結束後，將蒸餾掉乙酸之狀態之聚合容器以0.5℃/分鐘升溫，於槽內之熔融體溫度變成310℃時抽出聚合物，並冷卻固化。將所得之聚合物粉碎，粉碎至通過網眼為1.0 mm之篩之大小而獲得預聚物。 接著，將上述中所得之預聚物填充至柴田科學製造之玻璃管烘箱，一面旋轉一面花12小時將加熱器溫度自室溫升溫至290℃後，於290℃下保持溫度1小時而進行固相聚合。之後一面旋轉槽一面於室溫下自然散熱，獲得全芳香族液晶聚酯樹脂A。使用具備Mettler製造之顯微鏡用高溫載台FP82HT之Olympus(股)製造之偏光顯微鏡BH-2，使聚酯試樣於顯微鏡加熱載台上加熱熔融，根據光學各向異性之有無確認液晶性。 (實施例2：全芳香族液晶聚酯樹脂B) 除將單體添加變更為HBA 30莫耳%、HNA 15莫耳%、HQ 26莫耳%、BP 1.5莫耳%、TPA 27.5莫耳%以外，以與實施例1相同之方式獲得液晶聚酯樹脂B，並以與上述相同之方式確認液晶性。 (實施例3：全芳香族液晶聚酯樹脂C) 除將單體添加變更為HBA 30莫耳%、HNA 10莫耳%、HQ 21莫耳%、BP 9莫耳%、TPA 30莫耳%以外，以與實施例1相同之方式獲得液晶聚酯樹脂C，並以與上述相同之方式確認液晶性。 (實施例4：全芳香族液晶聚酯樹脂D) 除將單體添加變更為HBA 30莫耳%、HNA 10莫耳%、HQ 25莫耳%、BP 5 莫耳%、TPA 30莫耳%以外，以與實施例1相同之方式獲得液晶聚酯樹脂D，並以與上述相同之方式確認液晶性。 (比較例1：全芳香族液晶聚酯樹脂E) 除將單體添加變更為HBA 20莫耳%、HNA 20莫耳%、HQ 10莫耳%、BP 20莫耳%、TPA 30莫耳%以外，以與實施例1相同之方式，於乙醯化結束後獲得成為蒸餾掉乙酸之狀態之預聚物。 接著，將上述中所得之預聚物填充至柴田科學製造之玻璃管烘箱，欲藉由固相聚合而聚合至所需之分子量，結果，預聚物熔融，無法進一步實施固相聚合。之後，一面旋轉槽一面於室溫下自然散熱，獲得液晶聚酯樹脂E。 (比較例2：全芳香族液晶聚酯樹脂F) 除將單體添加變更為HBA 30莫耳%、HNA 10莫耳%、HQ 16莫耳%、BP 14莫耳%、TPA 30莫耳%以外，以與實施例1相同之方式，於乙醯化結束後獲得成為蒸餾掉乙酸之狀態之預聚物。 接著，將上述中所得之預聚物填充至柴田科學製造之玻璃管烘箱，欲藉由固相聚合而聚合至所需之分子量，結果，預聚物熔融，無法進一步實施固相聚合。之後，一面旋轉槽一面於室溫下自然散熱，獲得液晶聚酯樹脂F。 (比較例3：全芳香族液晶聚酯樹脂G) 除將單體添加變更為HBA 6莫耳%、HNA 10莫耳%、BP 42莫耳%、TPA 42莫耳%以外，以與實施例1相同之方式進行乙醯化反應。乙醯化結束後，將成為蒸餾掉乙酸之狀態之聚合容器以0.5℃/分鐘升溫至310℃，結果聚合物易固化，無法自聚合容器抽出。 (比較例4：全芳香族液晶聚酯樹脂H) 除將單體添加變更為HBA 60莫耳%、BP 20莫耳%、TPA 15莫耳%、間苯二甲酸5莫耳%以外，以與實施例1相同之方式獲得液晶聚酯樹脂H，並以與上述相同之方式確認液晶性。 ＜＜抽出性＞＞ 聚合容器之溫度達到特定之溫度後，觀察自聚合容器抽出聚合物時之行為，根據以下之評價基準評價抽出性。 (評價基準) ○：能夠容易地抽出。 ×：難以抽出，於容器內殘留樹脂。 ＜＜熔點之測定＞＞ 實施例及比較例中所得之液晶聚酯樹脂之熔點係藉由精工電子工業(股)製造之示差掃描熱量計(DSC)而測定。此時，以升溫速度20℃/分鐘自室溫升溫至380℃而使聚合物完全熔解後，以速度10℃/分鐘降溫至50℃，進而以20℃/分鐘之速度升溫至420℃，將此時所得之吸熱波峰之頂點設為熔點。將測定結果彙總於表1。 [表1]
Figure 106103627-A0304-0001
 ＜全芳香族液晶聚酯樹脂組合物之製造＞ 以成為與實施例1相同之單體組成之方式將對羥基苯甲酸663.0 g(30莫耳%)、6-羥基-2-萘甲酸301.1 g(10莫耳%)、對苯二酚422.8 g(24莫耳%)、4,4-二羥基聯苯178.8 g(6莫耳%)、對苯二甲酸797.4(30莫耳%)、作為觸媒之乙酸鉀0.30 g及乙酸鎂0.30 g添加至材質為SUS316且具有雙螺旋攪拌葉之內容積為6 L之聚合槽，於與實施例1相同之條件下獲得預聚物。 接著，將上述中所得之預聚物填充至固相聚合裝置，一面通入氮氣，一面於旋轉速度5 rpm下花1小時將加熱器溫度自室溫升溫至150℃後，花10小時升溫至250℃，並於250℃下保持2小時。 進而花6小時升溫至270℃，進而花6小時升溫至290℃，於290℃下保持2小時。進而花6小時升溫至310℃，於310℃下保持1小時，進行固相聚合。如此，獲得全芳香族液晶聚酯樹脂A。 相對於以上述方式獲得之全芳香族液晶聚酯樹脂A 100重量份，調配纖維狀填充劑(Central Glass Fiber(股)製造，商品名：EFH150-01)7重量份、板狀填充劑(雲母，(股)YAMAGUCHI MICA製造，商品名：AB-25S)36重量份、碳黑(Cabot(股)公司製造，商品名：REGAL99I)1重量份，並於雙軸擠出機熔融混練，將所得者顆粒化，獲得全芳香族液晶聚酯樹脂組合物A。 又，除將全芳香族液晶聚酯樹脂A變更為藉由比較例4而獲得之全芳香族液晶聚酯樹脂H以外，以相同方式獲得全芳香族液晶聚酯樹脂組合物H。 ＜＜填充性試驗(流動長之測定)＞＞ 使用射出成形機(Sodick製造，商品名：LD10EH2)，將料缸溫度設定為測定表觀熔融黏度(升溫)時熔融黏度之值開始穩定之溫度(360℃)，將模具溫度設為80℃，以射出速度133 mm/sec將所得之全芳香族液晶聚酯樹脂組合物A之顆粒向模具內射出。 填充性試驗中所使用之模具係如圖1所示者，使用具有寬度為2.0 mm、長度為40 mm、厚度為0.1 mm之薄壁部之模具，藉由射出之樹脂組合物流入至薄壁部而形成之薄壁部之長度評價樹脂組合物之填充性。 將該試驗反覆進行20次，將形成之薄壁部之長度之平均記載於表2。 對於全芳香族液晶聚酯樹脂組合物H亦進行相同之試驗，並將其結果記載於表2。 ＜＜機械強度試驗(彎曲強度之測定)＞＞ 使用射出成形機(住友重機械工業(股)製造，商品名：SG-25)，於上述料缸溫度下，將模具溫度設為80℃，以射出速度100 mm/sec將以上述方式獲得之樹脂組合物A之顆粒射出成形，製作依據ASTM D790之彎曲試片(寬度13 mm、長度130 mm、厚度3 mm)並測定彎曲強度。 又，使用樹脂組合物H同樣地製作試片並測定彎曲強度。將測定結果彙總於表2。 ＜＜耐起泡性試驗(耐起泡溫度之測定)＞＞ (試片之成形) 利用射出成形機(Sodick製造，商品名：LD10EH2)，於上述料缸溫度下，將模具溫度設為80℃，以射出速度150 mm/sec將以上述方式獲得之樹脂組合物A之顆粒射出成形，製作依據JIS K7160 2形之試片(寬度10 mm、長度60 mm、厚度0.4 mm)。 又，使用樹脂組合物H，同樣地製作試片。將以上述方式所獲得之試片於保持為特定之溫度之空氣烘箱中放置30分鐘，將於試片表面不發生起泡及變形之最高溫度設為耐起泡溫度。將測定結果彙總於表2。 ＜＜箱翹曲量之測定＞＞ 利用射出成形機(Sodick製造，商品名：LD10EH2)，將料缸溫度設為熔點＋10℃，將模具溫度設為100℃，以射出速度133 mm/sec將以上述方式所獲得之樹脂組合物A之顆粒射出成形，獲得圖2(a)及(b)所表示之箱型成形品。 將以上述方式所獲得之成形品於保持為260℃之空氣烘箱中放置10分鐘，使用一鍵3D顯微鏡((股)基恩士公司製造，商品名：VR-3100)測定加熱後之成形品之底面之翹曲(翹曲量)。將測定結果彙總於表2。再者，形狀穩定性越良好，翹曲量越小。 [表2]
Figure 106103627-A0304-0002
 (Wholly aromatic liquid crystal polyester resin) The wholly aromatic liquid crystal polyester resin of the present invention is composed of structural units (I) to (V) represented by the following formulas (I) to (V). The composition ratio (mol %) of the structural units (I) to (V) in the ester satisfies the following conditions. According to such a wholly aromatic liquid crystal polyester resin, it is possible to impart high mechanical strength, filling properties, blistering resistance, and low warpage to molded articles produced using the resin. [化11]
Figure 02_image023
[化12]
Figure 02_image025
[化13]
Figure 02_image027
[化14]
Figure 02_image029
[化15]
Figure 02_image031
15mol%≦structural unit (I)≦35mol% 5mol%≦structural unit (II)≦15mol% 21mol%≦structural unit (III)≦29mol% 1mol%≦ Structural unit (IV)≦9 mol% 25 mol%≦structural unit (V)≦40 mol% Structural unit (I) + structural unit (II) + structural unit (III) + structural unit (IV) + structure Unit (V) = 100 mol%. Regarding the blending ratio (mol%) of the structural unit (III) and the structural unit (IV) in the wholly aromatic liquid crystal polyester resin, the content of the structural unit (III) is preferably 2 of the content of the structural unit (IV) Times or more, more preferably 4 times or more. By setting the blending ratio (mol %) of the structural unit (III) and the structural unit (IV) to the above numerical range, the melting point of the wholly aromatic liquid crystal polyester resin can be increased. In addition, the melting point of the wholly aromatic liquid crystal polyester resin of the present invention is 320°C or higher. Since the wholly aromatic liquid crystal polyester resin of the present invention has a relatively high melting point, it can satisfy the heat resistance required as an electronic component. The melting point is based on ISO11357-3 and ASTM D3418, and can be measured by using a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc., for example. In addition, the temperature is increased from room temperature to 380°C at a heating rate of 20°C/min to completely melt the wholly aromatic liquid crystal polyester resin, and then the temperature is lowered to 50°C at a rate of 10°C/min, and then the temperature is increased at a rate of 20°C/min. At 420°C, the apex of the endothermic peak obtained at this time is set as the melting point. Hereinafter, each structural unit contained in the wholly aromatic liquid crystal polyester resin will be described. (Structural unit (I)) The wholly aromatic liquid crystal polyester resin contains the above-mentioned structural unit (I), and the composition ratio (mole%) of the structural unit (I) in the aromatic liquid crystal polyester is 15 mol %～35mol%. More preferably, it is 20 mol% to 35 mol%, and still more preferably 25 mol% to 35 mol%. Examples of monomers that provide the structural unit (I) include p-hydroxybenzoic acid (HBA, the following formula (1)), its acyl compounds, ester derivatives, and acyl halides. [化16]
Figure 02_image033
(Structural unit (II)) The wholly aromatic liquid crystal polyester resin is composed of the above-mentioned structural unit (II), and the composition ratio (mole%) of the structural unit (II) in the aromatic liquid crystal polyester is 5 mol %～15mol%. It is more preferably 8 mol% to 15 mol%, and still more preferably 8 mol% to 10 mol%. Examples of monomers that provide the structural unit (II) include 6-hydroxy-2-naphthoic acid (HNA, the following formula (2)), its acyl compounds, ester derivatives, and acyl halides. [化17]
Figure 02_image035
(Structural unit (III)) The wholly aromatic liquid crystal polyester resin contains the above-mentioned structural unit (III), and the composition ratio (mole%) of the structural unit (III) in the aromatic liquid crystal polyester is 21 mol %～29mol%. It is more preferably 21 mol% to 28 mol%, and still more preferably 22 mol% to 26 mol%. As a monomer providing the structural unit (III), hydroquinone (HQ, the following formula (3)), its acyl products, and the like can be cited. [化18]
Figure 02_image037
(Structural unit (IV)) The wholly aromatic liquid crystal polyester resin contains the above-mentioned structural unit (IV), and the composition ratio (mol%) of the structural unit (IV) in the aromatic liquid crystal polyester is 1 mol %～9mol%. It is more preferably 1.5 mol% to 9 mol%, and still more preferably 1.5 mol% to 7 mol%. As a monomer which provides the structural unit (IV), 4,4-dihydroxybiphenyl (BP, the following formula (4)), its acetone, and the like can be cited. [化19]
Figure 02_image039
(Structural unit (V)) The wholly aromatic liquid crystal polyester resin contains the above-mentioned structural unit (V), and the composition ratio (mole%) of the structural unit (V) in the aromatic liquid crystal polyester is 25 mol %～40mol%. More preferably, it is 25 mol% to 35 mol%, and still more preferably 27.5 mol% to 32.5 mol%. As a monomer which provides a structural unit (V), terephthalic acid (TPA, the following formula (5)), its ester derivative, an acyl halide, etc. are mentioned. [化20]
Figure 02_image041
(Method for producing wholly aromatic liquid crystal polyester resin) The wholly aromatic liquid crystal polyester resin of the present invention can be produced by polymerizing the monomers represented by the above formulas (1) to (5) by a previously known method. For example, the wholly aromatic liquid crystal polyester resin of the present invention can be manufactured only by melt polymerization. In addition, it can also be produced by producing a prepolymer by melt polymerization and then subjecting it to solid phase polymerization. Regarding melt polymerization, from the viewpoint of efficiently obtaining the wholly aromatic polyester compound of the present invention, it is preferable to set the monomers represented by the above formulas (1) to (5) in a specific combination to a total of 100 moles. Ear%, acetic anhydride having 1.05 to 1.15 molar equivalents relative to all hydroxyl groups of the monomers represented by the above formulas (1) to (4) is carried out under reflux of acetic acid. When the polymerization reaction is carried out by the two stages of melt polymerization and subsequent solid phase polymerization, the prepolymer obtained by the melt polymerization is cooled and solidified and then pulverized to make it into a powder or flake form, and then it is preferably A well-known solid-phase polymerization method is selected, for example, a method of heat-treating the prepolymer resin within a temperature range of 200-350°C for 1-30 hours under an inert gas atmosphere such as nitrogen or vacuum. The solid-phase polymerization can be carried out while stirring, or it can be carried out in a static state without stirring. In the polymerization reaction, a catalyst can be used or not. As the catalyst used, it is possible to use those previously known as catalysts for the polymerization of polyester, such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide. And other metal salt catalysts, nitrogen-containing heterocyclic compounds such as N-methylimidazole, etc., organic compound catalysts, etc. The amount of the catalyst used is not particularly limited, but it is preferably 0.0001 to 0.1 parts by weight relative to 100 parts by weight of the total amount of monomers. The polymerization reaction device in the melt polymerization is not particularly limited, and it is preferably a reaction device used for reaction using a general high-viscosity fluid. Examples of these reaction devices include, for example, a stirring tank type polymerization reaction device having a stirring device equipped with an anchor type, a multi-stage type, a spiral ribbon type, a spiral shaft type, etc., or various shapes of stirring blades deformed from the same. Equipment, or kneaders, roller mills, Bamburi mixers and other mixing equipment generally used for mixing resin. (Wholly Aromatic Liquid Crystal Polyester Resin Composition) The wholly aromatic liquid crystal polyester resin composition of the present invention contains the above-mentioned wholly aromatic liquid crystal polyester resin and an inorganic filler. The content of the wholly aromatic liquid crystal polyester resin in the wholly aromatic liquid crystal polyester resin composition is preferably 50% by weight or more, more preferably 60 to 90% by weight. In addition, as the inorganic filler contained in the wholly aromatic liquid crystal polyester resin composition, for example, those in the form of fibers, plates, and powders can be used, or they can be used together. Among them, it is preferable to use a fibrous filler and a plate-shaped filler together. Examples of inorganic fillers include glass fiber, ground glass, silica alumina fiber, alumina fiber, carbon fiber, aromatic polyamide fiber, potassium titanate whisker, aluminum borate whisker, wollastonite, talc, and mica. , Graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate and titanium oxide, etc. The wholly aromatic liquid crystal polyester resin composition may contain one or more of these. Relative to 100 parts by weight of the wholly aromatic liquid crystal polyester resin contained in the wholly aromatic liquid crystal polyester resin composition, the content of the inorganic filler in the wholly aromatic liquid crystal polyester resin composition is preferably 100 parts by weight or less, and more It is preferably 10 to 65 parts by weight. By setting the content of the inorganic filler within the above-mentioned numerical range, it is possible to prevent the occurrence of warpage during the manufacture of a molded product without hindering the filling property during molding. The wholly aromatic liquid crystal polyester resin composition of the present invention may contain resins other than the wholly aromatic liquid crystal polyester resin within a range that does not impair the effects of the present invention. For example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyamide, polyimide, polyether sulfide, polyether ether ketone, polyphenylene sulfide can be cited. , Polytetrafluoroethylene, etc., the wholly aromatic liquid crystal polyester resin composition may contain one or more of these. The wholly aromatic liquid crystal polyester resin composition of the present invention may also contain other additives, such as coloring agents, dispersants, plasticizers, antioxidants, flame retardants, and heat stabilizers, within the range that does not impair the effects of the present invention. , UV absorbers, antistatic agents, surfactants. (Method for manufacturing wholly aromatic liquid crystal polyester resin composition) The wholly aromatic liquid crystal polyester resin composition can be transformed into a wholly aromatic liquid crystal polyester resin composition by using a Bamburi mixer, kneader, uniaxial or biaxial extruder, etc. The liquid crystal polyester resin is obtained by blending fillers and the like by melting and kneading. (Molded product) The molded product of the present invention contains a wholly aromatic liquid crystal polyester resin composition, and can be obtained by injection molding and extrusion molding of the composition. In addition, the film, sheet, and non-woven fabric containing the wholly aromatic liquid crystal polyester resin composition can be obtained by the same method. Specific film forming methods include inflation molding, melt extrusion molding, solution casting molding, and the like. The film thus obtained may be a single-layer film containing a wholly aromatic polyester resin composition, or a multi-layer film composed of dissimilar materials. Furthermore, in order to improve the dimensional stability and mechanical properties of the film formed by melt extrusion molding and solution casting, it is also possible to perform stretching treatment on a uniaxial or biaxial extension. In addition, heat treatment may be performed in order to remove the anisotropy of these films. (Electronic component) The electronic component of the present invention contains the above-mentioned wholly aromatic liquid crystal polyester resin composition. Examples of electronic components include connectors for high-speed transmission, CPU (central processing unit, central processing unit) sockets, circuit boards, flexible circuit boards, multilayer circuit boards, anti-collision radar, and RFID (radio frequency identification). , Radio frequency identification) tags, capacitors, inverter parts, insulating films, lithium-ion batteries and other secondary battery insulation materials, speaker diaphragms, etc. Specifically, these electronic components are formed with molded products (for example, injection molded products) or films containing a wholly aromatic liquid crystal polyester resin composition. EXAMPLES Hereinafter, the present invention will be explained more specifically with examples, but the present invention is not limited to the examples. <Production of fully aromatic liquid crystal polyester resin> (Example 1: Fully aromatic liquid crystal polyester resin A) Add 24.9 g (30 mol%) of p-hydroxybenzoic acid (HBA) to a polymerization vessel with a stirring blade, 6 -Hydroxy-2-naphthoic acid (HNA) 11.3 g (10 mol%), hydroquinone (HQ) 15.9 g (24 mol%), 4,4-dihydroxybiphenyl (BP) 6.7 g (6 Mol%), terephthalic acid (TPA) 29.9 (30 mol%), potassium acetate and magnesium acetate were added as catalysts, the polymerization vessel was depressurized-nitrogen injection was performed 3 times, and nitrogen was replaced, and then 66.2 g of acetic anhydride (1.08 molar equivalent to the hydroxyl group) was added, the temperature was raised to 150°C, and the acetylation reaction was performed under reflux for 2 hours. After the acetylation is completed, the polymerization vessel in the state where the acetic acid has been distilled is heated up at 0.5°C/min. When the temperature of the melt in the tank becomes 310°C, the polymer is drawn out and cooled and solidified. The obtained polymer is pulverized and pulverized to a size that passes through a sieve with a mesh size of 1.0 mm to obtain a prepolymer. Next, the prepolymer obtained above was filled into a glass tube oven manufactured by Shibata Scientific, and the heater temperature was increased from room temperature to 290°C for 12 hours while rotating, and then the temperature was maintained at 290°C for 1 hour to perform solid phase. polymerization. After that, while rotating the tank, the heat is naturally dissipated at room temperature to obtain a wholly aromatic liquid crystal polyester resin A. Using a polarizing microscope BH-2 manufactured by Olympus (stock) equipped with a high-temperature microscope stage FP82HT manufactured by Mettler, the polyester sample was heated and melted on the microscope heating stage, and the liquid crystallinity was confirmed based on the presence or absence of optical anisotropy. (Example 2: Fully Aromatic Liquid Crystal Polyester Resin B) Except that the monomer addition was changed to HBA 30 mol%, HNA 15 mol%, HQ 26 mol%, BP 1.5 mol%, and TPA 27.5 mol% Otherwise, the liquid crystal polyester resin B was obtained in the same manner as in Example 1, and the liquid crystallinity was confirmed in the same manner as described above. (Example 3: Fully Aromatic Liquid Crystal Polyester Resin C) Except that the monomer addition was changed to HBA 30 mol%, HNA 10 mol%, HQ 21 mol%, BP 9 mol%, and TPA 30 mol% Other than that, the liquid crystal polyester resin C was obtained in the same manner as in Example 1, and the liquid crystallinity was confirmed in the same manner as described above. (Example 4: Fully Aromatic Liquid Crystal Polyester Resin D) Except that the monomer addition was changed to HBA 30 mol%, HNA 10 mol%, HQ 25 mol%, BP 5 mol%, and TPA 30 mol% Except this, a liquid crystal polyester resin D was obtained in the same manner as in Example 1, and the liquid crystallinity was confirmed in the same manner as described above. (Comparative Example 1: Fully Aromatic Liquid Crystal Polyester Resin E) Except that the monomer addition was changed to HBA 20 mol%, HNA 20 mol%, HQ 10 mol%, BP 20 mol%, and TPA 30 mol% Otherwise, in the same manner as in Example 1, a prepolymer in a state where acetic acid was distilled off was obtained after the acetylation was completed. Next, the prepolymer obtained in the above was filled into a glass tube oven manufactured by Shibata Scientific, and it was attempted to polymerize to a desired molecular weight by solid phase polymerization. As a result, the prepolymer melted and solid phase polymerization could not be further performed. Afterwards, while rotating the tank, the heat is naturally dissipated at room temperature to obtain the liquid crystal polyester resin E. (Comparative Example 2: Fully Aromatic Liquid Crystal Polyester Resin F) Except that the monomer addition was changed to HBA 30 mol%, HNA 10 mol%, HQ 16 mol%, BP 14 mol%, and TPA 30 mol% Otherwise, in the same manner as in Example 1, a prepolymer in a state where acetic acid was distilled off was obtained after the acetylation was completed. Next, the prepolymer obtained in the above was filled into a glass tube oven manufactured by Shibata Scientific, and it was attempted to polymerize to a desired molecular weight by solid phase polymerization. As a result, the prepolymer melted and solid phase polymerization could not be further performed. After that, while rotating the tank, the heat is naturally dissipated at room temperature to obtain a liquid crystal polyester resin F. (Comparative Example 3: Wholly Aromatic Liquid Crystal Polyester Resin G) Except that the monomer addition was changed to HBA 6 mol%, HNA 10 mol%, BP 42 mol%, and TPA 42 mol%, the same as the examples 1 Carry out the acetylation reaction in the same way. After the completion of acetylation, the polymerization vessel in a state where the acetic acid was distilled off was heated to 310°C at a rate of 0.5°C/min. As a result, the polymer was easily solidified and could not be drawn out from the polymerization vessel. (Comparative Example 4: Fully Aromatic Liquid Crystal Polyester Resin H) Except that the monomer addition was changed to HBA 60 mol%, BP 20 mol%, TPA 15 mol%, and isophthalic acid 5 mol%, The liquid crystal polyester resin H was obtained in the same manner as in Example 1, and the liquid crystallinity was confirmed in the same manner as described above. <<Extractability>> After the temperature of the polymerization vessel reaches a specific temperature, observe the behavior when the polymer is extracted from the polymerization vessel, and evaluate the extractability according to the following evaluation criteria. (Evaluation Criteria) ○: Can be extracted easily. ×: It is difficult to extract, and resin remains in the container. <<Melting point measurement>> The melting point of the liquid crystal polyester resin obtained in the examples and comparative examples was measured by a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc. At this time, after the polymer is completely melted from room temperature to 380°C at a heating rate of 20°C/min, the temperature is lowered to 50°C at a rate of 10°C/min, and then the temperature is increased to 420°C at a rate of 20°C/min. The apex of the endothermic peak obtained at this time is the melting point. The measurement results are summarized in Table 1. [Table 1]
Figure 106103627-A0304-0001
 <Production of a wholly aromatic liquid crystal polyester resin composition> 663.0 g (30 mol%) of p-hydroxybenzoic acid and 301.1 g of 6-hydroxy-2-naphthoic acid were prepared to have the same monomer composition as in Example 1. (10 mol%), hydroquinone 422.8 g (24 mol%), 4,4-dihydroxybiphenyl 178.8 g (6 mol%), terephthalic acid 797.4 (30 mol%), as 0.30 g of potassium acetate and 0.30 g of magnesium acetate as the catalyst were added to a polymerization tank made of SUS316 and having a double-spiral stirring blade with an inner volume of 6 L. The prepolymer was obtained under the same conditions as in Example 1. Next, the prepolymer obtained in the above was filled into the solid-phase polymerization device, while nitrogen was introduced, the heater temperature was raised from room temperature to 150°C for 1 hour at a rotation speed of 5 rpm, and then the temperature was raised to 250°C for 10 hours. ℃, and keep at 250 ℃ for 2 hours. The temperature was further increased to 270°C in 6 hours, and the temperature was increased to 290°C in 6 hours, and the temperature was maintained at 290°C for 2 hours. Furthermore, it heated up to 310 degreeC over 6 hours, and kept at 310 degreeC for 1 hour, and performed solid-phase polymerization. In this way, a wholly aromatic liquid crystal polyester resin A is obtained. With respect to 100 parts by weight of the fully aromatic liquid crystal polyester resin A obtained in the above manner, 7 parts by weight of fibrous filler (manufactured by Central Glass Fiber (stock), trade name: EFH150-01) and platy filler (mica , (Stock) manufactured by YAMAGUCHI MICA, trade name: AB-25S) 36 parts by weight, carbon black (manufactured by Cabot (stock) company, trade name: REGAL99I) 1 part by weight, and melted and kneaded in a twin-screw extruder to obtain The particles were granulated to obtain a wholly aromatic liquid crystal polyester resin composition A. In addition, except that the wholly aromatic liquid crystal polyester resin A was changed to the wholly aromatic liquid crystal polyester resin H obtained in Comparative Example 4, a wholly aromatic liquid crystal polyester resin composition H was obtained in the same manner. ＜＜Fillability test (measurement of flow length)＞＞ Using an injection molding machine (manufactured by Sodick, trade name: LD10EH2), set the cylinder temperature to the temperature at which the value of the melt viscosity begins to stabilize when the apparent melt viscosity (heating) is measured (360°C), set the mold temperature to 80°C, and inject the obtained particles of the wholly aromatic liquid crystal polyester resin composition A into the mold at an injection speed of 133 mm/sec. The mold used in the fillability test is shown in Figure 1. A mold with a thin wall with a width of 2.0 mm, a length of 40 mm, and a thickness of 0.1 mm is used. The injected resin composition flows into the thin wall The length of the thin-walled portion formed by the portion evaluates the fillability of the resin composition. This test was repeated 20 times, and the average length of the thin-walled portion formed was described in Table 2. The same test was also performed on the wholly aromatic liquid crystal polyester resin composition H, and the results are shown in Table 2. ＜＜Mechanical strength test (measurement of bending strength)＞＞ Using an injection molding machine (manufactured by Sumitomo Heavy Industries Co., Ltd., trade name: SG-25), set the mold temperature to 80°C at the above cylinder temperature, The pellets of the resin composition A obtained in the above manner were injection molded at an injection speed of 100 mm/sec, and a bending test piece (width 13 mm, length 130 mm, thickness 3 mm) according to ASTM D790 was produced and the bending strength was measured. In addition, using the resin composition H, a test piece was produced in the same manner, and the bending strength was measured. The measurement results are summarized in Table 2. ＜＜Bubbling resistance test (measurement of foaming resistance temperature)＞＞ (Forming of test piece) Using an injection molding machine (manufactured by Sodick, trade name: LD10EH2), set the mold temperature to 80 at the above cylinder temperature The pellets of the resin composition A obtained in the above manner were injection molded at a temperature of ℃ and an injection speed of 150 mm/sec to produce a test piece (width 10 mm, length 60 mm, thickness 0.4 mm) in accordance with JIS K7160. In addition, using the resin composition H, a test piece was produced in the same manner. The test piece obtained in the above manner is placed in an air oven maintained at a specific temperature for 30 minutes, and the highest temperature at which blistering and deformation of the surface of the test piece does not occur is set as the anti-foaming temperature. The measurement results are summarized in Table 2. ＜＜Measurement of box warpage＞＞ Using an injection molding machine (manufactured by Sodick, trade name: LD10EH2), set the cylinder temperature to the melting point + 10°C, the mold temperature to 100°C, and the injection speed 133 mm/sec. The resin composition A obtained in the above manner was pelletized by injection molding to obtain a box-shaped molded product as shown in Figs. 2(a) and (b). The molded product obtained in the above manner was placed in an air oven maintained at 260°C for 10 minutes, and the heated molded product was measured using a one-key 3D microscope (manufactured by Keyence Corporation, trade name: VR-3100) The warpage of the bottom surface (the amount of warpage). The measurement results are summarized in Table 2. Furthermore, the better the shape stability, the smaller the amount of warpage. [Table 2]
Figure 106103627-A0304-0002

圖1係於實施例之填充性試驗中所使用之模具之俯視圖及側視圖。 圖2(a)係於實施例之箱翹曲之測定中所製作之箱形成形品之仰視圖。 圖2(b)係於實施例之箱翹曲之測定中所製作之箱形成形品之前視圖。Fig. 1 is a top view and a side view of a mold used in the filling test of the embodiment. Fig. 2(a) is a bottom view of the box-shaped product produced in the measurement of the box warpage of the embodiment. Fig. 2(b) is a front view of the box-shaped product produced in the measurement of the box warpage of the embodiment.

Claims (9)

一種全芳香族液晶聚酯樹脂，其特徵在於：其係包含下述式(I)~(V)所表示之結構單元(I)~(V)而成者，
Figure 106103627-A0305-02-0022-1
Figure 106103627-A0305-02-0022-2
Figure 106103627-A0305-02-0022-3
Figure 106103627-A0305-02-0022-4
Figure 106103627-A0305-02-0023-5
 上述芳香族液晶聚酯中之結構單元(I)~(V)之組成比(莫耳%)滿足下述條件：15莫耳%≦結構單元(I)≦35莫耳% 5莫耳%≦結構單元(II)≦15莫耳% 21莫耳%≦結構單元(III)≦29莫耳% 1莫耳%≦結構單元(IV)≦9莫耳% 25莫耳%≦結構單元(V)≦40莫耳%結構單元(I)+結構單元(II)+結構單元(III)+結構單元(IV)+結構單元(V)=100莫耳%，且上述全芳香族液晶聚酯樹脂之熔點為320℃以上。 A wholly aromatic liquid crystal polyester resin characterized in that it contains structural units (I) to (V) represented by the following formulas (I) to (V),
Figure 106103627-A0305-02-0022-1
Figure 106103627-A0305-02-0022-2
Figure 106103627-A0305-02-0022-3
Figure 106103627-A0305-02-0022-4
Figure 106103627-A0305-02-0023-5
 The composition ratio (mol%) of the structural units (I) to (V) in the above aromatic liquid crystal polyester satisfies the following conditions: 15 mol%≦structural unit (I)≦35 mol% 5 mol%≦ Structural unit (II) ≦ 15 mol% 21 mol% ≦ structural unit (III) ≦ 29 mol% 1 mol% ≦ structural unit (IV) ≦ 9 mol% 25 mol% ≦ structural unit (V) ≦40 mol% structural unit (I) + structural unit (II) + structural unit (III) + structural unit (IV) + structural unit (V) = 100 mol%, and the above fully aromatic liquid crystal polyester resin The melting point is above 320°C. 如請求項1之全芳香族液晶聚酯樹脂，其中結構單元(III)之含量為結構單元(IV)之含量之2倍以上。 Such as the wholly aromatic liquid crystal polyester resin of claim 1, wherein the content of the structural unit (III) is more than twice the content of the structural unit (IV). 一種如請求項1或2之全芳香族液晶聚酯樹脂之製造方法，其包括使下述式(1)~(5)所表示之單體聚合之步驟：[化6]
Figure 106103627-A0305-02-0024-6
Figure 106103627-A0305-02-0024-7
Figure 106103627-A0305-02-0024-8
Figure 106103627-A0305-02-0024-9
Figure 106103627-A0305-02-0024-10
 A method for producing a wholly aromatic liquid crystal polyester resin as claimed in claim 1 or 2, which comprises the steps of polymerizing monomers represented by the following formulas (1) to (5): [form 6]
Figure 106103627-A0305-02-0024-6
Figure 106103627-A0305-02-0024-7
Figure 106103627-A0305-02-0024-8
Figure 106103627-A0305-02-0024-9
Figure 106103627-A0305-02-0024-10
 如請求項3之方法，其中上述單體之聚合步驟包括：於相對於上述式(1)~(4)所表示之單體所具有之所有羥基為1.05~1.15莫耳當量之乙酸酐 之存在下，使上述式(1)~(5)所表示之單體熔融聚合。 The method of claim 3, wherein the polymerization step of the above-mentioned monomer includes: acetic anhydride of 1.05 to 1.15 molar equivalents relative to all hydroxyl groups of the monomers represented by the above-mentioned formulas (1) to (4) In the presence of, the monomers represented by the above formulas (1) to (5) are melt-polymerized. 一種全芳香族液晶聚酯樹脂組合物，其係包含如請求項1或2之全芳香族液晶聚酯樹脂及無機填充劑而成。 A wholly aromatic liquid crystal polyester resin composition comprising the wholly aromatic liquid crystal polyester resin of claim 1 or 2 and an inorganic filler. 如請求項5之全芳香族液晶聚酯樹脂組合物，其中上述無機填充劑為纖維狀填充劑及板狀填充劑。 The wholly aromatic liquid crystal polyester resin composition of claim 5, wherein the above-mentioned inorganic filler is a fibrous filler and a plate-shaped filler. 如請求項6之全芳香族液晶聚酯樹脂組合物，其中相對於上述全芳香族液晶聚酯樹脂組合物所包含之全芳香族液晶聚酯樹脂100重量份，上述纖維狀填充劑及上述板狀填充劑之含量合計為100重量份以下。 The wholly aromatic liquid crystal polyester resin composition of claim 6, wherein the fibrous filler and the plate are based on 100 parts by weight of the wholly aromatic liquid crystal polyester resin contained in the wholly aromatic liquid crystal polyester resin composition The total content of the shaped filler is 100 parts by weight or less. 一種成形品，其係包含如請求項5至7中任一項之全芳香族液晶聚酯樹脂組合物而成。 A molded product comprising the wholly aromatic liquid crystal polyester resin composition according to any one of claims 5 to 7. 一種電子零件，其係包含如請求項5至7中任一項之全芳香族液晶聚酯樹脂組合物而成。 An electronic component comprising the wholly aromatic liquid crystal polyester resin composition according to any one of claims 5 to 7.
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