JP2003128893A - Liquid crystal polyester resin composition - Google Patents
Liquid crystal polyester resin compositionInfo
- Publication number
- JP2003128893A JP2003128893A JP2001330730A JP2001330730A JP2003128893A JP 2003128893 A JP2003128893 A JP 2003128893A JP 2001330730 A JP2001330730 A JP 2001330730A JP 2001330730 A JP2001330730 A JP 2001330730A JP 2003128893 A JP2003128893 A JP 2003128893A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal polyester
- group
- talc
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐熱性、成形品外
観に優れる液晶ポリエステル樹脂組成物に関するもので
ある。更に詳しくは、コネクター、ボビン、ケースなど
の電気電子部品、自動車部品などの多岐にわたる用途に
使用可能な液晶ポリエステル樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a liquid crystal polyester resin composition which is excellent in heat resistance and appearance of a molded product. More specifically, the present invention relates to a liquid crystal polyester resin composition which can be used in various applications such as electric and electronic parts such as connectors, bobbins and cases, automobile parts and the like.
【０００２】[0002]
【従来の技術】液晶ポリエステル樹脂は、パラヒドロキ
シ安息香酸と６−ヒドロキシ−２−ナフトエ酸との共重
合体、パラヒドロキシ安息香酸、４，４’−ジヒドロキ
シビフェニルおよびテレフタル酸、イソフタル酸の共重
合体等に代表され、その優れた流動性、耐熱性、剛性、
寸法精度等の物性により、近年電気電子部品用途を中心
に重要が拡大している。Liquid crystal polyester resin is a copolymer of para-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, para-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl and terephthalic acid, isophthalic acid. Represented by coalescing, its excellent fluidity, heat resistance, rigidity,
Due to physical properties such as dimensional accuracy, the importance is expanding in recent years mainly for electric and electronic parts.
【０００３】異方性等の改良を目的にタルクを全芳香族
ポリエステルに代表されるサーモトロピック液晶ポリマ
ーに配合した樹脂組成物が、従来より種々試みられてき
た。しかしながら、従来のタルクを配合した液晶ポリエ
ステル樹脂組成物は、耐熱性等が必ずしも充分ではな
く、特に、全芳香族ポリエステルにタルクを配合した樹
脂組成物の場合は、その溶融温度が通常のポリエステル
の場合と比較して高温であるので、熱分解や加水分解が
起こり易いという欠点があった。また、機械的強度等の
性能を向上しようとすると、配合するタルクはある程度
平均粒子径の小さいタルクが好ましいが、平均粒子径が
小さくなると嵩密度が低くなり、包含した空気等を溶融
混練時に除去することが困難になったり、タルクを均一
且つ多量に配合することが困難になるという問題もあっ
た。Various resin compositions have been hitherto tried in which talc is blended with a thermotropic liquid crystal polymer typified by wholly aromatic polyester for the purpose of improving anisotropy and the like. However, the conventional liquid crystal polyester resin composition containing talc does not always have sufficient heat resistance, and in particular, in the case of a resin composition containing talc in a wholly aromatic polyester, the melting temperature of the polyester composition Since the temperature is higher than that of the case, there is a drawback that thermal decomposition or hydrolysis easily occurs. Further, in order to improve the performance such as mechanical strength, the talc to be blended is preferably talc having a small average particle diameter to some extent, but when the average particle diameter becomes small, the bulk density becomes low, and the included air or the like is removed during melt-kneading. There is also a problem that it becomes difficult to do so, and it becomes difficult to mix talc uniformly and in a large amount.
【０００４】例えば、特開昭６０−１２４６４９号公報
では平均粒子径が１〜１０μｍのタルクを配合すること
が提案されているが、同公報記載の１〜１０μｍのタル
クは嵩密度が低くて溶融混練時の取扱い性（ハンドリン
グ性）が悪いという問題があり、また、特開平４−１３
７５８号公報では比表面積が５ｍ２／ｇ以下で平均粒子
径が４０μｍ以下のタルクを配合することが提案されて
いるが、同公報に開示されているようなタルクは同公報
の実施例記載のように粒子径が１０数μｍとなり機械的
強度が低下してしまうなど、何れも満足出来るものでは
なかった。For example, JP-A-60-124649 proposes to blend talc having an average particle diameter of 1 to 10 μm, but talc of 1 to 10 μm described in the publication has a low bulk density and is melted. There is a problem that the handling property (handling property) at the time of kneading is poor, and there is a problem in JP-A-4-13.
Japanese Patent No. 758 proposes to blend talc having a specific surface area of 5 m 2 / g or less and an average particle diameter of 40 μm or less. However, talc as disclosed in the publication is described in the examples of the publication. As described above, the particle diameter becomes 10 and several μm and the mechanical strength is deteriorated.
【０００５】[0005]
【発明が解決しようとする課題】従って、本発明の目的
は、機械的強度や耐熱性に優れ、成形品の表面外観が良
好な液晶ポリエステル樹脂組成物を提供することであ
る。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a liquid crystal polyester resin composition having excellent mechanical strength and heat resistance and a molded product having a good surface appearance.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決すべく鋭意検討を重ねた結果、液晶ポリエステル
（Ａ）と、成分（Ｂ）として見掛け比重が０．４ｇ／ｃ
ｍ３以上の圧縮微粉タルクを配合してなる液晶ポリエス
テル樹脂組成物により、機械的強度や耐熱性、成形品の
表面外観等が改善出来ることを見出し、本発明を完成さ
せるに至った。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the liquid crystalline polyester (A) and the component (B) have an apparent specific gravity of 0.4 g / c.
The inventors have found that a liquid crystal polyester resin composition prepared by mixing compressed fine powder talc of m 3 or more can improve mechanical strength, heat resistance, surface appearance of a molded product, etc., and completed the present invention.
【０００７】即ち、本発明は、液晶ポリエステル（Ａ）
１００重量部に対して、成分（Ｂ）として見掛け比重が
０．４ｇ／ｃｍ３以上の圧縮微粉タルクを１０〜１４０
重量部配合してなることを特徴とする液晶ポリエステル
樹脂組成物に関する。That is, the present invention relates to a liquid crystal polyester (A)
10 to 140 compressed fine powder talc having an apparent specific gravity of 0.4 g / cm 3 or more as the component (B) per 100 parts by weight.
The present invention relates to a liquid crystal polyester resin composition characterized by being mixed in parts by weight.
【０００８】[0008]
【発明の実施の形態】次いで、本発明を実施するにあた
り、必要な事項を具体的に以下に述べる。BEST MODE FOR CARRYING OUT THE INVENTION Next, necessary items for carrying out the present invention will be specifically described below.
【０００９】本発明の液晶ポリエステル樹脂組成物と
は、少なくとも、液晶ポリエステル（Ａ）と、見掛け比
重が０．４ｇ／ｃｍ３以上の圧縮微粉タルク（Ｂ）を含
有してなる。The liquid crystal polyester resin composition of the present invention contains at least liquid crystal polyester (A) and compressed fine powder talc (B) having an apparent specific gravity of 0.4 g / cm 3 or more.
【００１０】本発明の液晶ポリエステル樹脂組成物と
は、液晶ポリエステル（Ａ）１００重量部に対して、成
分（Ｂ）として見掛け比重が０．４ｇ／ｃｍ３以上の圧
縮微粉タルクを、好ましくは、１０〜１４０重量部配合
してなる。The liquid crystal polyester resin composition of the present invention is preferably a compressed fine powder talc having an apparent specific gravity of 0.4 g / cm 3 or more as the component (B) with respect to 100 parts by weight of the liquid crystal polyester (A), It is composed of 10 to 140 parts by weight.
【００１１】本発明で使用する液晶ポリエステル（Ａ）
は、サーモトロピック液晶ポリマーであるポリエステル
である。Liquid crystalline polyester (A) used in the present invention
Is a thermotropic liquid crystal polymer, polyester.
【００１２】本発明で使用する液晶ポリエステル（Ａ）
としては、例えば、芳香族ジカルボン酸と芳香族ジオ
ールと芳香族ヒドロキシカルボン酸とを反応させて得ら
れるもの、異種の芳香族ヒドロキシカルボン酸を反応
させて得られるもの、芳香族ジカルボン酸と核置換芳
香族ジオールを反応させて得られるもの、ポリエチレ
ンテレフタレートなどのポリエステルに芳香族ヒドロキ
シカルボン酸を反応させて得られるもの等が挙げられ、
４００℃以下の温度で異方性溶融相を形成するものであ
る。尚、これらの芳香族ジカルボン酸、芳香族ジオー
ル、及び芳香族ヒドロキシカルボン酸の代わりに、それ
らのエステル形成性誘導体を使用してもよい。Liquid crystalline polyester (A) used in the present invention
Examples thereof include those obtained by reacting an aromatic dicarboxylic acid, an aromatic diol, and an aromatic hydroxycarboxylic acid, those obtained by reacting a different aromatic hydroxycarboxylic acid, and an aromatic dicarboxylic acid and nuclear substitution. Those obtained by reacting an aromatic diol, those obtained by reacting a polyester such as polyethylene terephthalate with an aromatic hydroxycarboxylic acid, and the like,
It forms an anisotropic molten phase at a temperature of 400 ° C. or lower. Incidentally, instead of these aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids, their ester-forming derivatives may be used.
【００１３】本発明で使用する液晶ポリエステル（Ａ）
の繰り返し構造単位としては、下記の芳香族ジカルボン
酸に由来する繰り返し構造単位、芳香族ジオールに由来
する繰り返し構造単位、芳香族ヒドロキシカルボン酸に
由来する繰り返し構造単位などを例示することができる
が、これらに限定されるものではない。Liquid crystalline polyester (A) used in the present invention
As the repeating structural unit of, it is possible to exemplify a repeating structural unit derived from the following aromatic dicarboxylic acid, a repeating structural unit derived from an aromatic diol, a repeating structural unit derived from an aromatic hydroxycarboxylic acid, and the like, It is not limited to these.
【００１４】芳香族ジカルボン酸に由来する繰り返し構
造単位の例としては、以下のような構造が挙げられる。Examples of repeating structural units derived from aromatic dicarboxylic acids include the following structures.
【００１５】[0015]
【化４】 [Chemical 4]
【００１６】また、芳香族ジオールに由来する繰り返し
構造単位の例としては、以下のような構造が挙げられ
る。Further, examples of the repeating structural unit derived from the aromatic diol include the following structures.
【００１７】[0017]
【化５】 [Chemical 5]
【００１８】更に、芳香族ヒドロキシカルボン酸に由来
する繰り返し構造単位の例としては、以下のような構造
が挙げられる。Further, examples of the repeating structural unit derived from the aromatic hydroxycarboxylic acid include the following structures.
【００１９】[0019]
【化６】 [Chemical 6]
【００２０】本発明で使用する液晶ポリエステル（Ａ）
は、耐熱性、機械的特性、加工性等のバランスから、特
に好ましい液晶ポリエステルとしては、下記構造式
［７］で示される繰り返し構造単位を含むものである。Liquid crystalline polyester (A) used in the present invention
From the viewpoint of the balance of heat resistance, mechanical properties, processability, etc., a particularly preferable liquid crystal polyester is one containing a repeating structural unit represented by the following structural formula [7].
【００２１】[0021]
【化７】 [Chemical 7]
【００２２】上記の繰り返し構造単位（構造式［７］）
を含む液晶ポリエステル（Ａ）としては、例えば、下記
の繰り返し単位の組み合わせを含む液晶ポリエステル
〜などが挙げられる。尚、本発明においては、これら
の例に限定されるものではない。The above repeating structural unit (structural formula [7])
As the liquid crystal polyester (A) containing, for example, liquid crystal polyesters containing a combination of the following repeating units and the like can be mentioned. Note that the present invention is not limited to these examples.
【００２３】[0023]
【化８】 [Chemical 8]
【００２４】[0024]
【化９】 [Chemical 9]
【００２５】[0025]
【化１０】 [Chemical 10]
【００２６】[0026]
【化１１】 [Chemical 11]
【００２７】[0027]
【化１２】 [Chemical 12]
【００２８】[0028]
【化１３】 [Chemical 13]
【００２９】[0029]
【化１４】 [Chemical 14]
【００３０】本発明で使用する液晶ポリエステル〜
の製法については、例えば、特公昭４７−４７８７０号
公報、特公昭６３−３８８８号公報、特公昭６３−３８
９１号公報、特公昭５６−１８０１６号公報、特公平２
−５１５２３号公報、特公平７−４７６２５号公報など
に記載されている。これらの中で好ましくは〜の組
み合わせであり、より好ましくは、の組み合せであ
る。Liquid Crystal Polyester Used in the Present Invention
For the production method, for example, JP-B-47-47870, JP-B-63-3888, and JP-B-63-38.
No. 91, Japanese Patent Publication No. 56-18016, Japanese Patent Publication No. 2
-51523 and Japanese Patent Publication No. 7-47625. Among these, a combination of is preferable, and a combination of is more preferable.
【００３１】本発明で使用する液晶ポリエステル（Ａ）
は、融点３００℃以上の全芳香族ポリエステルであるこ
とが好ましい。Liquid crystalline polyester (A) used in the present invention
Is preferably a wholly aromatic polyester having a melting point of 300 ° C. or higher.
【００３２】本発明で使用する液晶ポリエステル（Ａ）
とは、下記構造式の（グループａ）、（グループｂ）、
（グループｃ）から選ばれる繰り返し単位からなり、
（グループａ）が構造式［１］、及び／又は構造式
［２］、Liquid crystalline polyester (A) used in the present invention
And (group a), (group b) of the following structural formula,
Consists of repeating units selected from (group c),
(Group a) is structural formula [1] and / or structural formula [2],
【００３３】[0033]
【化１５】 [Chemical 15]
【００３４】（グループｂ）が構造式［３］、及び／又
は構造式［４］、及び／又は構造式［５］、及び／又は
構造式［６］、(Group b) is structural formula [3] and / or structural formula [4], and / or structural formula [5], and / or structural formula [6],
【００３５】[0035]
【化１６】 [Chemical 16]
【００３６】（グループｃ）が構造式［７］であり、(Group c) is structural formula [7],
【００３７】[0037]
【化１７】 [Chemical 17]
【００３８】各構造式の繰り返し単位のモル比が［２］
／［１］＝０〜１．５モル比の範囲であり、〔［３］＋
［４］〕／〔［５］＋［６］〕が１〜１０モル比の範囲
であり、（グループｂ）の合計モル比に対する（グルー
プａ）の合計モル比が実質的に１：１であり、更に、
（グループｃ）／（グループａ）が１〜６モル比の範囲
であり、［４］／［３］が０〜２モル比の範囲であり、
［６］／［５］が０〜２モル比の範囲であることが好ま
しい。かかるモル比の液晶ポリエステル樹脂は、機械的
強度などの力学特性や耐熱性、流動性などに優れ、高度
にバランスしている。The molar ratio of repeating units of each structural formula is [2].
/ [1] = 0 to 1.5 in the molar ratio range, [[3] +
[4] / [[5] + [6]] is in the range of 1 to 10 and the total molar ratio of (group a) to the total molar ratio of (group b) is substantially 1: 1. Yes, and
(Group c) / (group a) is in the range of 1 to 6 molar ratio, [4] / [3] is in the range of 0 to 2 molar ratio,
[6] / [5] is preferably in the range of 0 to 2 molar ratio. The liquid crystal polyester resin having such a molar ratio is excellent in mechanical properties such as mechanical properties, heat resistance and fluidity, and is highly balanced.
【００３９】更に、本発明の液晶ポリエステル樹脂組成
物は、成分（Ｂ）として圧縮微粉タルクを含有する。Further, the liquid crystal polyester resin composition of the present invention contains compressed fine powder talc as the component (B).
【００４０】本発明で云う「圧縮微粉タルク」とは、例
えば、微粉タルクの粒子内及び／又は粒子間に存在する
空気等の気体を真空装置等の適当な手段により初期脱気
した後、更にローラー、プレス等の圧縮可能な手段によ
り更に圧縮脱気した安定した凝集状態のタルクが例示出
来る。The term "compressed fine talc" as used in the present invention means, for example, that the gas such as air existing in and / or between the fine talc particles is initially degassed by an appropriate means such as a vacuum device, and then Talc in a stable agglomerated state that has been further decompressed by a compressible means such as a roller or a press can be exemplified.
【００４１】本発明で使用する圧縮微粉タルク（Ｂ）と
は、圧縮前の平均粒子径が好ましくは０．２〜１０μｍ
であり、より好ましくは０．５〜５μｍ、見掛け比重
０．１〜０．４ｇ／ｃｍ３の所謂、微粉タルクを圧縮し
て、タルク内に含まれる気体の３０％以上を脱気したも
のであり、圧縮後の平均粒子径が、好ましくは１５０μ
ｍ以上、より好ましくは１５０〜６００μｍの範囲であ
り、見掛け比重が好ましくは０．４ｇ／ｃｍ３以上、よ
り好ましくは０．４５〜１．２ｇ／ｃｍ３の範囲であ
る。The compressed fine powder talc (B) used in the present invention has an average particle size before compression of preferably 0.2 to 10 μm.
More preferably, the so-called fine powder talc having an apparent specific gravity of 0.5 to 5 μm and an apparent specific gravity of 0.1 to 0.4 g / cm 3 is compressed to degas 30% or more of the gas contained in the talc. And the average particle size after compression is preferably 150μ
m or more, more preferably in the range of 150～600Myuemu, apparent specific gravity is preferably 0.4 g / cm 3 or more, more preferably in the range of 0.45~1.2g / cm 3.
【００４２】本発明において、圧縮微粉タルク（Ｂ）を
使用することにより、樹脂組成物の均一分散性が良好
で、混練作業性が改善され、機械的特性を改善出来る。In the present invention, by using the compressed fine powder talc (B), uniform dispersion of the resin composition is good, kneading workability is improved, and mechanical properties can be improved.
【００４３】本発明で使用する圧縮微粉タルク（Ｂ）の
添加量は、液晶ポリエステル（Ａ）１００重量部に対し
て、好ましくは１０〜１４０重量部であり、より好まし
くは２０〜１００重量部である。圧縮微粉タルク（Ｂ）
の添加量がかかる範囲であれば、成形品の表面状態が良
好で、機械的強度に優れる樹脂組成物を得ることが出来
る。The addition amount of the compressed fine powder talc (B) used in the present invention is preferably 10 to 140 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the liquid crystal polyester (A). is there. Compressed fine powder talc (B)
When the addition amount of is within such a range, it is possible to obtain a resin composition in which the surface condition of the molded product is good and the mechanical strength is excellent.
【００４４】本発明の液晶ポリエステル樹脂組成物に
は、本発明の目的を損なわない範囲で、必要に応じて、
更に、酸化防止剤、熱安定剤、光安定剤、難燃剤、滑
剤、帯電防止剤、無機又は有機系着色剤（染料、顔
料）、防錆剤、架橋剤、可塑剤、蛍光剤、表面平滑剤、
表面光沢改良剤、離型剤（フッ素樹脂、ポリオレフィン
ワックス等）などの各種添加剤や他の熱可塑性樹脂を製
造工程中あるいはその後の加工工程において添加するこ
とができる。The liquid crystal polyester resin composition of the present invention may be added to the liquid crystal polyester resin composition of the present invention, if necessary, within a range not impairing the object of the present invention.
Furthermore, antioxidants, heat stabilizers, light stabilizers, flame retardants, lubricants, antistatic agents, inorganic or organic colorants (dyes, pigments), rust inhibitors, cross-linking agents, plasticizers, fluorescent agents, surface smoothing. Agent,
Various additives such as a surface gloss improver and a release agent (fluorine resin, polyolefin wax, etc.) and other thermoplastic resins can be added during the manufacturing process or in the subsequent processing process.
【００４５】本発明の液晶ポリエステル樹脂組成物は、
少なくとも、上記の液晶ポリエステル（Ａ）と圧縮微粉
タルク（Ｂ）を配合し溶融混練することにより得られる
ものである。該配合、及び、溶融混練には公知の種々の
方法を用いることが出来る。該配合、及び、溶融混練は
バッチ式で行ってもよく、連続式で行ってもよく、特に
限定はしない。尚、配合、及び、混練の順序は任意に選
択でき、例えば、液晶ポリエステル（Ａ）と圧縮微粉タ
ルク（Ｂ）を同時に配合し混合して溶融混練してもよ
く、先ず、液晶ポリエステル（Ａ）を溶融混練した後、
更に圧縮微粉タルク（Ｂ）を加えて溶融混練してもよ
い。The liquid crystal polyester resin composition of the present invention is
It is obtained by blending at least the above liquid crystal polyester (A) and compressed fine powder talc (B) and melt-kneading. Various known methods can be used for the blending and the melt kneading. The blending and melt-kneading may be performed in a batch system or a continuous system, and there is no particular limitation. The order of compounding and kneading can be arbitrarily selected. For example, liquid crystal polyester (A) and compressed fine powder talc (B) may be simultaneously compounded and mixed to be melt-kneaded. First, liquid crystal polyester (A) After melt kneading,
Further, compressed fine powder talc (B) may be added and melt-kneaded.
【００４６】溶融混練する温度は、使用する液晶ポリエ
ステル樹脂の種類により、適宜設定可能であるが、通
常、２００〜４００℃の範囲である。The temperature for melt-kneading can be appropriately set depending on the type of liquid crystal polyester resin used, but is usually in the range of 200 to 400 ° C.
【００４７】尚、本発明の態様は、上述したように、液
晶ポリエステル（Ａ）１００重量部に対して、成分
（Ｂ）として見掛け比重が０．４ｇ／ｃｍ３以上の圧縮
微粉タルクを１０〜１４０重量部配合してなることを特
徴とする液晶ポリエステル樹脂組成物にかかるものであ
る。In the embodiment of the present invention, as described above, 10 parts of compressed fine powder talc having an apparent specific gravity of 0.4 g / cm 3 or more as the component (B) is added to 100 parts by weight of the liquid crystal polyester (A). The present invention relates to a liquid crystal polyester resin composition characterized by containing 140 parts by weight.
【００４８】本発明の他の態様の一つとしては、液晶ポ
リエステル（Ａ）が、融点３００℃以上の全芳香族ポリ
エステルである上記の液晶ポリエステル樹脂組成物にか
かるものである。As another embodiment of the present invention, the above liquid crystal polyester resin composition is one in which the liquid crystal polyester (A) is a wholly aromatic polyester having a melting point of 300 ° C. or higher.
【００４９】本発明の他の態様の一つとしては、液晶ポ
リエステルが（Ａ）が、下記構造式の（グループａ）、
（グループｂ）、（グループｃ）から選ばれる繰り返し
単位からなり、（グループａ）が構造式［１］、及び／
又は構造式［２］、In another embodiment of the present invention, the liquid crystal polyester (A) has the following structural formula (group a),
A repeating unit selected from (group b) and (group c), wherein (group a) is structural formula [1], and /
Or structural formula [2],
【００５０】[0050]
【化１８】 [Chemical 18]
【００５１】（グループｂ）が構造式［３］、及び／又
は構造式［４］、及び／又は構造式［５］、及び／又は
構造式［６］、(Group b) is structural formula [3] and / or structural formula [4], and / or structural formula [5], and / or structural formula [6],
【００５２】[0052]
【化１９】 [Chemical 19]
【００５３】（グループｃ）が構造式［７］であり、(Group c) is structural formula [7],
【００５４】[0054]
【化２０】 [Chemical 20]
【００５５】各構造式の繰り返し単位のモル比が［２］
／［１］＝０〜１．５モル比の範囲であり、〔［３］＋
［４］〕／〔［５］＋［６］〕＝１〜１０モル比の範囲
であり、（グループｂ）の合計モル比に対する（グルー
プａ）の合計モル比が実質的に１：１であり、更に、
（グループｃ）／（グループａ）＝１〜６モル比の範囲
であり、［４］／［３］＝０〜２モル比の範囲であり、
［６］／［５］＝０〜２モル比の範囲である上記の各液
晶ポリエステル樹脂組成物にかかるものである。The molar ratio of repeating units of each structural formula is [2].
/ [1] = 0 to 1.5 in the molar ratio range, [[3] +
[4]] / [[5] + [6]] = 1 to 10 molar ratio, and the total molar ratio of (group a) to the total molar ratio of (group b) is substantially 1: 1. Yes, and
(Group c) / (group a) = 1 to 6 molar ratio range, [4] / [3] = 0 to 2 molar ratio range,
The present invention relates to each of the above liquid crystal polyester resin compositions in the range of [6] / [5] = 0 to 2 molar ratio.
【００５６】本発明の他の態様の一つとしては、圧縮微
粉タルク（Ｂ）が、平均粒子径が０．５〜５μｍの範囲
であるタルクを圧縮し得られたものである上記の各液晶
ポリエステル樹脂組成物にかかるものである。In another aspect of the present invention, the compressed fine powder talc (B) is obtained by compressing talc having an average particle size of 0.5 to 5 μm. The present invention relates to a polyester resin composition.
【００５７】[0057]
【実施例】以下、本発明を実施例と比較例により、一
層、具体的に説明するが、本発明の範囲はこれら実施例
に限定されるものではない。以下において、例中特に断
らない限り、「％」は重量％を、「部」は重量部をそれ
ぞれ表す。EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples. In the following, "%" represents% by weight and "part" represents parts by weight, unless otherwise specified.
【００５８】《合成例１》ＬＣＰ−１の液晶ポリエステ
ルの合成
ハイドロキノン５５．１ｇ（０．５モル）、４，４’−
ジヒドロキシビフェニル９３．１ｇ（０．５モル）、テ
レフタル酸１１６．３ｇ（０．７モル）、２，６−ナフ
タレンジカルボン酸６４．９ｇ（０．３モル）、４−ヒ
ドロキシ安息香酸６２１．５ｇ（４．５モル）、無水酢
酸６１２．５ｇ（６モル）を冷却器及び撹拌機を備えた
反応容器中に仕込み窒素ガス雰囲気下で撹拌しながら昇
温し、１７０℃で６０分環流した。次いで、副生成物の
酢酸を除去しながら４時間かけて反応容器を３７０℃に
徐々に上昇させ、更に、３７０℃で反応系を２５ｋＰａ
に減圧した。更にその温度で副生成物の酢酸を除去しな
がら圧力を２時間にわたって０．５〜１ｋＰａまで減圧
し重合を行った。Synthesis Example 1 Synthesis of Liquid Crystal Polyester of LCP-1 Hydroquinone 55.1 g (0.5 mol), 4,4'-
Dihydroxybiphenyl 93.1 g (0.5 mol), terephthalic acid 116.3 g (0.7 mol), 2,6-naphthalenedicarboxylic acid 64.9 g (0.3 mol), 4-hydroxybenzoic acid 621.5 g ( 4.5 mol) and 612.5 g (6 mol) of acetic anhydride were charged into a reaction vessel equipped with a condenser and a stirrer, the temperature was raised with stirring under a nitrogen gas atmosphere, and the mixture was refluxed at 170 ° C. for 60 minutes. Then, the reaction vessel was gradually raised to 370 ° C. over 4 hours while removing the by-product acetic acid, and the reaction system was further heated to 370 ° C. at 25 kPa.
The pressure was reduced to. Further, the pressure was reduced to 0.5 to 1 kPa over 2 hours while removing acetic acid as a by-product at that temperature to carry out polymerization.
【００５９】次いで、３７０℃で１時間重合を行った。
この間に副生する酢酸を除去しながら、強力な撹拌下で
重合を行い、その後、系を徐々に冷却し、２００℃で得
られたポリマーを系外へ取出した。示差走査熱量計（パ
ーキンエルマー社製ＤＳＣ７）を用いて融点を測定（Ｊ
ＩＳ Ｋ ７１２１に準拠）したところ、３５０℃であっ
た。Then, polymerization was carried out at 370 ° C. for 1 hour.
Polymerization was performed under strong stirring while removing by-product acetic acid during this period, and then the system was gradually cooled, and the polymer obtained at 200 ° C. was taken out of the system. The melting point was measured using a differential scanning calorimeter (DSC7 manufactured by Perkin Elmer Co., Ltd.) (J
According to IS K 7121), it was 350 ° C.
【００６０】《合成例２》ＬＣＰ−２の液晶ポリエステ
ルの合成
ハイドロキノン５５．１ｇ（０．５モル）、４，４’−
ジヒドロキシビフェニル９３．１ｇ（０．５モル）、テ
レフタル酸１１６．３ｇ（０．７モル）、２，６−ナフ
タレンジカルボン酸４３．３ｇ（０．２モル）、４，
４’−ビフェニルジカルボン酸２４．２ｇ（０．１モ
ル）、４−ヒドロキシ安息香酸６２１．５ｇ（４．５モ
ル）、無水酢酸６１２．５ｇ（６モル）を使用する以外
は上記ＬＣＰ−１と同様に重合を行った。上記と同様に
測定した融点は３６５℃であった。Synthesis Example 2 Synthesis of Liquid Crystal Polyester of LCP-2 Hydroquinone 55.1 g (0.5 mol), 4,4'-
Dihydroxybiphenyl 93.1 g (0.5 mol), terephthalic acid 116.3 g (0.7 mol), 2,6-naphthalenedicarboxylic acid 43.3 g (0.2 mol), 4,
With LCP-1 except that 24.2 g (0.1 mol) of 4'-biphenyldicarboxylic acid, 621.5 g (4.5 mol) of 4-hydroxybenzoic acid and 612.5 g (6 mol) of acetic anhydride were used. Polymerization was performed in the same manner. The melting point measured in the same manner as above was 365 ° C.
【００６１】《合成例３》ＬＣＰ−３の液晶ポリエステ
ルの合成
ハイドロキノン１１０．１ｇ（１モル）、テレフタル酸
５８．１ｇ（０．３５モル）、イソフタル酸５８．１ｇ
（０．３５モル）、２，６−ナフタレンジカルボン酸６
４．９ｇ（０．３モル）、４−ヒドロキシ安息香酸６２
１．５ｇ（４．５モル）、無水酢酸６１２．５ｇ（６モ
ル）を使用する以外は上記ＬＣＰ−１と同様に重合を行
った。上記と同様に測定した融点は３２８℃であった。Synthesis Example 3 Synthesis of Liquid Crystal Polyester of LCP-3 110.1 g (1 mol) of hydroquinone, 58.1 g (0.35 mol) of terephthalic acid, 58.1 g of isophthalic acid
(0.35 mol), 2,6-naphthalenedicarboxylic acid 6
4.9 g (0.3 mol), 4-hydroxybenzoic acid 62
Polymerization was performed in the same manner as in LCP-1 except that 1.5 g (4.5 mol) and acetic anhydride 612.5 g (6 mol) were used. The melting point measured in the same manner as above was 328 ° C.
【００６２】《実施例又は比較例に用いたタルクの性
状》実施例又は比較例に用いたタルクの性状は以下の通
りである。
タルク−１：見掛け比重０．２０ｇ／ｃｍ３の微粉タル
ク、平均粒子径２．７μｍ。
タルク−２：上記タルク−１の微粉タルクを圧縮したタ
ルクであり、見掛け比重０．８ｇ／ｃｍ３の圧縮微粉タ
ルク、平均粒子径３５０μｍ。
タルク−３：上記タルク−１の微粉タルクを圧縮したタ
ルクであり、見掛け比重０．５ｇ／ｃｍ３の圧縮微粉タ
ルク、平均粒子径２５０μｍ。<< Properties of Talc Used in Examples or Comparative Examples >> Properties of talc used in Examples or Comparative Examples are as follows. Talc-1: Fine powder talc having an apparent specific gravity of 0.20 g / cm 3 , and an average particle diameter of 2.7 μm. Talc-2: Talc obtained by compressing the fine powder talc of the above talc-1, compressed fine powder talc having an apparent specific gravity of 0.8 g / cm 3 , and an average particle diameter of 350 μm. Talc-3: Talc obtained by compressing the fine powder talc of the above talc-1, compressed fine powder talc having an apparent specific gravity of 0.5 g / cm 3 , and an average particle diameter of 250 μm.
【００６３】《実施例１〜８》上記ＬＣＰ−１、ＬＣＰ
−２及びＬＣＰ−３と、タルク−１、タルク−２及びタ
ルク−３を表１及び表２に示すような配合比で配合し、
３００〜３６０℃で押し出し、ペレット化した。得られ
たペレットを用いて、射出成形機にてＡＳＴＭ４号ダン
ベルを射出成形し、該成形品を用いてＡＳＴＭ Ｄ−６
３８に準拠して引張試験を行った。また、該成形品を２
６０℃の熱風乾燥機中に１時間放置し、ブリスタの発生
の有無により耐熱性を評価した。本発明の液晶ポリエス
テル樹脂組成物の評価結果を表１及び表２に示す。<< Examples 1 to 8 >> The above LCP-1 and LCP
-2 and LCP-3 and talc-1, talc-2 and talc-3 were compounded in a compounding ratio as shown in Table 1 and Table 2,
It was extruded at 300 to 360 ° C. and pelletized. The obtained pellets were used to injection-mold an ASTM No. 4 dumbbell with an injection molding machine, and the molded product was used to prepare ASTM D-6.
According to No. 38, a tensile test was conducted. In addition, the molded product
It was left in a hot air dryer at 60 ° C. for 1 hour, and heat resistance was evaluated by the presence or absence of blister generation. The evaluation results of the liquid crystal polyester resin composition of the present invention are shown in Tables 1 and 2.
【００６４】《比較例１〜３》表２に示すような配合比
で実施例と同様に押し出し、ペレット化、射出成形を行
い、実施例と同様の評価を行った。その評価結果を表２
に示す。<< Comparative Examples 1 to 3 >> Extrusion, pelletization and injection molding were carried out at the compounding ratios shown in Table 2 in the same manner as in Examples, and the same evaluations as in Examples were carried out. The evaluation results are shown in Table 2.
Shown in.
【００６５】[0065]
【表１】 [Table 1]
【００６６】[0066]
【表２】 [Table 2]
【００６７】[0067]
【発明の効果】本発明によれば、機械的強度や耐熱性に
優れ、成形品の表面外観が良好な液晶ポリエステル樹脂
組成物を提供することが出来る。本発明の液晶ポリエス
テル樹脂組成物は、コネクター、ボビン、ケースなどの
電気電子部品、自動車部品等の幅広い分野に利用可能で
ある。According to the present invention, it is possible to provide a liquid crystal polyester resin composition which is excellent in mechanical strength and heat resistance and has a good surface appearance of a molded product. The liquid crystal polyester resin composition of the present invention can be used in a wide range of fields such as electrical and electronic parts such as connectors, bobbins and cases, automobile parts and the like.
フロントページの続き Ｆターム(参考） 4J002 CF161 DJ046 4J029 AA04 AB01 AC02 AD06 AD09 AE01 BB04A BB05A BB10A BB12A BB13A BC05A BC06A BE05A BG03 BG05Y CB05A CB06A CB06B CB10A CC06A CF15 CG06 EB04A EB05A EB05B EC05A EC06A EE05 KB02 Continued front page F-term (reference) 4J002 CF161 DJ046 4J029 AA04 AB01 AC02 AD06 AD09 AE01 BB04A BB05A BB10A BB12A BB13A BC05A BC06A BE05A BG03 BG05Y CB05A CB06A CB06B CB10A CC06A CF15 CG06 EB04A EB05A EB05B EC05A EC06A EE05 KB02
Claims (5)
対して、成分（Ｂ）として見掛け比重が０．４ｇ／ｃｍ
３以上の圧縮微粉タルクを１０〜１４０重量部配合して
なることを特徴とする液晶ポリエステル樹脂組成物。1. The apparent specific gravity of the component (B) is 0.4 g / cm based on 100 parts by weight of the liquid crystal polyester (A).
A liquid crystal polyester resin composition comprising 10 to 140 parts by weight of 3 or more compressed fine powder talc.
℃以上の全芳香族ポリエステルである請求項１記載の液
晶ポリエステル樹脂組成物。2. The liquid crystal polyester (A) has a melting point of 300.
The liquid crystal polyester resin composition according to claim 1, which is a wholly aromatic polyester having a temperature of ℃ or more.
式の（グループａ）、（グループｂ）、（グループｃ）
から選ばれる繰り返し単位からなり、（グループａ）が
構造式［１］、及び／又は構造式［２］、 【化１】 （グループｂ）が構造式［３］、及び／又は構造式
［４］、及び／又は構造式［５］、及び／又は構造式
［６］、 【化２】 （グループｃ）が構造式［７］であり、 【化３】 各構造式の繰り返し単位のモル比が［２］／［１］＝０
〜１．５モル比の範囲であり、〔［３］＋［４］〕／
〔［５］＋［６］〕＝１〜１０モル比の範囲であり、
（グループｂ）の合計モル比に対する（グループａ）の
合計モル比が実質的に１：１であり、更に、（グループ
ｃ）／（グループａ）＝１〜６モル比の範囲であり、
［４］／［３］＝０〜２モル比の範囲であり、［６］／
［５］＝０〜２モル比の範囲である請求項１又は２記載
の液晶ポリエステル樹脂組成物。3. The liquid crystal polyester (A) has the following structural formulas (group a), (group b) and (group c):
And (group a) is a structural formula [1] and / or a structural formula [2]: (Group b) is structural formula [3] and / or structural formula [4], and / or structural formula [5], and / or structural formula [6], (Group c) is structural formula [7], and The molar ratio of repeating units of each structural formula is [2] / [1] = 0
To [1.5] and a molar ratio of [[3] + [4]] /
[[5] + [6]] = 1 to 10 molar ratio range,
The total molar ratio of (group a) to the total molar ratio of (group b) is substantially 1: 1, and further, (group c) / (group a) = 1 to 6 molar ratio,
[4] / [3] = 0 to 2 molar ratio range, [6] /
The liquid crystal polyester resin composition according to claim 1, wherein [5] = 0 to 2 in a molar ratio range.
０．５〜５μｍの範囲であるタルクを圧縮し得られたも
のである請求項１又は２記載の液晶ポリエステル樹脂組
成物。4. The liquid crystal polyester resin composition according to claim 1, wherein the compressed fine powder talc (B) is obtained by compressing talc having an average particle diameter of 0.5 to 5 μm.
０．５〜５μｍの範囲であるタルクを圧縮し得られたも
のである請求項３記載の液晶ポリエステル樹脂組成物。5. The liquid crystal polyester resin composition according to claim 3, wherein the compressed fine powder talc (B) is obtained by compressing talc having an average particle size of 0.5 to 5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001330730A JP4368078B2 (en) | 2001-10-29 | 2001-10-29 | Liquid crystalline polyester resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001330730A JP4368078B2 (en) | 2001-10-29 | 2001-10-29 | Liquid crystalline polyester resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003128893A true JP2003128893A (en) | 2003-05-08 |
| JP4368078B2 JP4368078B2 (en) | 2009-11-18 |
Family
ID=19146411
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001330730A Expired - Fee Related JP4368078B2 (en) | 2001-10-29 | 2001-10-29 | Liquid crystalline polyester resin composition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100139105A (en) | 2008-03-28 | 2010-12-31 | 제이엑스 닛코닛세키에너지주식회사 | Liquid-crystal polyester resin composition for camera modules |
| CN103194078A (en) * | 2013-04-27 | 2013-07-10 | 苏州正豪塑胶电子有限公司 | High-strength and high temperature resistant plug connector |
| CN111825833A (en) * | 2019-04-16 | 2020-10-27 | 上野制药株式会社 | Liquid crystalline polyester resin |
| TWI844641B (en) | 2019-04-16 | 2024-06-11 | 日商上野製藥股份有限公司 | Liquid crystal polyester resin |
-
2001
- 2001-10-29 JP JP2001330730A patent/JP4368078B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100139105A (en) | 2008-03-28 | 2010-12-31 | 제이엑스 닛코닛세키에너지주식회사 | Liquid-crystal polyester resin composition for camera modules |
| US8192645B2 (en) | 2008-03-28 | 2012-06-05 | Jx Nippon Oil & Energy Corporation | Liquid crystal polyester resin composition for camera module |
| CN103194078A (en) * | 2013-04-27 | 2013-07-10 | 苏州正豪塑胶电子有限公司 | High-strength and high temperature resistant plug connector |
| CN111825833A (en) * | 2019-04-16 | 2020-10-27 | 上野制药株式会社 | Liquid crystalline polyester resin |
| JP2020176174A (en) * | 2019-04-16 | 2020-10-29 | 上野製薬株式会社 | Liquid crystal polyester resin |
| JP7175834B2 (en) | 2019-04-16 | 2022-11-21 | 上野製薬株式会社 | liquid crystal polyester resin |
| TWI844641B (en) | 2019-04-16 | 2024-06-11 | 日商上野製藥股份有限公司 | Liquid crystal polyester resin |
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