JP2003128893A - Liquid crystal polyester resin composition - Google Patents

Liquid crystal polyester resin composition

Info

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
Application number
JP2001330730A
Other languages
Japanese (ja)
Other versions
JP4368078B2 (en
Inventor
Takahiro Kawabata
隆広 川端
Kazuyoshi Oji
一能 尾地
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dainippon Ink and Chemicals Co Ltd filed Critical Dainippon Ink and Chemicals Co Ltd
Priority to JP2001330730A priority Critical patent/JP4368078B2/en
Publication of JP2003128893A publication Critical patent/JP2003128893A/en
Application granted granted Critical
Publication of JP4368078B2 publication Critical patent/JP4368078B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal composition capable of forming moldings having excellent mechanical strength, heat resistance and good surface appearance. SOLUTION: The liquid crystal polyester resin composition comprises 100 pts.wt. of a liquid crystal polyester (A) and 10-140 pts.wt. of compressed fine powdered talc having an apparent specific gravity of at least 0.4 g/cm<3> . The composition is characterized by containing a whole aromatic polyester having a melting point of >=300 deg.C as a liquid crystal (A).

Description

【発明の詳細な説明】Detailed Description of the Invention

【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5m/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
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/cm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/cm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/cm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/cm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/cm以上、よ
り好ましくは0.45〜1.2g/cm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/cm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/cm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/cm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/cm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)

【特許請求の範囲】[Claims] 【請求項1】 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/cm
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.
【請求項2】 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.
【請求項3】 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]、 【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.
【請求項4】 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.
【請求項5】 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.
JP2001330730A 2001-10-29 2001-10-29 Liquid crystalline polyester resin composition Expired - Fee Related JP4368078B2 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
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

Cited By (7)

* Cited by examiner, † Cited by third party
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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