JP3598180B2 - High heat resistant resin composition - Google Patents

Description

【０００７】
（但し、Ｘ ：アルキレン（Ｃ_１〜Ｃ_４）、アルキリデン、−Ｏ− 、−ＳＯ−、−ＳＯ_２− 、−Ｓ− 、−ＣＯ−より選ばれる基
Ｙ ：−（ＣＨ_２）_ｎ−（ｎ ＝１〜４）、−Ｏ（ＣＨ_２）_ｎＯ−（ｎ ＝１〜４）より選ばれる基）
である。
又、本発明に使用される液晶性ポリエステルは、上述の構成成分の他に同一分子鎖中に部分的に異方性溶融相を示さないポリアルキレンテレフタレートであってもよい。この場合のアルキル基の炭素数は２乃至４である。
上述の構成成分の内、ナフタレン化合物、ビフェニル化合物、パラ位置換ベンゼン化合物より選ばれる１種若しくは２種以上の化合物を必須の構成成分として含むものが更に好ましい例である。又、ｐ−位置換ベンゼン化合物の内、ｐ−ヒドロキシ安息香酸、メチルハイドロキノン及び１−フェニルエチルハイドロキノンは特に好ましい例である。
構成成分となるエステル形成性の官能基を有する化合物の具体例及び本発明で用いられるのに好ましい異方性溶融相を形成するポリエステルの具体例については特公昭６３−３６６３３号公報に記載されている。
上記の芳香族ポリエステル及びポリエステルアミドはまた、６０℃でペンタフルオロフェノールに ０．１重量％濃度で溶解したときに、少なくとも約 ２．０ｄｌ／ｇ、例えば約 ２．０〜１０．０ｄｌ／ｇの対数粘度（Ｉ．Ｖ．）を一般に示す。
【０００８】
次に、本発明の樹脂組成物に必須成分として用いられるホウ素化合物は、下記一般式（Ｉ）又は（ＩＩ）で示されるホウ素化合物、それらの縮合体又は塩の中から選ばれた１種又は２種以上のものである。
【０００９】
【化３】

【００１０】
（式（Ｉ）及び（ＩＩ）中のＸ 、Ｙ 、Ｚ 及びＸ’、Ｙ’、Ｚ’、Ｑ は、−ＯＲ 又は１価の有機基である。ここでＲ は、Ｈ 、Ｐ 又は１価の有機基である。但し、Ｒ がＰ の場合は、縮合体である。Ｘ 、Ｙ 、Ｚ 或いはＸ’、Ｙ’、Ｚ’、Ｑ は、各々同一であっても相異なっていてもよい、又これらの２つ以上が連結して環を形成していてもよい。）
ホウ素化合物としては、無機ホウ素化合物と有機ホウ素化合物があり、無機ホウ素化合物としては、オルトホウ酸、メタホウ酸及び四ホウ酸等のホウ酸化合物、二酸化二ホウ素、三酸化二ホウ素、三酸化四ホウ素、五酸化四ホウ素等の酸化ホウ素、ホウ酸のアンモニウム塩や金属塩、リン酸ホウ素等が挙げられる。中でも、オルトホウ酸、メタホウ酸、四ホウ酸、酸化ホウ素は効果が高く、好ましく用いられる。
有機ホウ素化合物としては、ボロキシン、フェニルホウ酸、ジフェニルホウ酸及び、ホウ酸とアルコール化合物或いはフェノール化合物とのホウ酸エステル化合物等が挙げられる。例えば、Ｃ_１〜Ｃ_２０ の脂肪族モノアルコール、多価アルコール（エチレングリコール、テトラブチレングリコール、グリセリン、ペンタエリスリトールなど）、フェノール化合物（フェノール、カテコール、レソルシノール、ハイドロキノン、クレゾールなど）とのホウ酸モノ、ジ、トリ或いはテトラエステル化合物やそれらの混合物、さらにはそれらの金属塩が挙げられる。これらのホウ素化合物は、市販品を用いることができる。
また、使用されるホウ素化合物の粒径は、特に制限はないが、粒子系が小さい方が効果に優れ、１０μｍ 以下のものが好ましく用いられる。
本発明においては、上記の如き特定のホウ素化合物の配合量は液晶性ポリエステル１００ 重量部に対し ０．００１〜１０重量部、好ましくは ０．００５〜５重量部、更に好ましくは、０．０１〜３重量部である。この様に、少量の配合により、大きな改質効果が発現する。配合量が ０．００１重量部未満では本発明の企図するガス発生及び昇華物発生の抑制効果が乏しく、１０重量部を越えると過剰なホウ素化合物が色相や成形性を悪くし、組成物の物性を低下させる。
【００１１】
また、本発明においては、更に有機燐化合物を液晶性ポリエステル１００ 重量部に対し０．０５〜５．０ 重量部配合することにより、ガス発生及び昇華物発生の抑制効果が一層改善される。有機燐化合物はそれ単独で配合しても本発明の目的に対して効果が少ないが、ホウ素化合物と併用することにより、ガス発生及び昇華物発生抑制効果を増大させる。この有機燐化合物とは分子中に燐原子を有するものであり、燐化物、燐酸化合物、亜燐酸化合物等が挙げられるが、亜燐酸化合物のものが好ましく、特に好ましくは、ペンタエリスリトール型の亜燐酸化合物であり、例えば、ビス（２，６ −ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジホスファイトが好ましいものとして例示される。
この有機燐化合物の配合量は、異方性溶融相を形成しうる溶融加工性ポリエステル １００重量部に０．０５〜５．０ 重量部が好ましく、特に ０．１〜３重量部が好ましい。配合量が０．０５重量部未満であると併用効果が少なく、５重量部を越えて配合すると配合した有機燐化合物のガスが多量に発生して、本発明の目的を損なうことになる。
【００１２】
また、本発明の樹脂組成物には、その目的に応じ前記成分の他に、他の樹脂を補助的に少量併用することも可能である。ここで液晶性ポリエステルと混合される樹脂の例を示せば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリシクロヘキシレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート等の芳香族ジカルボン酸とジオール或いはオキシカルボン酸等からなる芳香族ポリエステル、ポリオレフィン、ポリアミド、ポリアセタール、ポリスチレン、スチレン−ブタジエン共重合体、アクリロニトリル−ブタジエン−スチレン共重合体、スチレン−ブタジエン−アクリル酸（又はそのエステル）共重合体、アクリロニトリル−スチレン共重合体、ポリウレタン、フッ素樹脂、ポリフェニレンオキシド、ポリフェニレンサルファイド、ポリスルホン、ポリエーテルスルホン、ポリケトン、ポリエーテルケトン、ポリイミド、ポリエーテルイミド、ポリベンゾイミダゾール、ポリブタジエン、ブチルゴム、シリコーン樹脂、オレフィン系熱可塑性エラストマー、スチレン系熱可塑性エラストマー、ウレタン系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、ポリアミド系熱可塑性エラストマー、ポリエーテル系熱可塑性エラストマー、ポリアクリレートを主とするコアシェル型の多層グラフト共重合体等或いはこれらの変性体である。これらの物質は必須成分ではないが、目的とする性質に応じて併用することができ、その種類、配合量は適宜選択することができる。
【００１３】
本発明の効果は、無機質充填剤を含まない液晶性ポリエステル樹脂組成物のガス発生と昇華物の低減に有効であるのは勿論のこと、一般の熱可塑性樹脂及び熱硬化性樹脂に添加される無機充填剤を添加した組成物に対しても顕著な効果を示す。
例えば、繊維状充填剤としては、ガラス繊維、アスベスト繊維、シリカ繊維、シリカ・アルミナ繊維、アルミナ繊維、ジルコニア繊維、窒化ホウ素繊維、窒化珪素繊維、カーボン繊維、ボロン繊維、チタン酸カリウム繊維、更にステンレス、アルミニウム、チタン、銅、真鍮等の金属繊維等の無機質繊維状物質が挙げられる。
一方、粉粒状充填剤としては、カーボンブラック、黒鉛、シリカ、石英粉末、ガラスビーズ、ミルドガラスファイバー、ガラスバルーン、ガラス粉、珪酸カルシウム、珪酸アルミニウム、カオリン、タルク、クレー、珪藻土、ウォラストナイトの如き珪酸塩、酸化鉄、酸化チタン、酸化亜鉛、三酸化アンチモン、アルミナの如き金属の酸化物、炭酸カルシウム、炭酸マグネシウムの如き金属の炭酸塩、硫酸カルシウム、硫酸バリウムの如き金属の硫酸塩、その他フェライト、炭化珪素、窒化珪素、窒化硼素、各種金属粉末等が挙げられる。
また、板状充填剤としてはマイカ、ガラスフレーク、各種の金属箔等が挙げられる。
これらの無機充填剤は一種又は二種以上併用することが出来る。
また本発明に用いられる無機充填剤は、所望される物性によっては公知の表面処理剤を併用することが可能である。例を示せば、エポキシ系化合物、イソシアネート系化合物、チタネート系化合物、シラン系化合物等の官能性化合物である。
好ましくは、エポキシ化合物又はポリアミド化合物などアミノ系化合物以外の化合物で処理したものが良い。
ここで、無機充填剤の配合量は液晶性ポリエステル１００ 重量部に対し１〜３００ 重量部が好ましい。
これらの充填剤はあらかじめ表面処理を施して用いるか、又は材料の調製の際同時に添加しても良い。
【００１４】
また、本発明の組成物には酸化防止剤及び熱安定剤、紫外線吸収剤、滑剤及び離型剤、染料、顔料を含む着色剤、帯電防止剤、界面活性剤、難燃剤、難燃助剤、耐熱性有機充填剤などの通常の添加剤を１種以上添加することもできる。
【００１５】
本発明の調製は、従来の樹脂組成物調製法として一般に用いられる公知の方法により容易に調製される。例えば、各成分を混合した後、押出機により練り込み押出してペレットを調製する方法、一旦組成の異なるペレットを調製し、そのペレットを所定量混合して成形に供し、成形後に目的組成の成形品を得る方法、成形機に各成分の１又は２以上を直接仕込む方法等、何れも使用できる。
また、本発明の必須成分であるホウ素化合物は、その全部又は一部を液晶性ポリエステルの製造・加工工程中の任意の時期に加えることが可能である。
【００１６】
【実施例】
次に本発明を実施例及び比較例をもってさらに具体的に説明するが、本発明はこれらに限定されるものではない。尚、各樹脂の評価は以下の通り行った。
（１）加熱減量測定
熱重量分析装置（パーキンエルマー、ＴＧＡ−７）によりペレットより切り出したサンプル２０ｍｇを用いて、３４５ ℃で溶融加熱し、溶融時間５分から２５分の間の２０分間における重量減少率を測定した。また、成形片より切り出したサンプル２０ｍｇを用いて、 ２６０℃で加熱し、加熱時間５分から２５分の間の２０分間における重量減少率を測定した。
実施例１〜１４
後述の液晶性ポリエステル樹脂Ａと表１に示す各成分を混合し、通常の押出機でペレット化したものと、それを通常の射出成形機で ０．２ｍｍ厚の試験片を成形し、それを評価した。
比較例１〜２
実施例１〜２からホウ素化合物を除いた以外は実施例１〜２と同様に評価した。
実施例１５〜１８、比較例３〜６
液晶性ポリエステル樹脂ＡをＢ〜Ｅに変えた以外は実施例２と同様に評価を行った。
実施例１９
有機燐化合物としてジ（２，６ −ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジフォスファイトを添加した以外は実施例２と同様に評価した。
【００１７】
【表１】

【００１８】
【表２】

【００１９】
【表３】

【００２０】
尚、実施例、比較例で使用した液晶性ポリエステルは、下記の構造単位を有するものである。
【００２１】
【化４】

【００２２】
【発明の効果】
以上の説明、並びに実施例にて本発明の効果は明らかな如く、液晶性ポリエステルにホウ素化合物を配合することにより、著しくガス発生と昇華物の低減された液晶性ポリエステル樹脂組成物を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a resin composition suitable for use as a relay material which generates a small amount of gas when used at a high temperature and has a small amount of sublimate during melt processing, and which has a problem in the generation of gas at a high temperature at an electric / electronic component, particularly at a high temperature. .
[0002]
Problems to be solved by the prior art and the invention
Melt-processable polyesters (hereinafter abbreviated as liquid crystalline polyesters) that can form an anisotropic molten phase have excellent mechanical, electrical, chemical, and physical properties. -Used for a wide range of applications such as electronic equipment. However, liquid crystalline polyester has a problem in the molding process that, when heated in a molten state, decomposition of the resin generates gas and sublimate, which causes fine blisters called blisters in the molded product. There's a problem. In addition, molded products made of these liquid crystalline polyesters generate gas and sublimate even when used at high temperatures, and contaminate or corrode metal contacts in electrical or electronic components such as relays, switches, and connectors. Has occurred. Thus, the reduction of gas generation and sublimation in molded articles is also a highly desired problem.
[0003]
[Means for Solving the Problems]
In view of the above problems, the present inventors have conducted intensive searches and examinations to obtain a material with reduced gas generation and sublimate during melt processing and from a molded product. It has been found that gas generation and sublimation generation can be remarkably suppressed while utilizing the properties of the liquid crystalline polyester, and the present invention has been completed.
That is, the present invention provides a high heat resistant resin composition in which 0.001 to 10 parts by weight of a boron compound is added to 100 parts by weight of a liquid crystalline polyester. Heretofore, it has not been expected at all that the boron compound is effective in suppressing gas generation and sublimation of liquid crystalline polyester.
[0004]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the components constituting the composition of the present invention will be described in detail.
The liquid crystalline polyester used in the present invention has a molecular orientation in a molten state and exhibits optical anisotropy. Observation of the anisotropy in the molten state can be confirmed by a conventional polarization inspection method using a crossed polarizer. More specifically, confirmation of the anisotropic molten phase can be performed by using a Leitz polarizing microscope and observing the molten sample placed on the Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere. When tested between crossed polarizers, the polymers of the present invention transmit polarized light and exhibit optical anisotropy, even in the melt-static state.
This can be observed as an optical pattern peculiar to the liquid crystal phase in a certain temperature range when gradually heated. Also, in X-ray diffraction, a phase-specific diffraction pattern can be observed. In thermal analysis, a differential scanning calorimeter is generally used, and entropy changes and transition temperatures of various phase transitions can be measured.
Liquid crystalline polymers suitable for use in the present invention tend to be substantially insoluble in common solvents and are therefore unsuitable for solution processing. However, as already mentioned, these polymers can be easily processed by conventional melt processing methods.
The polyester exhibiting an anisotropic melt phase used in the present invention is preferably an aromatic polyester and an aromatic polyesteramide, and a polyester partially containing the aromatic polyester and the aromatic polyesteramide in the same molecular chain is also a preferable example. .
Particularly preferred are liquid crystalline aromatic polyesters and liquid crystalline aromatic polyesteramides having at least one compound selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines and aromatic diamines as constituents.
More specifically,
1) Polyester mainly composed of one or more aromatic hydroxycarboxylic acids and derivatives thereof 2) Mainly a) One or more aromatic hydroxycarboxylic acids and derivatives thereof and b) Aromatic dicarboxylic acids and fats A) a polyester comprising one or more cyclic dicarboxylic acids and derivatives thereof and c) at least one or two or more aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof 3) mainly a) fragrance One or more aromatic hydroxycarboxylic acids and derivatives thereof and b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof and c) aromatic dicarboxylic acids, alicyclic dicarboxylic acids and the like. Polyesteramide comprising one or more derivatives 4) Mainly a) aromatic hydroxycarboxylic acid and derivatives thereof One or more and b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof and c) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof And d) an aromatic diol, an alicyclic diol, an aliphatic diol and at least one or more of its derivatives.
[0005]
Further, a molecular weight modifier may be used in combination with the above constituent components as necessary.
Preferred examples of the specific compound constituting the liquid crystalline polyester of the present invention include 2,6-naphthalenedicarboxylic acid, 2,6-dihydroquininaphthalene, 1,4-dihydroxynaphthalene and 6-hydroxy-2-naphthoic acid. Biphenyl compounds such as naphthalene compounds, 4,4'-diphenyldicarboxylic acid and 4,4'-dihydroxybiphenyl; para-substituted compounds such as p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol and p-phenylenediamine Benzene compounds and their nuclei-substituted benzene compounds (substituents are selected from chlorine, bromine, methyl, phenyl and 1-phenylethyl), meta-substituted benzene compounds such as isophthalic acid and resorcinol. Preferred examples of the specific compound include naphthalene compounds such as 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene and 6-hydroxy-2-naphthoic acid, and 4,4′-diphenyl Dicarboxylic acid, biphenyl compound such as 4,4′-dihydroxybiphenyl, a compound represented by the following general formula (III), (IV) or (V):
[0006]
Embedded image

[0007]
(However, X: a group selected from alkylene (C _{1 to} C ₄ ), alkylidene, —O—, —SO—, —SO ₂ —, —S—, and —CO— Y: — (CH ₂ ) _n — ( _{n = 1~4), - O (} CH 2) n O- (n = 1~4) from the group selected)
It is.
The liquid crystalline polyester used in the present invention may be a polyalkylene terephthalate which does not partially show an anisotropic molten phase in the same molecular chain, in addition to the above-mentioned constituent components. In this case, the alkyl group has 2 to 4 carbon atoms.
Among the above-mentioned components, those containing one or more compounds selected from a naphthalene compound, a biphenyl compound and a para-substituted benzene compound as essential components are more preferable examples. Among the p-substituted benzene compounds, p-hydroxybenzoic acid, methylhydroquinone and 1-phenylethylhydroquinone are particularly preferred examples.
Specific examples of the compound having an ester-forming functional group as a constituent component and specific examples of a polyester forming an anisotropic molten phase preferable for use in the present invention are described in JP-B-63-36633. I have.
The aromatic polyesters and polyesteramides described above also have at least about 2.0 dl / g, such as about 2.0 to 10.0 dl / g, when dissolved in pentafluorophenol at 0.1% strength by weight at 60 ° C. Logarithmic viscosities (IV) are generally indicated.
[0008]
Next, the boron compound used as an essential component in the resin composition of the present invention is one selected from a boron compound represented by the following general formula (I) or (II), a condensate thereof or a salt thereof. Two or more types.
[0009]
Embedded image

[0010]
(X, Y, Z and X ′, Y ′, Z ′, Q in the formulas (I) and (II) are —OR 2 or a monovalent organic group. Here, R 1 is H 2, P 2 or 1 Is a condensate when R 1 is P. X 1, Y 2, Z 3 or X ′, Y ′, Z ′, Q 2 may be the same or different. Or two or more of these may be linked to form a ring.)
Examples of the boron compound include an inorganic boron compound and an organic boron compound.Examples of the inorganic boron compound include boric acid compounds such as orthoboric acid, metaboric acid and tetraboric acid, diboron dioxide, diboron trioxide, and tetraboron trioxide. Examples thereof include boron oxide such as tetraboron pentoxide, ammonium salts and metal salts of boric acid, and boron phosphate. Among them, orthoboric acid, metaboric acid, tetraboric acid and boron oxide have high effects and are preferably used.
Examples of the organic boron compound include boroxine, phenylboric acid, diphenylboric acid, and a boric acid ester compound of boric acid with an alcohol compound or a phenol compound. For example, monoboric acid with C _{1 to} C ₂₀ aliphatic monoalcohols, polyhydric alcohols (such as ethylene glycol, tetrabutylene glycol, glycerin, and pentaerythritol) and phenol compounds (such as phenol, catechol, resorcinol, hydroquinone, and cresol) , Di, tri or tetra ester compounds, mixtures thereof, and metal salts thereof. Commercial products can be used as these boron compounds.
The particle size of the boron compound to be used is not particularly limited, but the smaller the particle system is, the more excellent the effect is.
In the present invention, the compounding amount of the specific boron compound is 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, more preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the liquid crystalline polyester. 3 parts by weight. As described above, a small amount of the compound exhibits a large modifying effect. If the compounding amount is less than 0.001 part by weight, the effect of suppressing the generation of gas and sublimate intended by the present invention is poor, and if it exceeds 10 parts by weight, the excess boron compound deteriorates the hue and moldability, and the physical properties of the composition Lower.
[0011]
Further, in the present invention, the effect of suppressing the generation of gas and the generation of sublimates is further improved by adding 0.05 to 5.0 parts by weight of the organic phosphorus compound to 100 parts by weight of the liquid crystalline polyester. Although the organophosphorus compound alone has little effect on the object of the present invention even when blended alone, the combined use with the boron compound increases the effect of suppressing gas generation and sublimate generation. The organic phosphorus compound has a phosphorus atom in the molecule, and includes phosphides, phosphoric acid compounds, phosphite compounds, etc., and is preferably a phosphite compound, particularly preferably a pentaerythritol type phosphite. The compound is, for example, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite.
The compounding amount of the organic phosphorus compound is preferably 0.05 to 5.0 parts by weight, particularly preferably 0.1 to 3 parts by weight, per 100 parts by weight of the melt-processable polyester capable of forming an anisotropic molten phase. If the compounding amount is less than 0.05 part by weight, the effect of the combined use is small, and if the compounding amount exceeds 5 parts by weight, a large amount of the compounded organic phosphorus compound gas is generated, which impairs the object of the present invention.
[0012]
Further, in the resin composition of the present invention, in addition to the above components, a small amount of another resin may be used in combination depending on the purpose. Here, examples of the resin mixed with the liquid crystalline polyester include polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and other aromatic dicarboxylic acids and diols or oxycarboxylic acids. Aromatic polyester, polyolefin, polyamide, polyacetal, polystyrene, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene-acrylic acid (or ester thereof) copolymer, acrylonitrile-styrene copolymer , Polyurethane, fluororesin, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyether sulfone, polyketone, polyetherketone, polyamide , Polyetherimide, polybenzimidazole, polybutadiene, butyl rubber, silicone resin, olefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, urethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polyether-based Core-shell type multilayer graft copolymers mainly composed of thermoplastic elastomers and polyacrylates and the like or modified products thereof. These substances are not essential components, but can be used in combination depending on the desired properties, and the types and amounts of the substances can be appropriately selected.
[0013]
The effect of the present invention is effective in reducing gas generation and sublimation of a liquid crystalline polyester resin composition containing no inorganic filler, as well as being added to general thermoplastic resins and thermosetting resins. It shows a remarkable effect even on a composition to which an inorganic filler is added.
For example, fibrous fillers include glass fiber, asbestos fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, carbon fiber, boron fiber, potassium titanate fiber, and stainless steel. And inorganic fibrous substances such as metal fibers such as aluminum, titanium, copper, and brass.
On the other hand, as the particulate filler, carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, wollastonite Metal oxides such as silicates, iron oxides, titanium oxides, zinc oxides, antimony trioxides, aluminas, carbonates of metals such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, etc. Examples include ferrite, silicon carbide, silicon nitride, boron nitride, and various metal powders.
Examples of the plate-like filler include mica, glass flake, various metal foils, and the like.
These inorganic fillers can be used alone or in combination of two or more.
As the inorganic filler used in the present invention, a known surface treatment agent can be used in combination depending on desired physical properties. Examples include functional compounds such as epoxy compounds, isocyanate compounds, titanate compounds, and silane compounds.
Preferably, those treated with a compound other than an amino compound such as an epoxy compound or a polyamide compound are good.
Here, the compounding amount of the inorganic filler is preferably 1 to 300 parts by weight based on 100 parts by weight of the liquid crystalline polyester.
These fillers may be used after being subjected to a surface treatment in advance, or may be added simultaneously with the preparation of the material.
[0014]
Further, the composition of the present invention includes an antioxidant and a heat stabilizer, an ultraviolet absorber, a lubricant and a release agent, a coloring agent including a dye and a pigment, an antistatic agent, a surfactant, a flame retardant, and a flame retardant auxiliary. One or more ordinary additives such as heat-resistant organic fillers may be added.
[0015]
The preparation of the present invention is easily prepared by a known method generally used as a conventional resin composition preparation method. For example, a method of mixing each component, kneading and extruding with an extruder to prepare pellets, once preparing pellets having a different composition, mixing the pellets in a predetermined amount and subjecting the mixture to molding, and after molding, a molded article of the desired composition And a method of directly charging one or two or more of each component to a molding machine.
The boron compound, which is an essential component of the present invention, can be added in whole or in part at any time during the production and processing steps of the liquid crystalline polyester.
[0016]
【Example】
Next, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. The evaluation of each resin was performed as follows.
(1) Heating loss measurement Using a 20 mg sample cut from a pellet by a thermogravimetric analyzer (Perkin Elmer, TGA-7), melt-heat at 345 ° C, and lose weight for 20 minutes during a melting time of 5 to 25 minutes. The rate was measured. In addition, 20 mg of a sample cut out of the molded piece was heated at 260 ° C., and the weight loss rate during a heating time of 5 minutes to 25 minutes for 20 minutes was measured.
Examples 1 to 14
A liquid crystalline polyester resin A described below and each of the components shown in Table 1 were mixed and pelletized with a normal extruder, and a 0.2 mm thick test piece was molded with a normal injection molding machine. evaluated.
Comparative Examples 1-2
Evaluation was performed in the same manner as in Examples 1 and 2, except that the boron compound was removed from Examples 1 and 2.
Examples 15 to 18, Comparative Examples 3 to 6
Evaluation was performed in the same manner as in Example 2 except that the liquid crystalline polyester resin A was changed to BE.
Example 19
Evaluation was performed in the same manner as in Example 2 except that di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite was added as the organic phosphorus compound.
[0017]
[Table 1]

[0018]
[Table 2]

[0019]
[Table 3]

[0020]
The liquid crystalline polyester used in Examples and Comparative Examples has the following structural units.
[0021]
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[0022]
【The invention's effect】
As apparent from the above description and Examples, the effects of the present invention are clearly shown. By blending a boron compound with a liquid crystalline polyester, a liquid crystalline polyester resin composition having significantly reduced gas generation and sublimates is provided. Can be.

Claims (7)

To 100 parts by weight of a melt-processable polyester capable of forming an anisotropic molten phase, one or two kinds selected from boron compounds represented by the following general formula (I) or ( II ), condensates or salts thereof A highly heat-resistant resin composition containing the above boron compound in an amount of 0.001 to 10 parts by weight.

( X , Y , Z and X ′ , Y ′ , Z ′ , Q in the formulas (I) and ( II ) are —OR or a monovalent organic group, wherein R is H , P or 1 A condensate when R is P. X , Y , Z or X ′ , Y ′ , Z ′ , Q may be the same or different Or two or more of these may be linked to form a ring.) The resin according to claim 1, wherein the boron compound is one or more selected from orthoboric acid, metaboric acid, tetraboric acid, boric acid, boron phosphate, borate ester, phenylboric acid, and boroxine. Composition. 3. The resin composition according to claim 1, further comprising 0.05 to 5.0 parts by weight of an organic phosphorus compound per 100 parts by weight of a melt-processable polyester capable of forming an anisotropic molten phase . The resin composition according to claim 3, wherein the organic phosphorus compound is a pentaerythritol-type phosphite compound . The resin composition according to any one of claims 1 to 4, further comprising an inorganic compound . An electric / electronic part comprising the resin composition according to claim 1. The electric / electronic component according to claim 6, wherein the electric / electronic component is for a relay.