JP2007002230A - All aromatic liquid crystal polyester resin composition and optical pickup lens holder - Google Patents
All aromatic liquid crystal polyester resin composition and optical pickup lens holder Download PDFInfo
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本発明は、情報記録再生装置に使用される光ピックアップレンズホルダーに使用される全芳香族液晶ポリエステル樹脂組成物および該樹脂組成物の射出成形体を構成部材として含む光ピックアップレンズホルダーに関する。 The present invention relates to a wholly aromatic liquid crystal polyester resin composition used for an optical pickup lens holder used in an information recording / reproducing apparatus, and an optical pickup lens holder including an injection molded body of the resin composition as a constituent member.
光ピックアップは、コンパクトディスク、レーザーディスク、ビデオディスク、光磁気ディスク等に用いられ、半導体レーザーをレンズで数μｍ径スポットまで絞って照射し、ディスク上に記録された情報を読み取るものであり、一般に発光素子、受光素子、ミラー等の光学素子等を固定する光フレームと、対物レンズ、対物レンズホルダーを光ディスクの動きに追従させるためのアクチュエーター部と、このアクチュエーター部を保持し光フレームとの光学路を形成するベースフレームとから構成されている。 An optical pickup is used for compact discs, laser discs, video discs, magneto-optical discs, etc., and irradiates a semiconductor laser with a lens down to a few μm diameter spot to read information recorded on the disc. An optical frame for fixing optical elements such as a light emitting element, a light receiving element and a mirror, an actuator part for causing the objective lens and the objective lens holder to follow the movement of the optical disc, and an optical path between the optical frame holding the actuator part And a base frame that forms
光ピックアップの軽量化、低コスト化が促進され、構成材料を金属から樹脂に代替する試みがなされており、特に液晶ポリエステル樹脂は、熱可塑性樹脂の中でも、機械的特性、成形性、寸法精度、耐熱性および制振性に優れていることからレンズホルダー、ベースフレーム等の光ピックアップ部材として注目されてきた。しかし、近年のデジタルディスク駆動装置の扱う情報の大容量化、高速化に伴い、制振特性に対する要求が厳しくなっており、これを構成する液晶ポリエステル樹脂組成物にも高度の特性が要求されるようになった。 The weight reduction and cost reduction of optical pickups have been promoted, and attempts have been made to replace the constituent material from metal to resin. In particular, liquid crystal polyester resin, among thermoplastic resins, has mechanical properties, moldability, dimensional accuracy, It has been attracting attention as an optical pickup member such as a lens holder and a base frame because of its excellent heat resistance and vibration damping properties. However, with the recent increase in capacity and speed of information handled by digital disk drive devices, the demand for vibration damping characteristics has become stricter, and the liquid crystal polyester resin composition that constitutes this demands advanced characteristics. It became so.
近年の光ピックアップレンズホルダーピックにおいては、特に厚さ０．３ｍｍ以下の部分を含むものにおいては、全芳香族液晶ポリエステル樹脂組成物のみで射出成形体を製造した場合、射出成形製品の表面でのフィブリルの発生・剥離等が問題となる場合がある。
さらに、例えば、０．３ｍｍ以下の厚み部分を含むものにおいても、共振周波数２５００Ｈｚ以上かつ損失係数０．１０以上が要求されるようになっている。また、これらは、低消費電力で駆動されることを前提としているから、金属材料では、低比重であるマグネシユウムでも比重１．８であり、損失係数は小さいから満足することができない。
In recent optical pickup lens holder picks, especially those including a portion having a thickness of 0.3 mm or less, when an injection-molded article is produced only with a wholly aromatic liquid crystal polyester resin composition, Generation of fibrils and peeling may become a problem.
Further, for example, even those including a thickness portion of 0.3 mm or less are required to have a resonance frequency of 2500 Hz or more and a loss factor of 0.10 or more. Further, since these are premised on being driven with low power consumption, even with a metal material having a low specific gravity, the specific gravity is 1.8, and the loss factor is small, which is not satisfactory.
従来から、光ピックアップ部材に適した液晶ポリエステル樹脂組成物としては、液晶ポリエステルとガラス繊維からなる樹脂組成物（特許文献１参照。）、液晶ポリエステルと炭素繊維からなる樹脂組成物（特許文献２、３参照。）が提案された。しかし、通常、ガラス繊維を充填した樹脂組成物では２次共振周波数が低くなる傾向があり、炭素繊維を充填した組成物では、２次共振周波数は高くなるが、損失係数が低くなる傾向がある。また公知の充填材を多量に含有させた場合、全芳香族ポリエステルの優れた制振性効果が十分に発揮されない場合がある。
本発明の課題は、光ピックアップレンズホルダー部品において、近年のデジタルディスク駆動装置の扱う情報の大容量化、高速化に対応する制振特性を、特定の液晶ポリエステル樹脂と特定の充填材配合とからなるポリエステル樹脂組成物を使用して解決する手段を提供することを目的とする。 An object of the present invention is to provide a vibration damping characteristic corresponding to an increase in capacity and speed of information handled by a digital disk drive device in recent years in an optical pickup lens holder part from a specific liquid crystal polyester resin and a specific filler composition. It aims at providing the means to solve using the polyester resin composition which becomes.
すなわち、本発明の第1は、ｐ−ヒドロキシ安息香酸６０〜７０モル％、テレフタル酸および４，４’−ジヒドロキシジフェニルあわせて４０〜３０モル％、イソフタル酸および／またはヒドロキノン０〜５モル％（いずれにおいてもこれらの誘導体を含む。これらの合計を１００モル％とする。）を重縮合してなる全芳香族液晶ポリエステル樹脂１００質量部と、
下式（１）を充足する、相対粒子量が５０体積％における粒径（Ｄ５０）が５〜２００μｍの球状無機中空充填材Ｘ質量部および／または数平均平均径５〜２０μｍの繊維状無機充填材Ｙ質量部とを溶融混練してなる光ピックアップレンズホルダーの射出成形に用いられる全芳香族液晶ポリエステル樹脂組成物に関するものである。
３≦Ｘ＋０．１Ｙ≦３３ （１）
但し、０≦Ｘ≦３３、０≦Ｙ≦１００ とする
That is, the first of the present invention is 60-70 mol% of p-hydroxybenzoic acid, 40-30 mol% of terephthalic acid and 4,4′-dihydroxydiphenyl together, 0-5 mol% of isophthalic acid and / or hydroquinone ( In any case, 100 parts by mass of a wholly aromatic liquid crystal polyester resin obtained by polycondensation of these derivatives is included.
Spherical inorganic hollow filler X part by mass and / or number average average diameter of 5 to 20 μm, satisfying the following formula (1), and having a particle size (D 50 ) of 5 to 200 μm at a relative particle amount of 50% by volume The present invention relates to a wholly aromatic liquid crystal polyester resin composition used for injection molding of an optical pickup lens holder obtained by melt-kneading filler Y parts by mass.
3 ≦ X + 0.1Y ≦ 33 (1)
However, 0 ≦ X ≦ 33, 0 ≦ Y ≦ 100
本発明の第２は、本発明の第１において、球状無機中空充填材が体積中空率５０％〜８０％であることを特徴とする全芳香族液晶ポリエステル樹脂組成物に関するものである。 A second aspect of the present invention relates to a wholly aromatic liquid crystal polyester resin composition according to the first aspect of the present invention, wherein the spherical inorganic hollow filler has a volume hollowness of 50% to 80%.
本発明の第３は、本発明の第１または第２において、繊維状無機充填材がガラス繊維であることを特徴とする全芳香族液晶ポリエステル樹脂組成物に関するものである。 A third aspect of the present invention relates to a wholly aromatic liquid crystal polyester resin composition according to the first or second aspect of the present invention, wherein the fibrous inorganic filler is a glass fiber.
本発明の第４は、本発明の第１〜第３のいずれかにおいて、光ピックアップレンズホルダーが厚さ０．３ｍｍ以下の部分を含むことを特徴とする全芳香族液晶ポリエステル樹脂組成物に関するものである。 A fourth aspect of the present invention relates to a wholly aromatic liquid crystal polyester resin composition according to any one of the first to third aspects of the present invention, wherein the optical pickup lens holder includes a portion having a thickness of 0.3 mm or less. It is.
本発明の第５は、本発明の第１〜３のいずれかの全芳香族液晶ポリエステル樹脂組成物を射出成形してなる光ピックアップレンズホルダーに関するものである。 5th of this invention is related with the optical pick-up lens holder formed by injection-molding the wholly aromatic liquid-crystal polyester resin composition in any one of 1-3 of this invention.
本発明の第６は、本発明の第５の光ピックアップレンズホルダーが厚さ０．３ｍｍ以下の部分を含むことを特徴とする光ピックアップレンズホルダーに関するものである。 A sixth aspect of the present invention relates to an optical pickup lens holder, wherein the fifth optical pickup lens holder of the present invention includes a portion having a thickness of 0.3 mm or less.
本発明によれば、薄肉部を有する光ピックアップレンズホルダーであっても、制振性が制御された光ピックアップレンズホルダーを得ることができる。 According to the present invention, it is possible to obtain an optical pickup lens holder with controlled damping properties even with an optical pickup lens holder having a thin wall portion.
以下、本発明を詳細に説明する。
本発明で用いる全芳香族液晶ポリエステル樹脂は、ｐ−ヒドロキシ安息香酸６０〜７０モル％、テレフタル酸および４，４’−ジヒドロキシジフェニルあわせて４０〜３０モル％、イソフタル酸および／またはヒドロキノン０〜５モル％（いずれにおいてもこれらの誘導体を含む。以下、特に断らない限り誘導体を含む。）を使用し、これらの合計を１００モル％とした原料を重縮合してなる。イソフタル酸および／またはヒドロキノンは、要求性能に応じて、任意成分として適宜使用することができる。これらの誘導体としては、公知の誘導体のいずれも用いることができるが、フェノール性水酸基をアシル化したもの、例えば、酢酸または無水酢酸によるアセチル化誘導体またはフェノール類によるフェニルエステル化誘導体が溶融重合の進行が早く副反応を抑制でき、モノマー原料の配合が全芳香族ポリエステル樹脂の分子構造に反映されるので好ましい。
Hereinafter, the present invention will be described in detail.
The wholly aromatic liquid crystal polyester resin used in the present invention is composed of 60-70 mol% of p-hydroxybenzoic acid, 40-30 mol% of terephthalic acid and 4,4′-dihydroxydiphenyl, isophthalic acid and / or hydroquinone 0-5. Mol% (in any case, including these derivatives. In the following, unless otherwise specified, derivatives are included), and these materials are polycondensed with a total of 100 mol%. Isophthalic acid and / or hydroquinone can be appropriately used as an optional component depending on the required performance. As these derivatives, any of known derivatives can be used, but those obtained by acylating a phenolic hydroxyl group, for example, an acetylated derivative with acetic acid or acetic anhydride or a phenylesterified derivative with phenols, proceed with melt polymerization. This is preferable because side reactions can be suppressed quickly and the blending of monomer raw materials is reflected in the molecular structure of the wholly aromatic polyester resin.
本発明者らは、ｐ−ヒドロキシ安息香酸、テレフタル酸、４、４´−ジヒドロキシビフェニルが全モノマーの９５〜１００モル％からなることにより全芳香族ポリエステル分子構造に高い剛直性が付与されること、かつ、その分子構造の６０〜７０モル％を特に剛直付与効果が高いｐ−ヒドロキシ安息香酸が占めること、ベンゼン環が炭素結合およびエステル結合等で連結される構造を有すること等が相乗効果的に光ピックアップレンズホルダー等に対する制振性付与に大きな効果を与えていると考えている。
特に、ｐ−ヒドロキシ安息香酸の含有量は重要であって、これは、６０モル％以下では剛直性の付与が十分でなく、７０モル％以上では溶融温度が高目となり、通常の射出成形において分解等が生じるためか成形体中での上記分子構造効果の出現が不十分となる。
The present inventors have imparted high rigidity to the wholly aromatic polyester molecular structure when p-hydroxybenzoic acid, terephthalic acid, and 4,4′-dihydroxybiphenyl are composed of 95 to 100 mol% of all monomers. In addition, it is synergistic that 60-70 mol% of the molecular structure is occupied by p-hydroxybenzoic acid, which has a particularly high rigidity imparting effect, and that the benzene ring has a structure linked by a carbon bond and an ester bond. In addition, it is considered that it has a great effect on imparting vibration damping properties to the optical pickup lens holder and the like.
In particular, the content of p-hydroxybenzoic acid is important, and it is not sufficient to impart rigidity at 60 mol% or less, and the melting temperature is high at 70 mol% or more, and in normal injection molding. Appearance of the molecular structure effect in the molded body becomes insufficient because of decomposition or the like.
全芳香族ポリエステルの融点あるいは射出成形温度の低下調整の目的で任意成分として併用可能なモノマーとしては数多くのモノマーが公知であるが、本発明の全芳香族液晶ポリエステルにおいては、上記制振特性を維持するために、イソフタル酸、ヒドロキノンを使用することが好ましい。ただし、これらの芳香族化合物が５モル％を超えると、分子構造の剛直性低下のためか制振特性が低下するので好ましくない。これらが好ましい理由は明らかではないが、これらが芳香族環を１つのみ有する構造を有していることから、これらの含有にかかわらず、全芳香族ポリエステルの分子構造において、ベンゼン環が炭素結合およびエステル結合等で連結される基本構造が保たれるためと推定される。 Many monomers are known as monomers that can be used in combination as optional components for the purpose of adjusting the melting point or injection molding temperature of the wholly aromatic polyester. In the wholly aromatic liquid crystal polyester of the present invention, the above-mentioned vibration damping characteristics are obtained. In order to maintain, it is preferable to use isophthalic acid or hydroquinone. However, if these aromatic compounds exceed 5 mol%, it is not preferable because the vibration damping characteristics deteriorate due to the decrease in the rigidity of the molecular structure. The reason why these are preferable is not clear, but because they have a structure having only one aromatic ring, the benzene ring has a carbon bond in the molecular structure of the wholly aromatic polyester, regardless of their inclusion. It is presumed that the basic structure linked by an ester bond or the like is maintained.
本発明の全芳香族液晶ポリエステルの製造は、これらのモノマーを使用して公知の溶融重縮合、または、溶融重縮合と固相重縮合で行うことができる。重縮合反応において触媒は使用してもしなくてもよい。使用する触媒としては、ポリエステルの重縮合用触媒として従来公知の触媒を使用することができ、酢酸マグネシウム、酢酸第一錫、テトラブチルチアネート、酢酸鉛、酢酸ナトリウム、酢酸カリウム、三酸化アンチモンなどの金属塩触媒、Ｎ−メチルイミダゾールなどの有機化合物触媒等が挙げられる。 Production of the wholly aromatic liquid crystal polyester of the present invention can be carried out using these monomers by known melt polycondensation, or melt polycondensation and solid phase polycondensation. A catalyst may or may not be used in the polycondensation reaction. As the catalyst to be used, a conventionally known catalyst can be used as a polyester polycondensation catalyst, such as magnesium acetate, stannous acetate, tetrabutylthianate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, etc. And an organic compound catalyst such as N-methylimidazole.
また,溶融重縮合における重合器は特に限定されるものではないが,一般の高粘度反応に用いられる攪拌設備、例えば錨型、多段型、螺旋帯、螺旋軸等の各種形状の攪拌機またはそれらを変形したものを有する攪拌槽型重合器、具体的にはワーナー式ミキサー、バンバリーミキサー、ポニーミキサー、ミュラーミキサー、ロールミル、連続操作可能のコニーダー、パグミル、ギアーコンパウンダーなどから選ぶことが望ましい。 In addition, the polymerization apparatus in the melt polycondensation is not particularly limited, but a stirring apparatus used for general high viscosity reaction, for example, a stirrer having various shapes such as a vertical type, a multistage type, a spiral band, a helical shaft, or the like. It is desirable to select from a stirred tank type polymerizer having a modified one, specifically, a Warner mixer, a Banbury mixer, a pony mixer, a Muller mixer, a roll mill, a continuous kneader, a pug mill, a gear compounder, and the like.
本発明においては、下式（１）を充足する、相対粒子量が５０体積％における粒径（Ｄ５０）が５〜２００μｍの球状無機中空充填材Ｘ質量部および／または数平均径５〜２０μｍの繊維状充填材Ｙ質量部を用い、上記全芳香族液晶ポリエステル樹脂に溶融混練する。
３ ≦Ｘ＋０．１Ｙ ≦３３ （１）
但し、０≦Ｘ≦３３、０≦Ｙ≦１００ とする
In the present invention, the spherical inorganic hollow filler X part by mass and / or the number average diameter of 5 to 20 μm satisfying the following formula (1) and having a particle size (D 50 ) of 5 to 200 μm at a relative particle amount of 50% by volume. The fibrous filler Y part by mass is melt kneaded into the wholly aromatic liquid crystal polyester resin.
3 ≦ X + 0.1Y ≦ 33 (1)
However, 0 ≦ X ≦ 33, 0 ≦ Y ≦ 100
相対粒子量が５０体積％における粒径（Ｄ５０）が５〜２００μｍの本発明に用いる球状無機中空充填材は、他の充填材と比較して低比重であることから、光ピックアップレンズホルダーにおいて本発明に係る全芳香族ポリエステルの制振性を有効に発揮できるが、全芳香族液晶ポリエステル樹脂１００質量部に対して３３質量部を越える量を配合すると、薄肉部を有する光ピックアップレンズホルダーを成形するときの流動性に問題を生じることがある。その材質の具体例としては、アルミナ、シリカ、ジルコニア、マグネシア、ガラス、シラス、フライアッシュ、ホウ酸塩，リン酸塩、セラミックス等の無機質材料からなるものが挙げられる。これら球状無機中空充填材は組成物の製造工程、成形工程等での応力の履歴を受けることによって破損が不可避であるので、強度が高いほど好ましいが、強度を追求するあまり比重の大きい材料からなる中空体を採用すると成形体が重くなって商品価値が低下することがある。これらのバランスの観点から好ましいものをあげれば、ガラスバルーンもしくはシラスバルーン、セラミックバルーンと称する微小中空体であり、最も好ましいのはガラスバルーンである。 Since the spherical inorganic hollow filler used in the present invention having a relative particle amount of 50% by volume (D 50 ) of 5 to 200 μm has a lower specific gravity than other fillers, Although the vibration damping property of the wholly aromatic polyester according to the present invention can be effectively exhibited, when an amount exceeding 33 parts by mass with respect to 100 parts by mass of the wholly aromatic liquid crystal polyester resin is blended, an optical pickup lens holder having a thin part is obtained. There may be a problem with fluidity during molding. Specific examples of the material include those made of inorganic materials such as alumina, silica, zirconia, magnesia, glass, shirasu, fly ash, borate, phosphate and ceramics. Since these spherical inorganic hollow fillers are inevitably damaged by receiving a history of stress in the production process, molding process, etc. of the composition, the higher the strength, the better. When a hollow body is adopted, the molded body becomes heavy and the commercial value may be lowered. From the viewpoint of these balances, preferred are glass hollows, shirasu balloons, and micro hollow bodies called ceramic balloons, and most preferred are glass balloons.
本発明に用いる球状無機中空充填材の形状は概球体であり、その長径と短径の比は２以下が好ましい。この比が２を超えると中空体が破損しやすく好ましくない。
また本発明に用いる球状無機中空充填材の相対粒子量が５０体積％における粒径（Ｄ５０）は５〜２００μｍのものが好ましい。粒径が５μｍ未満の場合は、得られた組成物の流動性が著しく低下してしまい好ましくなく、２００μｍを超えると溶融混練および射出成形中に球状無機中空充填材が破損し比重が変動してしまうため好ましくない。特に好ましくは平均１０〜１００μｍである。
本発明に用いる球状無機中空充填材の体積中空率は、光ピックアップレンズホルダー製品の低熱伝導率化および比重低下のためには５０％以上のものが好ましく、また、球状無機中空充填材の破損率制御のために８０％以下のものが好ましい。即ち、球状無機中空充填材の体積中空率が８０％を超えると、溶融混練において球状無機中空充填材の破損率が上昇し、得られる組成物の熱伝導率および比重にばらつき生じるため好ましくない。なお、体積中空率とは、１００×（１−微小中空体の真比重／微小中空体の材料比重）で求めることができる。球状無機中空充填材の体積中空率が５０％以下では、製品の熱伝導率および比重を低下させる効果が低く好ましくない。
The shape of the spherical inorganic hollow filler used in the present invention is almost spherical, and the ratio of the major axis to the minor axis is preferably 2 or less. If this ratio exceeds 2, the hollow body tends to break, which is not preferable.
The particle size relative particle amount of the spherical inorganic hollow filler used in the present invention in 50 volume% (D 50) is preferably from 5 to 200 [mu] m. When the particle size is less than 5 μm, the fluidity of the resulting composition is remarkably lowered, which is not preferable. When it exceeds 200 μm, the spherical inorganic hollow filler is damaged during melt-kneading and injection molding, and the specific gravity varies. Therefore, it is not preferable. Most preferably, it is 10-100 micrometers on average.
The volumetric hollow ratio of the spherical inorganic hollow filler used in the present invention is preferably 50% or more in order to reduce the thermal conductivity and decrease the specific gravity of the optical pickup lens holder product. 80% or less is preferable for control. That is, when the volumetric hollow ratio of the spherical inorganic hollow filler exceeds 80%, the damage ratio of the spherical inorganic hollow filler increases during melt-kneading, and the thermal conductivity and specific gravity of the resulting composition vary. The volumetric hollow ratio can be obtained by 100 × (1−true specific gravity of micro hollow body / material specific gravity of micro hollow body). When the volumetric hollow ratio of the spherical inorganic hollow filler is 50% or less, the effect of lowering the thermal conductivity and specific gravity of the product is low, which is not preferable.
球状無機中空充填材の具体的な例示としては、住友スリーエム(株)製のグラスバブルス（商品名：スコッチライトＳ−６０）、東海工業(株)製のガラス微小中空体（商品名：セルスターＰＺ−６０００）などが挙げられる。これらは必要に応じて全芳香族液晶ポリエステルとの密着性を向上させるために、シランカップリング剤などによる予備処理を施すこともできる。 Specific examples of the spherical inorganic hollow filler include glass bubbles (trade name: Scotchlite S-60) manufactured by Sumitomo 3M Limited, and glass micro hollow bodies (trade name: Cellstar PZ manufactured by Tokai Kogyo Co., Ltd.). -6000). These may be subjected to a pretreatment with a silane coupling agent or the like in order to improve the adhesion with the wholly aromatic liquid crystalline polyester as necessary.
本発明に用いる繊維状無機充填材のアスペクト比は２０以上が好ましい。アスペクト比２０以上の場合は全芳香族液晶ポリエステルの射出成形時の流動性を向上させるのに有効である。アスペクト比２０未満の場合は弾性特性の向上効果が発現せず、比重を大きくする弊害が発生してしまうので好ましくない。
本発明に用いる繊維状無機充填材の全芳香族液晶ポリエステル樹脂１００質量部に対する配合量は１００質量部以下であり、例えばガラス繊維は比重が約２．７程度あるため、１００質量部を越えて配合すると光ピックアップレンズホルダー自体の比重と全芳香族ポリエステルとの比重（約１．４）との解離が大きくなるためか、本発明に係る全芳香族ポリエステルの制振性に係る特性を十分に発揮することができなくなることがある。
本発明に用いる繊維状無機充填材の具体的な例としては、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、チタン酸カリウム繊維、炭素もしくは黒鉛繊維、さらにアルミニウム、チタン、銅などの金属の繊維状物質、タルク、マイカ、ガラスフレーク、ウオラストナイトがあげられる。
これらの中でも、数平均径５〜２０μｍのガラス繊維が射出成形時の流動特性の点から好ましい。数平均径が５μｍ未満の場合は、人体に与える影響を勘案すると好ましくなく、２０μｍを超えると弾性特性の向上効果が充分でなくで好ましくない。さらに好ましい平均径は、射出成形時の流動性および成形体の表面特性から、７〜１５μｍ、特に好ましくは、９〜１２μｍである。繊維状無機充填材は混練作業中に切断が生じることを考慮して適切な長さのものを使用する。ガラス繊維ロービングのような長繊維の繊維状無機充填材であっても、常法に従い、適宜混練条件または混練機を選択すれば、混練操作中に切断が生じて、適切な繊維長に収まる。
The aspect ratio of the fibrous inorganic filler used in the present invention is preferably 20 or more. When the aspect ratio is 20 or more, it is effective for improving the fluidity at the time of injection molding of the wholly aromatic liquid crystal polyester. An aspect ratio of less than 20 is not preferable because the effect of improving the elastic properties is not manifested and the adverse effect of increasing the specific gravity occurs.
The blending amount of the fibrous inorganic filler used in the present invention with respect to 100 parts by mass of the wholly aromatic liquid crystalline polyester resin is 100 parts by mass or less. For example, glass fiber has a specific gravity of about 2.7. If blended, the dissociation between the specific gravity of the optical pickup lens holder itself and the specific gravity of the wholly aromatic polyester (about 1.4) will increase, so the characteristics related to vibration damping of the wholly aromatic polyester according to the present invention will be sufficient. You may not be able to demonstrate it.
Specific examples of the fibrous inorganic filler used in the present invention include glass fibers, asbestos fibers, silica fibers, silica alumina fibers, potassium titanate fibers, carbon or graphite fibers, and metals such as aluminum, titanium, and copper. Examples include fibrous substances, talc, mica, glass flakes, and wollastonite.
Among these, glass fibers having a number average diameter of 5 to 20 μm are preferable from the viewpoint of flow characteristics at the time of injection molding. When the number average diameter is less than 5 μm, it is not preferable in view of the influence on the human body, and when it exceeds 20 μm, the effect of improving the elastic properties is not sufficient, which is not preferable. A more preferable average diameter is 7 to 15 μm, particularly preferably 9 to 12 μm, from the fluidity during injection molding and the surface characteristics of the molded body. A fibrous inorganic filler having an appropriate length is used in consideration of the fact that cutting occurs during the kneading operation. Even in the case of a long-fiber fibrous inorganic filler such as glass fiber roving, if an appropriate kneading condition or kneader is selected according to a conventional method, cutting occurs during the kneading operation, and the fiber becomes an appropriate fiber length.
相対粒子量が５０体積％における粒径（Ｄ５０）が５〜２００μｍの本発明の全芳香族液晶ポリエステル樹脂組成物の球状無機中空充填材の配合量Ｘ質量部と数平均径５〜２０μｍの、繊維状充填材の配合量Ｙ質量部との間に、次の関係式（１）が成り立つことが必要である。
３ ≦Ｘ＋０．１Ｙ ≦３３ （１）
（但し、０≦Ｘ≦３３、０≦Ｙ≦１００）
Ｘ＋０．１Ｙが３より小さいときは、まず、フィブリルの生成可能性に起因する表面特性低下の観点から好ましくない。Ｘ＋０．１Ｙが３３より大きいときは、射出成形時の流動性不足に起因する表面特性低下の観点から好ましくない。Ｘ＋０．１Ｙの特に好ましい範囲は、５〜１５である。
The amount X of the spherical inorganic hollow filler of the wholly aromatic liquid crystal polyester resin composition of the present invention having a relative particle amount of 50% by volume (D 50 ) of 5 to 200 μm and a number average diameter of 5 to 20 μm. The following relational expression (1) needs to be established between the amount Y of the fibrous filler and Y part by mass.
3 ≦ X + 0.1Y ≦ 33 (1)
(However, 0 ≦ X ≦ 33, 0 ≦ Y ≦ 100)
When X + 0.1Y is smaller than 3, first, it is not preferable from the viewpoint of surface property degradation due to the possibility of fibril formation. When X + 0.1Y is larger than 33, it is not preferable from the viewpoint of deterioration of surface characteristics due to insufficient fluidity during injection molding. A particularly preferred range of X + 0.1Y is 5-15.
本発明では、その効果を妨げない範囲で他の充填材、例えば、カーボンブラック、黒鉛、シリカ、石英粉末、ガラスビーズ、ガラス粉、ケイ酸カルシウム、ケイ酸アルミニウム、タルク、クレー、ケイ藻土、などのケイ酸塩、酸化鉄、酸化チタン、酸化亜鉛、三酸化アンチモン、アルミナ、硫酸カルシウム、その他各種金属粉末、各種金属箔、フッ素系ポリマー、芳香族ポリエステル、芳香族ポリイミド、ポリアミドなどからなる耐熱性高強度の繊維のような有機充填材などが挙げられる。 In the present invention, other fillers, such as carbon black, graphite, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, talc, clay, diatomaceous earth, as long as the effect is not hindered. Heat resistance made of silicate, iron oxide, titanium oxide, zinc oxide, antimony trioxide, alumina, calcium sulfate, other various metal powders, various metal foils, fluorine-based polymer, aromatic polyester, aromatic polyimide, polyamide, etc. Organic fillers such as high strength fibers.
更に、本発明の組成物には、本発明の目的を損なわない範囲で、酸化防止剤および熱安定剤（たとえばヒンダードフェノール、ヒドロキノン、ホスファイト類およびこれらの置換体など）、紫外線吸収剤（たとえばレゾルシノール、サリシレート、ベンゾトリアゾール、ベンゾフェノンなど）、滑剤および離型剤（モンタン酸およびその塩、そのエステル、そのハーフエステル、ステアリルアルコール、ステアラミドおよびポリエチレンワックスなど）、染料（たとえばニグロシンなど）および顔料（たとえば硫化カドミウム、フタロシアニン、カーボンブラックなど）を含む着色剤、可塑剤、帯電防止剤、難燃剤などの通常の添加剤や他の熱可塑性樹脂を添加して、所定の特性を付与することができる。 Furthermore, the composition of the present invention includes an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and substituted products thereof), an ultraviolet absorber (in the range not detracting from the object of the present invention). Such as resorcinol, salicylate, benzotriazole, benzophenone), lubricants and mold release agents (such as montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax), dyes (such as nigrosine) and pigments (such as nigrosine) For example, colorants including cadmium sulfide, phthalocyanine, carbon black, etc.), ordinary additives such as plasticizers, antistatic agents, flame retardants, and other thermoplastic resins can be added to impart predetermined characteristics. .
本発明の全芳香族液晶ポリエステル樹脂組成物は、当該技術分野で一般的に使用されている溶融混練方法で得ることができるものであり、製造方法に特に制限はない。好ましい製造法としては、１対の２条スクリュを有する混練機で、ホッパーから投入した全芳香族液晶ポリエステルを溶融後、中途フィード口から充填材、すなわち繊維状無機充填材および／または球状無機中空充填材、を投入する方法が挙げられる。この混練機は、２軸混練機と呼ばれるものであり、その中でも切り替えし機構を有することで充填材の均一分散を可能とする同方向回転式であるもの、充填材の食い込みが容易となるバレル−スクリュウ間の空隙が大きい４０ｍｍφ以上のシリンダー径を有するものが好ましい。さらに、スクリュウ間の大きいかみ合い率１．４５以上のものを使用すると、充填材の破損が避けることができ、本発明に係る全芳香族ポリエステル樹脂組成物が効率よく得ることができる。 The wholly aromatic liquid crystal polyester resin composition of the present invention can be obtained by a melt-kneading method generally used in the technical field, and the production method is not particularly limited. As a preferable production method, a wholly aromatic liquid crystal polyester charged from a hopper is melted in a kneader having a pair of two-screws, and then a filler, that is, a fibrous inorganic filler and / or a spherical inorganic hollow is fed from a midway feed port. A method of charging the filler is mentioned. This kneading machine is called a twin-screw kneading machine. Among them, it is a co-rotating type that enables uniform dispersion of the filler by switching and having a mechanism, and a barrel that can easily bite the filler. -What has the cylinder diameter of 40 mmφ or more with a large space | gap between screws is preferable. Further, when a material having a large engagement ratio between screws of 1.45 or more can be used, damage to the filler can be avoided, and the wholly aromatic polyester resin composition according to the present invention can be obtained efficiently.
このようにして得られる全芳香族液晶ポリエステル樹脂組成物は、2次共振周波数と損失係数が共に優れており、０．５ｍｍ以下、好ましくは０．３〜０．０５ｍｍの厚みを有する光ピックアップレンズホルダー部材として好適である。 The fully aromatic liquid crystal polyester resin composition thus obtained has an excellent secondary resonance frequency and loss factor, and is an optical pickup lens having a thickness of 0.5 mm or less, preferably 0.3 to 0.05 mm. Suitable as a holder member.
以下、実施例および比較例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。
なお実施例、比較例に示した比重については、６５ｍｍ×１２．７ｍｍ×３．０ｍｍの射出成形品を用いて、ＡＳＴＭ Ｄ７９０に準拠して測定した。
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.
In addition, about the specific gravity shown to the Example and the comparative example, it measured based on ASTM D790 using the injection molded product of 65 mm x 12.7 mm x 3.0 mm.
以下のとおり全芳香族液晶ポリエステルＡ〜Ｆを製造した。全芳香族液晶ポリエステルＡ〜Ｃは本発明の要件を充足するものであり、全芳香族液晶ポリエステルＤ〜Ｆは本発明の要件を充足しないものである。 Fully aromatic liquid crystal polyesters A to F were produced as follows. The wholly aromatic liquid crystal polyesters A to C satisfy the requirements of the present invention, and the wholly aromatic liquid crystal polyesters D to F do not satisfy the requirements of the present invention.
全芳香族液晶ポリエステルＡの製造：
溶融重縮合：ＳＵＳ３１６を材質とし、ダブルヘリカル攪拌翼を有する１７００Ｌ重合槽（神戸製鋼所製）にｐ−ヒドロキシ安息香酸１９７．５ｋｇ（１．４３キロモル：６５モル％）、４，４’−ジヒドロキシジフェニル７１．７ｋｇ（０．３８５キロモル：１７．５モル％）、テレフタル酸６４．０ｋｇ（０．３８５キロモル：１７．５モル％）、触媒として酢酸カリウム０．０６ｋｇを仕込み、重合槽の減圧−窒素注入を２回行って窒素置換した後、無水酢酸２４２．６ｋｇ（２．３キロモル）を添加し、攪拌翼の回転数４５ｒｐｍで１５０℃まで１．５時間で昇温して還流状態で２時間アセチル化反応を行った。アセチル化終了後、酢酸留出状態にして０．５℃／分で昇温して、３０５℃において重合物を重合槽下部の抜き出し口から取り出した。
Production of wholly aromatic liquid crystalline polyester A:
Melt polycondensation: p-hydroxybenzoic acid 197.5 kg (1.43 kgol: 65 mol%), 4,4′-dihydroxy in a 1700 L polymerization tank (manufactured by Kobe Steel) made of SUS316 and having a double helical stirring blade Diphenyl 71.7 kg (0.385 kgol: 17.5 mol%), terephthalic acid 64.0 kg (0.385 kgol: 17.5 mol%) and 0.06 kg of potassium acetate as a catalyst were charged, and the pressure in the polymerization tank was reduced. Nitrogen was injected twice to replace the nitrogen, and then 242.6 kg (2.3 kgol) of acetic anhydride was added, and the temperature was raised to 150 ° C. for 1.5 hours with a stirring blade rotating at 45 rpm. A time acetylation reaction was performed. After the completion of acetylation, acetic acid was distilled off, the temperature was raised at 0.5 ° C./min, and the polymer was taken out from the outlet at the bottom of the polymerization tank at 305 ° C.
固相重縮合：
取り出した該重合体を冷却固化した後、ホソカワミクロン株式会社製の粉砕機により粉砕してプレポリマーを得た。得られたプレポリマーは、高砂工業株式会社製のロータリーキルンを用い固相重縮合を行った。キルン内筒の形状は概ね正６角形であり、一辺の長さ５００ｍｍ、全長３５００ｍｍである。プレポリマーを該キルンに１５０ｋｇ充填し、窒素を１５Ｎｍ３／時間流通し、回転数２ｒｐｍでヒーター内の温度を室温から４００℃まで５時間で昇温し、４００℃で１２時間保持した。粉砕物の温度が３４０℃に到達したことを確認し、加熱を停止してロータリーキルンを回転しながら７時間冷却して全芳香族液晶ポリエステルＡを得た。
Solid phase polycondensation:
The polymer taken out was cooled and solidified, and then pulverized by a pulverizer manufactured by Hosokawa Micron Corporation to obtain a prepolymer. The obtained prepolymer was subjected to solid phase polycondensation using a rotary kiln manufactured by Takasago Industry Co., Ltd. The shape of the kiln inner cylinder is generally a regular hexagon, and has a side length of 500 mm and a total length of 3500 mm. The kiln was filled with 150 kg of the prepolymer, nitrogen was supplied at 15 Nm 3 / hour, the temperature in the heater was raised from room temperature to 400 ° C. in 5 hours at a rotation speed of 2 rpm, and held at 400 ° C. for 12 hours. After confirming that the temperature of the pulverized product reached 340 ° C., the heating was stopped and the rotary kiln was rotated and cooled for 7 hours to obtain a wholly aromatic liquid crystal polyester A.
全芳香族液晶ポリエステルＢの製造：
全芳香族液晶ポリエステルＡにおける原料の配合を、ｐ−ヒドロキシ安息香酸１９７．５ｋｇ（１．４３キロモル：６５モル％）、４，４’−ジヒドロキシジフェニル７１．７ｋｇ（０．３８５キロモル：１７．５モル％）、テレフタル酸６０．３ｋｇ（０．３６３キロモル：１６．５モル％）、イソフタル酸３．６５ｋｇ（０．０２２キロモル：１．０モル％）、に変え、以下全芳香族液晶ポリエステルＡと同様に溶融重縮合と固相重縮合を行い、全芳香族液晶ポリエステルＢを得た。
Production of wholly aromatic liquid crystal polyester B:
The composition of the raw materials in the wholly aromatic liquid crystal polyester A is 197.5 kg (1.43 kgol: 65 mol%) of p-hydroxybenzoic acid, 71.7 kg (0.385 kgol: 17.5 kg) of 4,4′-dihydroxydiphenyl. Mol%), terephthalic acid 60.3 kg (0.363 kgol: 16.5 mol%), isophthalic acid 3.65 kg (0.022 kgol: 1.0 mol%), In the same manner as above, melt polycondensation and solid phase polycondensation were performed to obtain wholly aromatic liquid crystal polyester B.
全芳香族液晶ポリエステルＣの製造：
全芳香族液晶ポリエステルＡにおける原料の配合を、ｐ−ヒドロキシ安息香酸１９７．５ｋｇ（１．４３キロモル：６５モル％）、４，４’−ジヒドロキシジフェニル７１．７ｋｇ（０．３８５キロモル：１７．５モル％）、テレフタル酸６０．３ｋｇ（０．３６３キロモル：１６．５モル％）、ヒドロキノン２．４２ｋｇ（０．０２２キロモル：１．０モル％）、に変え、以下全芳香族液晶ポリエステルＡと同様に溶融重縮合と固相重縮合を行い、全芳香族液晶ポリエステルＣを得た。
Production of wholly aromatic liquid crystal polyester C:
The composition of the raw materials in the wholly aromatic liquid crystal polyester A is 197.5 kg (1.43 kgol: 65 mol%) of p-hydroxybenzoic acid, 71.7 kg (0.385 kgol: 17.5 kg) of 4,4′-dihydroxydiphenyl. Mol%), terephthalic acid 60.3 kg (0.363 kgol: 16.5 mol%), hydroquinone 2.42 kg (0.022 kgol: 1.0 mol%), Similarly, melt polycondensation and solid phase polycondensation were carried out to obtain wholly aromatic liquid crystal polyester C.
全芳香族液晶ポリエステルＤの製造：
全芳香族液晶ポリエステルＡにおける原料の配合を、ｐ−ヒドロキシ安息香酸１５１．９ｋｇ（１．１キロモル：５０モル％）、４，４’−ジヒドロキシジフェニル１０２．４ｋｇ（０．５５キロモル：２５モル％）、テレフタル酸９１．４ｋｇ（０．５５キロモル：２５モル％）、に変え、以下全芳香族液晶ポリエステルＡと同様に溶融重縮合と固相重縮合を行い、全芳香族液晶ポリエステルＤを得た。
Production of wholly aromatic liquid crystal polyester D:
The blend of the raw materials in the wholly aromatic liquid crystal polyester A is p-hydroxybenzoic acid 151.9 kg (1.1 kgol: 50 mol%), 4,4′-dihydroxydiphenyl 102.4 kg (0.55 kgol: 25 mol%). ), 91.4 kg (0.55 kgol: 25 mol%) of terephthalic acid, and thereafter, melt polycondensation and solid phase polycondensation are carried out in the same manner as wholly aromatic liquid crystal polyester A to obtain wholly aromatic liquid crystal polyester D. It was.
全芳香族液晶ポリエステルＥの製造：
全芳香族液晶ポリエステルＡにおける原料の配合を、ｐ−ヒドロキシ安息香酸２２７．９ｋｇ（１．６５キロモル：７５モル％）、４，４’−ジヒドロキシジフェニル５１．２ｋｇ（０．２７５キロモル：１２．５モル％）、テレフタル酸４５．７ｋｇ（０．２７５キロモル：１２．５モル％）、に変え、以下全芳香族液晶ポリエステルＡと同様に溶融重縮合と固相重縮合を行い、全芳香族液晶ポリエステルＥを得た。
Production of wholly aromatic liquid crystal polyester E:
The composition of the raw materials in the wholly aromatic liquid crystal polyester A is 227.9 kg (1.65 kg: 75 mol%) of p-hydroxybenzoic acid, 51.2 kg (0.275 kgol: 12.5 kg) of 4,4′-dihydroxydiphenyl. Mol%) and 45.7 kg (0.275 kgol: 12.5 mol%) of terephthalic acid, and then, as in the case of the wholly aromatic liquid crystal polyester A, melt polycondensation and solid phase polycondensation are performed to obtain wholly aromatic liquid crystals. Polyester E was obtained.
全芳香族液晶ポリエステルＦの製造：
全芳香族液晶ポリエステルＡにおける原料の配合を、ｐ−ヒドロキシ安息香酸１９７．５ｋｇ（１．４３キロモル：６５モル％）、４，４’−ジヒドロキシジフェニル７１．７ｋｇ（０．３８５キロモル：１７．５モル％）、テレフタル酸６０．３ｋｇ（０．３６３キロモル：１６．５モル％）、２，６−ナフタレンジカルボン酸４．７６ｋｇ（０．０２２キロモル：１．０モル％）、に変え、以下同様の溶融重合と固相重縮合を行い、全芳香族液晶ポリエステルＦを得た。
Production of wholly aromatic liquid crystal polyester F:
The composition of the raw materials in the wholly aromatic liquid crystal polyester A is 197.5 kg (1.43 kgol: 65 mol%) of p-hydroxybenzoic acid, 71.7 kg (0.385 kgol: 17.5 kg) of 4,4′-dihydroxydiphenyl. Mol%), terephthalic acid 60.3 kg (0.363 kgol: 16.5 mol%), 2,6-naphthalenedicarboxylic acid 4.76 kg (0.022 kgol: 1.0 mol%), and so on. Was subjected to melt polymerization and solid phase polycondensation to obtain wholly aromatic liquid crystal polyester F.
全芳香族液晶ポリエステルＧの製造：
全芳香族液晶ポリエステルＡにおける原料の配合を、ｐ−ヒドロキシ安息香酸１９１．４ｋｇ（１．３８６キロモル：６３モル％）、４，４’−ジヒドロキシジフェニル７５．８ｋｇ（０．４０７キロモル：１８．５モル％）、テレフタル酸６７．６ｋｇ（０．４０７キロモル：１８．５モル％）、に変え、以下全芳香族液晶ポリエステルＡと同様に溶融重縮合と固相重縮合を行い、全芳香族液晶ポリエステルＧを得た。
Production of wholly aromatic liquid crystal polyester G:
The total aromatic liquid crystal polyester A was blended with raw materials of 191.4 kg of p-hydroxybenzoic acid (1.386 kgol: 63 mol%), 75.8 kg of 4,4′-dihydroxydiphenyl (0.407 kgol: 18.5). Mol%) and 67.6 kg of terephthalic acid (0.407 kilomol: 18.5 mol%), and then, as in the case of the wholly aromatic liquid crystal polyester A, melt polycondensation and solid phase polycondensation are performed to obtain wholly aromatic liquid crystals. Polyester G was obtained.
全芳香族液晶ポリエステルＨの製造：
全芳香族液晶ポリエステルＡにおける原料の配合を、ｐ−ヒドロキシ安息香酸２０６．６ｋｇ（１．４９６キロモル：６８モル％）、４，４’−ジヒドロキシジフェニル６５．５ｋｇ（０．３５２キロモル：１６モル％）、テレフタル酸５８．５ｋｇ（０．３５２キロモル：１６モル％）、に変え、以下全芳香族液晶ポリエステルＡと同様に溶融重縮合と固相重縮合を行い、全芳香族液晶ポリエステルＨを得た。
Production of wholly aromatic liquid crystal polyester H:
The total aromatic liquid crystal polyester A was blended with raw materials of 206.6 kg of p-hydroxybenzoic acid (1.496 kgol: 68 mol%) and 65.5 kg of 4,4′-dihydroxydiphenyl (0.352 kgol: 16 mol%). ), 58.5 kg (0.352 kgol: 16 mol%) of terephthalic acid, and thereafter, polycondensation and solid-phase polycondensation are carried out in the same manner as for the wholly aromatic liquid crystalline polyester A to obtain wholly aromatic liquid crystalline polyester H. It was.
充填材は以下のものを、市場から入手してそのまま使用した。
（１）繊維状無機充填材（ガラス繊維）：ＰＸ−１：旭ファイバーグラス（株）製のガラス繊維（チョップドガラスファイバー）。（アスペクト比３５０、数平均繊維径１０μｍ、数平均繊維長さ３．５ｍｍ、比重２．５４）
数平均繊維径の測定方法：ガラス繊維をルツボ中で焼成した後、そのガラス繊維１００ｍｇを１００ｃｃの石鹸水中に分散させ、その分散液をスパチュラでスライドガラス上に置き、顕微鏡下に観察して写真撮影した。その写真に投影されたガラス繊維の繊維径を５０本測定して数平均繊維径を求めた。
（２）球状無機中空充填材：
Ｓ−６０：住友３Ｍ（株）製のソーダ石灰ホウケイ酸ガラス球状中空体。（アスペクト比１、相対粒子量が５０体積％における粒径（Ｄ５０）３０μｍ、真比重０．６０、材料比重２．５０、体積中空率７６％）
粒径（Ｄ５０）の測定方法：レーザー回折／散乱式粒度分布測定装置により、分散媒として純水を使用し、超音波バスを用いて分散させ、循環系により相対粒子量が５０体積％における粒径（Ｄ５０）を測定した。
The following fillers were obtained from the market and used as they were.
(1) Fibrous inorganic filler (glass fiber): PX-1: Glass fiber (chopped glass fiber) manufactured by Asahi Fiber Glass Co., Ltd. (Aspect ratio 350, number average fiber diameter 10 μm, number average fiber length 3.5 mm, specific gravity 2.54)
Number average fiber diameter measurement method: After firing glass fibers in a crucible, 100 mg of the glass fibers are dispersed in 100 cc soapy water, and the dispersion is placed on a slide glass with a spatula and observed under a microscope to photograph I took a picture. The number average fiber diameter was determined by measuring the fiber diameter of 50 glass fibers projected on the photograph.
(2) Spherical inorganic hollow filler:
S-60: Soda lime borosilicate glass spherical hollow body manufactured by Sumitomo 3M Co., Ltd. (Aspect ratio 1, particle size (D 50 ) 30 μm, relative particle amount 50 volume%, true specific gravity 0.60, material specific gravity 2.50, volume hollowness 76%)
Measuring method of particle size (D 50 ): Using a laser diffraction / scattering particle size distribution measuring device, pure water is used as a dispersion medium, dispersed using an ultrasonic bath, and the relative particle amount is 50% by volume using a circulation system. The particle size (D 50 ) was measured.
全芳香族液晶ポリエステル樹脂組成物の製造：
表１に記載の配合割合の全芳香族液晶ポリエステル、ガラス繊維、および球状無機中空充填材を用いて、全芳香族液晶ポリエステルと所定量のガラス繊維とをあらかじめリボンブレンダーで混合し、この混合物を２軸押出機（（株）神戸製鋼所製ＫＴＸ−４６）のホッパーから投入して、シリンダーの最高温度４１０℃で溶融混練してペレットを得た。なお、無機中空球体は、途中のベント孔から投入した。
Production of wholly aromatic liquid crystal polyester resin composition:
Using the wholly aromatic liquid crystal polyester, glass fiber, and spherical inorganic hollow filler in the blending ratio shown in Table 1, the wholly aromatic liquid crystal polyester and a predetermined amount of glass fiber are mixed in advance with a ribbon blender, and this mixture is mixed. The pellets were obtained by charging from a hopper of a twin screw extruder (KTX-46 manufactured by Kobe Steel) and melt kneading at a maximum temperature of 410 ° C. of the cylinder. The inorganic hollow sphere was introduced through a vent hole in the middle.
光ピックアップレンズホルダーとしての制振特性等の評価：
試験片：各樹脂組成物のペレットから、射出成形機（住友重機械工業（株）製ＳＧ−２５）を用いてシリンダー温度４１０℃の条件で、下記試験用の試験片を各５個づつ成形した。
Evaluation of vibration control characteristics as an optical pickup lens holder:
Test piece: Five test pieces for each of the following tests were molded from pellets of each resin composition using an injection molding machine (SG-25 manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 410 ° C. did.
試験方法：
（１）２次共振周波数、損失係数
幅１２．７ｍｍ、厚み０．３ｍｍ、長さ４０ｍｍの試験片により、ＪＩＳ Ｇ ０６０２に準じて測定を行った。上記試験片をブリュエルケア−社の加振器に有効長２０ｍｍとなるように試験片の１端を取り付け、ポリテック社のレーザー振動計にて測定を行った。２次共振点の周波数を共振周波数とし、そのときの損失係数を半値幅法により求めた．
（２）成形性（成形品外観）
幅１２．７ｍｍ、厚さ０．３ｍｍ、長さ５０ｍｍの試験片について、ルーペにて成形性を観察し、表面にフィブリル等の剥離、流動性不良による面荒れの有無を確認した。
Test method:
(1) Secondary resonance frequency, loss factor Measurement was performed according to JIS G 0602 with a test piece having a width of 12.7 mm, a thickness of 0.3 mm, and a length of 40 mm. One end of the test piece was attached to a Bruel Care-excited vibrator so as to have an effective length of 20 mm, and the measurement was performed with a polytec laser vibrometer. The frequency at the secondary resonance point was taken as the resonance frequency, and the loss factor at that time was determined by the half-width method.
(2) Formability (Appearance of molded product)
With respect to a test piece having a width of 12.7 mm, a thickness of 0.3 mm, and a length of 50 mm, the moldability was observed with a magnifying glass, and the presence or absence of surface roughness due to peeling of fibrils and poor fluidity on the surface was confirmed.
表１にそれぞれの樹脂組成物の射出成形品の評価結果を示した。
表１に示すように、本発明に従って製造された実施例１〜９の全芳香族ポリエステル樹脂組成物は、良好な成形性を示し、得られた射出成形品は、２次共振周波数および損失係数ともに良好な結果となり、制振性能に優れていた。これに対し、全芳香族液晶ポリエステルＤ〜Ｆを使用した比較例１〜４の樹脂組成物および成形品、全芳香族液晶ポリエステルＡ〜Ｃを用いたが充填材の配合量が本発明の範囲外の比較例５，６，７の樹脂組成物および成形品は、成形性、制振性のいずれかまたは両方が、本発明に従って製造されたものより劣っていた。 As shown in Table 1, the wholly aromatic polyester resin compositions of Examples 1 to 9 produced according to the present invention showed good moldability, and the obtained injection-molded product had a secondary resonance frequency and a loss factor. Both showed good results and excellent damping performance. In contrast, the resin compositions and molded articles of Comparative Examples 1 to 4 using wholly aromatic liquid crystal polyesters D to F and wholly aromatic liquid crystal polyesters A to C were used, but the blending amount of the filler was within the scope of the present invention. The resin compositions and molded articles of the other Comparative Examples 5, 6, and 7 were inferior in moldability and / or vibration damping properties to those produced according to the present invention.
本発明の全芳香族液晶ポリエステル樹脂成形体は、薄肉部を有する光ピックアップレンズホルダー成形材料として、特に、近年のデジタルディスク駆動装置の扱う情報の大容量化、高速化に伴い、制振特性に対する要求が厳しい光ピックアップレンズホルダー成形材料として使用でき、得られた光ピックアップレンズホルダーは、優れた制振性能を有する。 The wholly aromatic liquid crystal polyester resin molding of the present invention is an optical pickup lens holder molding material having a thin-walled portion, and in particular, with respect to vibration damping characteristics with the increase in capacity and speed of information handled in recent digital disk drive devices. The optical pickup lens holder can be used as a demanding optical pickup lens holder molding material, and the obtained optical pickup lens holder has excellent vibration damping performance.
Claims (6)
３≦Ｘ＋０．１Ｙ≦３３ （１）
但し、０≦Ｘ≦３３、０≦Ｙ≦１００ とする 60-70 mol% of p-hydroxybenzoic acid, 40-30 mol% of terephthalic acid and / or 4,4′-dihydroxydiphenyl in total, 0-5 mol% of isophthalic acid and / or hydroquinone (in any case, these derivatives are used) And 100 parts by mass of a wholly aromatic liquid crystalline polyester resin obtained by polycondensation) and a particle size (relative particle amount of 50% by volume) satisfying the following formula (1): D 50 ) is used for injection molding of an optical pickup lens holder formed by melt-kneading a spherical inorganic hollow filler X part by mass of 5 to 200 μm and / or a fibrous inorganic filler Y part by mass of a mean diameter of 5 to 20 μm. Wholly aromatic liquid crystal polyester resin composition.
3 ≦ X + 0.1Y ≦ 33 (1)
However, 0 ≦ X ≦ 33, 0 ≦ Y ≦ 100
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011519478A (en) * | 2008-04-15 | 2011-07-07 | エーエスエムエル ホールディング エヌ．ブイ． | Apparatus for supporting an optical element and method for manufacturing the same |
| JP2013203908A (en) * | 2012-03-28 | 2013-10-07 | Sumitomo Chemical Co Ltd | Liquid crystal polymer molded product |
| JP2014218546A (en) * | 2013-05-01 | 2014-11-20 | スリーエム イノベイティブプロパティズカンパニー | Composite material and molded goods comprising the same |
| US20210075162A1 (en) * | 2019-09-10 | 2021-03-11 | Ticona Llc | Electrical Connector Formed from a Polymer Composition having a Low Dielectric Constant and Dissipation Factor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005089652A (en) * | 2003-09-18 | 2005-04-07 | Nippon Petrochemicals Co Ltd | Wholly aromatic liquid crystal polyester resin composition and optical pick-up member |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005089652A (en) * | 2003-09-18 | 2005-04-07 | Nippon Petrochemicals Co Ltd | Wholly aromatic liquid crystal polyester resin composition and optical pick-up member |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011519478A (en) * | 2008-04-15 | 2011-07-07 | エーエスエムエル ホールディング エヌ．ブイ． | Apparatus for supporting an optical element and method for manufacturing the same |
| US8947634B2 (en) | 2008-04-15 | 2015-02-03 | Asml Holding N.V. | Apparatus for supporting an optical element, and method of making same |
| JP2013203908A (en) * | 2012-03-28 | 2013-10-07 | Sumitomo Chemical Co Ltd | Liquid crystal polymer molded product |
| JP2014218546A (en) * | 2013-05-01 | 2014-11-20 | スリーエム イノベイティブプロパティズカンパニー | Composite material and molded goods comprising the same |
| US9822242B2 (en) | 2013-05-01 | 2017-11-21 | 3M Innovative Properties Company | Composite material and molded goods comprising the same |
| US20210075162A1 (en) * | 2019-09-10 | 2021-03-11 | Ticona Llc | Electrical Connector Formed from a Polymer Composition having a Low Dielectric Constant and Dissipation Factor |
| CN114391029A (en) * | 2019-09-10 | 2022-04-22 | 提克纳有限责任公司 | Electrical connectors formed from polymer compositions having low dielectric constants and dissipation factors |
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