JP4787547B2 - Polyester composition and biaxially oriented film comprising the same - Google Patents
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Description
本発明は、耐水性および寸法安定性の改善されたポリエステル組成物に関するものである。さらに詳しくは、ビニル系重合体が分散された、機械的特性および寸法安定性にも優れた成形物を得るに適したポリエステル組成物に関するものである。 The present invention relates to polyester compositions with improved water resistance and dimensional stability. More specifically, the present invention relates to a polyester composition suitable for obtaining a molded article in which a vinyl polymer is dispersed and excellent in mechanical properties and dimensional stability.
ポリエステル、特にポリエチレンナフタレート(PEN)は、抗張力、伸度、ヤング率、弾性回復率等の機械的性質、耐熱性、寸法安定性等の物理的性質、耐薬品性、耐水性等の化学的性質に優れ、繊維、タイヤコード、ボトル、フィルム等の分野で広く用いられ、例えばフィルムの分野では、磁気記録媒体、コンデンサー、フレキシブル基板、光学部材、食品包装、装飾用などとして多く用いられている。 Polyester, especially polyethylene naphthalate (PEN), has chemical properties such as mechanical properties such as tensile strength, elongation, Young's modulus, elastic recovery rate, physical properties such as heat resistance and dimensional stability, chemical resistance, and water resistance. It has excellent properties and is widely used in the fields of fibers, tire cords, bottles, films, etc. For example, in the field of films, it is widely used as a magnetic recording medium, condenser, flexible substrate, optical member, food packaging, decoration, etc. .
しかしながら、PENなどのポリエステルは、極性が比較的大きいエステル結合に起因して、特に湿熱下での耐水性や寸法安定性が十分ではなく、また電気的特性例えば絶縁耐電圧などもまだ十分ではなく、近年ますます高度な物理特性が要求されている分野、例えば自動車部品、電子部品、電照板、耐熱食品容器等の分野では使用が制限されてきた。 However, polyesters such as PEN have insufficient water resistance and dimensional stability, particularly under wet heat, due to ester bonds having a relatively large polarity, and electrical characteristics such as insulation withstand voltage are not yet sufficient. In recent years, use has been limited in fields where increasingly high physical properties are required, such as automobile parts, electronic parts, lighting plates, and heat-resistant food containers.
例えば磁気記録媒体、特にデータストレージ用磁気記録媒体では、テープの記憶容量の高容量化や高密度化に伴って、ベースフィルムにテープ幅方向の寸法変化の抑制が求められており、湿度変化に対する寸法安定性の改善が求められている。 For example, magnetic recording media, particularly magnetic recording media for data storage, are required to suppress the dimensional change in the tape width direction as the storage capacity of the tape increases and the density increases. There is a need for improved dimensional stability.
このような要求に答えるため、特開平5−212787号公報(特許文献1)、国際公開第99/29488号パンフレット(特許文献2)、国際公開第00/76749号パンフレット(特許文献3)には、フィルムの製造条件を選択することによってテープ幅方向の湿度膨張係数を低減することが提案されている。しかしながら、これらに提案されている方法は、延伸条件やその後の熱固定処理条件の適正化のみによって達成するものであるため、ポリエステルが極性ポリマーであるが故に湿度の影響を受けやすいという根本的な問題の解決は未だ不十分であった。 In order to answer such a request, Japanese Patent Laid-Open No. 5-212787 (Patent Document 1), International Publication No. 99/29488 (Patent Document 2), International Publication No. 00/76749 (Patent Document 3) It has been proposed to reduce the humidity expansion coefficient in the tape width direction by selecting the film production conditions. However, since the methods proposed in these methods are achieved only by optimizing the stretching conditions and the subsequent heat setting treatment conditions, the polyester is a polar polymer and is therefore susceptible to humidity. The solution to the problem was still inadequate.
一方、ポリエステルに非相溶な熱可塑性樹脂を混合した樹脂組成物は、特許第3551120号公報(特許文献4)に提案されている。しかしながら、ここでは該熱可塑性樹脂とポリエステルの界面が破壊されやすい特性を生かし、フィルム中にミクロボイドを形成して、例えば光学用の白色フィルムを提供するものであり、このようなミクロボイドを有するフィルムは、強度、伸度、ヤング率などの機械特性や絶縁耐電圧が低下するなどの問題がある。 On the other hand, a resin composition obtained by mixing an incompatible thermoplastic resin with polyester has been proposed in Japanese Patent No. 3551120 (Patent Document 4). However, here, taking advantage of the property that the interface between the thermoplastic resin and the polyester is easily broken, a microvoid is formed in the film to provide, for example, a white film for optical use. A film having such a microvoid is There are problems such as mechanical properties such as strength, elongation and Young's modulus, and a decrease in dielectric strength.
本発明は、上記背景技術を鑑みなされたもので、その目的は、ポリエステルの有する機械的特性を維持しつつ、特に湿熱下でも優れた耐水性や寸法安定性を有するポリエステル組成物を提供することにある。 The present invention has been made in view of the background art described above, and an object thereof is to provide a polyester composition having excellent water resistance and dimensional stability even under wet heat while maintaining the mechanical properties of the polyester. It is in.
本発明者らは上記目的を達成するために鋭意研究した結果、ポリエステルに特定の構造を有するビニル系重合体を、ポリフェニレンエーテル系重合体を併用して混合すれば、該ビニル系重合体が安定した状態でポリエステル中に微分散され、機械的特性および電気的特性に優れると同時に湿熱下での耐水性や寸法安定性にも優れ、しかも、安定した成形が可能で、得られる成形品中のミクロボイド形成も抑制することができることを見出だし、本発明に到達した。 As a result of diligent research to achieve the above object, the present inventors have found that if a vinyl polymer having a specific structure is mixed with a polyester together with a polyphenylene ether polymer, the vinyl polymer is stable. In such a state, it is finely dispersed in the polyester, and has excellent mechanical and electrical properties, as well as excellent water resistance and dimensional stability under wet heat, and can be molded stably. It has been found that microvoid formation can also be suppressed, and the present invention has been achieved.
かくして本発明によれば、「組成物重量を基準として、全繰返し単位の80モル%以上がエチレンナフタレート単位であるポリエステル(A)を70〜90重量%、シンジオタクチック構造を有するビニル系重合体(B)を1〜30重量%、および、ポリフェニレンエーテル系重合体(C)を5〜30重量%含有することを特徴とするポリエステル組成物。」が提供される。 Thus, according to the present invention, based on the weight of the composition, 70 to 90% by weight of the polyester (A) in which 80% by mole or more of all repeating units are ethylene naphthalate units, and a vinyl-based weight having a syndiotactic structure. A polyester composition comprising 1 to 30% by weight of the blend (B) and 5 to 30% by weight of the polyphenylene ether polymer (C) is provided. "
また、本発明によれば、好ましい態様として、ビニル系重合体(B)がポリスチレン系重合体であること、ポリフェニレンエーテル系重合体(C)が不飽和カルボン酸を0.1〜10モル%共重合した変性ポリフェニレンエーテルであること、ポリエステルの全繰返し単位の80モル%以上がエチレンナフタレート単位であること、の少なくともいずれかの要件を具備するポリエステル組成物およびそれらからなる二軸配向フィルムが提供される。 According to the present invention, as a preferred embodiment, the vinyl polymer (B) is a polystyrene polymer, and the polyphenylene ether polymer (C) contains an unsaturated carboxylic acid in an amount of 0.1 to 10 mol%. it is polymerized modified polyphenylene ether, 80 that more mole% are ethylene naphthalate units, the polyester compositions and biaxially oriented film consisting of comprising at least one of the requirements to provide for the total repeating units of the polyester Is done.
本発明のポリエステル組成物は、ポリフェニレンエーテル系重合体を併用してシンジオタクチック構造を有するビニル系重合体を混合しているため、該ビニル系重合体がポリエステル中に安定して分散されると共にこれらの界面の親和性が向上してミクロボイドの形成が抑制されるためと推定され、機械的性能や透明性を損なうことなく、湿熱下における耐水性や寸法安定性が改善された種々の成形品を安定して製造することができ、工業的に極めて有用なものである。 In the polyester composition of the present invention, since a vinyl polymer having a syndiotactic structure is mixed using a polyphenylene ether polymer in combination, the vinyl polymer is stably dispersed in the polyester. A variety of molded products with improved water resistance and dimensional stability under wet heat, presumed to be due to the improved affinity of these interfaces and the suppression of microvoid formation. Can be produced stably and is extremely useful industrially.
先ず、本発明で用いられるポリエステル(A)は、例えばテレフタル酸、2,6−ナフタレンジカルボン酸、2,7−ナフタレンジカルボン酸、4,4′−ジフェニルジカルボン酸等の芳香族ジカルボン酸成分と、例えばエチレングリコール、1,3−プロパンジオール、1,4−ブタンジオール、1,4−シクロヘキサンジメタノール等のグリコール成分とから構成される芳香族ポリエステルが好ましく、なかでもポリエチレンナフタレートが好ましく、特にポリエチレン−2,6−ナフタレンジカルボキシレートが、湿熱下の耐水性や寸法安定性がより向上するので好ましい。これらのポリエステルは、ホモポリエステルであっても第3成分を共重合したコポリエステルであってもよいが、共重合成分の割合は多くなりすぎると耐熱性や機械的特性が低下する場合があるので、全繰返し単位を基準として20モル%以下、好ましくは10モル%以下とすることが好ましく、特にホモポリエステルが好ましい。 First, the polyester (A) used in the present invention includes an aromatic dicarboxylic acid component such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, and the like. For example, an aromatic polyester composed of glycol components such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol is preferable, and polyethylene naphthalate is particularly preferable. -2,6-naphthalenedicarboxylate is preferred because it improves water resistance and dimensional stability under wet heat. These polyesters may be homopolyesters or copolyesters obtained by copolymerization of the third component, but if the proportion of the copolymerization component increases too much, heat resistance and mechanical properties may be deteriorated. , Based on the total repeating units, 20 mol% or less, preferably 10 mol% or less is preferable, and homopolyester is particularly preferable.
かかるポリエステルの固有粘度(重量比が6/4のフェノール/トリクロロエタン混合溶媒を用いて温度35℃で測定)は、小さすぎると機械的性能が不十分となる場合があり、逆に大きすぎると成形が難しくなる場合があるので、0.4〜0.8dl/g、特に0.5〜0.7dl/gの範囲であることが好ましい。なお、本発明の目的を阻害しない範囲内で、従来公知の各種添加剤を含有していてもよく、例えば有機または無機の滑剤粒子、着色剤、帯電防止剤、酸化防止剤、紫外線吸収剤、潤滑剤などをあげることができる。 If the intrinsic viscosity of the polyester (measured at a temperature of 35 ° C. using a phenol / trichloroethane mixed solvent having a weight ratio of 6/4) is too small, the mechanical performance may be insufficient. May be difficult, and is preferably in the range of 0.4 to 0.8 dl / g, particularly 0.5 to 0.7 dl / g. In addition, within the range not inhibiting the purpose of the present invention, it may contain various conventionally known additives such as organic or inorganic lubricant particles, colorants, antistatic agents, antioxidants, ultraviolet absorbers, Lubricants can be listed.
また、本発明で用いられるビニル系重合体は、その立体規則性がシンジオタクチック構造を有している必要があり、イソタクチック構造やアタクチック構造である場合には得られる組成物の耐熱性や機械的性能が低下するので好ましくない。好ましく用いられるシンジオタクチック構造を有するビニル系重合体(B)としては、シンジオタクチック構造を有する、ポリスチレン系重合体、ポリプロピレン系重合体、ポリ−α−メチルスチレン系重合体、ポリメチルメタクリレート系重合体などをあげることができる。なかでもポリスチレン系重合体、例えばポリスチレン、α−メチルスチレン共重合ポリスチレンが、高強度、高寸法安定性、耐湿熱性、高絶縁破壊電圧といった特性が得られるので好ましい。なお、上記ビニル系重合体はホモ重合体であることが好ましいが、40モル%以下、特に10モル%以下の範囲内であれば共重合成分を含有していても構わない。 Further, the vinyl polymer used in the present invention needs to have a syndiotactic structure for the stereoregularity, and in the case of an isotactic structure or an atactic structure, the heat resistance and mechanical properties of the resulting composition This is not preferable because the physical performance is lowered. The vinyl polymer (B) having a syndiotactic structure preferably used includes a polystyrene polymer, a polypropylene polymer, a poly-α-methylstyrene polymer, and a polymethyl methacrylate polymer having a syndiotactic structure. A polymer etc. can be mention | raise | lifted. Of these, polystyrene-based polymers such as polystyrene and α-methylstyrene copolymer polystyrene are preferable because they provide characteristics such as high strength, high dimensional stability, heat and humidity resistance, and high breakdown voltage. The vinyl polymer is preferably a homopolymer, but may contain a copolymer component as long as it is in the range of 40 mol% or less, particularly 10 mol% or less.
なお、好ましく用いられるポリスチレン系重合体は、その分子量分布(重量平均分子量/数平均分子量)が大きくなりすぎると得られる組成物を成型する際に物性斑が発生しやすくなるので3.0以下、特に2.0以下とするのが好ましい。 The polystyrene-based polymer preferably used has a molecular weight distribution (weight average molecular weight / number average molecular weight) that is too large, and physical properties are likely to occur when the resulting composition is molded. In particular, it is preferably 2.0 or less.
また、ポリエステル(A)中へのビニル系重合体(B)の分散度を高めるために、ビニル系重合体(B)の溶融粘度はポリエステル(A)の溶融粘度に近い範囲で大きいことが好ましく、両者の溶融粘度の比(前者:後者)は4:1〜1:1、特に2:1〜1:1の範囲であることが好ましい。このような粘度比とするためには、用いられるポリエステルとビニル系重合体の種類によって変わるが、ポリエステルとしてポリエチレンナフタレートを用い、ビニル系重合体としてポリスチレン系重合体を用いる場合には、ビニル系重合体の重量平均分子量は5万〜40万、特に10万〜30万の範囲であることが好ましい。 In order to increase the degree of dispersion of the vinyl polymer (B) in the polyester (A), the melt viscosity of the vinyl polymer (B) is preferably large in the range close to the melt viscosity of the polyester (A). The ratio of the melt viscosity of the two (the former: the latter) is preferably in the range of 4: 1 to 1: 1, particularly 2: 1 to 1: 1. In order to obtain such a viscosity ratio, it varies depending on the type of polyester and vinyl polymer used. However, when polyethylene naphthalate is used as the polyester and polystyrene polymer is used as the vinyl polymer, the vinyl type is used. The weight average molecular weight of the polymer is preferably in the range of 50,000 to 400,000, particularly 100,000 to 300,000.
本発明の組成物においては、上記ポリエステルおよびシンジオタクチック構造を有するビニル系重合体に加えて、ポリフェニレンエーテル系重合体(C)を含有していることが肝要である。ここで用いられるポリフェニレンエーテル系重合体とは、主鎖が2,6−ジ置換フェニレンオキシ単位を繰返し単位とするポリフェニレンエーテルであって、繰返し単位の20モル%以下の範囲であればその他の繰返し単位を有するものであってもよいが、実質的に2,6−ジ置換フェニレンオキシ単位のみからなるものが好ましい。 In the composition of the present invention, it is important that the composition contains a polyphenylene ether polymer (C) in addition to the polyester and the vinyl polymer having a syndiotactic structure. The polyphenylene ether polymer used here is a polyphenylene ether having a main chain of 2,6-disubstituted phenyleneoxy units as repeating units, and other repeating units within a range of 20 mol% or less of the repeating units. Although what may have a unit may be sufficient, what consists only of a 2, 6- disubstituted phenyleneoxy unit is preferable.
さらにかかるポリフェニレンエーテル系重合体は、例えば不飽和カルボン酸およびそのモノまたはジエステル、不飽和ポリエステルなどを反応させた変性ポリフェニレンエーテルであることが、シンジオタクチック構造を有するビニル系重合体のポリエステル中への分散がより安定するので好ましい。なお、ここで用いられる不飽和カルボン酸または不飽和ポリエステルの酸成分である不飽和カルボン酸としては、具体的にはフマル酸、マレイン酸が好ましく、なかでもフマル酸が好ましい。変性はグラフト重合によるのが好ましく、その変性割合は、前記ポリフェニレンエーテルの繰返し単位を基準として、不飽和カルボン酸の量が0.1〜30モル%となる範囲が好ましく、特に1〜10モル%の範囲が好ましい。 Further, the polyphenylene ether polymer is, for example, a modified polyphenylene ether obtained by reacting an unsaturated carboxylic acid and a mono- or diester thereof, an unsaturated polyester, etc. into a polyester of a vinyl polymer having a syndiotactic structure. This is preferable because the dispersion of is more stable. In addition, as the unsaturated carboxylic acid which is an acid component of the unsaturated carboxylic acid or unsaturated polyester used here, specifically, fumaric acid and maleic acid are preferable, and fumaric acid is particularly preferable. The modification is preferably performed by graft polymerization, and the modification ratio is preferably in the range where the amount of unsaturated carboxylic acid is 0.1 to 30 mol%, particularly 1 to 10 mol%, based on the repeating unit of the polyphenylene ether. The range of is preferable.
また、かかるポリフェニレンエーテル系重合体エステルの固有粘度(クロロホルムを溶媒として用い温度25℃で測定)は、0.2〜0.8dl/gの範囲が適当であり、特に0.3〜0.6dl/gの範囲が好ましい。 Further, the intrinsic viscosity of the polyphenylene ether polymer ester (measured at a temperature of 25 ° C. using chloroform as a solvent) is suitably in the range of 0.2 to 0.8 dl / g, particularly 0.3 to 0.6 dl. A range of / g is preferred.
本発明のポリエステル組成物は、上記のポリエステル(A)、シンジオタクチック構造を有するビニル系重合体(B)およびポリフェニレンエーテル系重合体(C)を含有してなるものであるが、それぞれの含有量は、該組成物重量を基準として、ポリエステル(A)が50〜90重量%、好ましくは60〜85重量%、シンジオタクチック構造を有するビニル系重合体(B)は1〜30重量%、好ましくは2〜25重量%、特に好ましくは5〜20重量%、ポリフェニレンエーテル系重合体(C)は1〜30重量%、好ましくは2〜20重量%の範囲である必要がある。ポリエステル(A)の含有量が50重量%未満の場合には、ポリエステル自体が有する機械的性能や耐熱性が発現されなくなり、一方90重量%を超える場合にはビニル系重合体(B)およびポリフェニレンエーテル系重合体(C)の含有量が低下して湿熱下での耐水性や寸法安定性の改善効果が不十分となるので好ましくない。一方、ビニル系重合体(B)の含有量が1重量%未満の場合には、湿熱下での耐水性や寸歩安定性の改善効果が不十分となり、逆に30重量%を超える場合には、ポリフェニレンエーテル系重合体を併用しても成形性が不十分となるだけでなく、機械的性能も不十分となるので好ましくない。さらに、ポリフェニレンエーテル系重合体(C)の含有量が1重量%未満の場合には、ビニル系重合体(B)のポリエステル中への分散性改善効果が不十分となり、逆に30重量%を超える場合には、該分散性の改善効果は飽和してそれ以上の効果が期待できないので好ましくない。 The polyester composition of the present invention comprises the polyester (A), a vinyl polymer (B) having a syndiotactic structure, and a polyphenylene ether polymer (C). The amount of the polyester (A) is 50 to 90% by weight, preferably 60 to 85% by weight, and the vinyl polymer (B) having a syndiotactic structure is 1 to 30% by weight, based on the weight of the composition. It is preferably 2 to 25% by weight, particularly preferably 5 to 20% by weight, and the polyphenylene ether polymer (C) needs to be in the range of 1 to 30% by weight, preferably 2 to 20% by weight. When the content of the polyester (A) is less than 50% by weight, the mechanical performance and heat resistance of the polyester itself are not expressed. On the other hand, when the content exceeds 90% by weight, the vinyl polymer (B) and the polyphenylene are lost. This is not preferable because the content of the ether polymer (C) is lowered and the effect of improving water resistance and dimensional stability under wet heat becomes insufficient. On the other hand, when the content of the vinyl polymer (B) is less than 1% by weight, the effect of improving the water resistance and walking stability under wet heat becomes insufficient, and conversely when the content exceeds 30% by weight. Is not preferable even when a polyphenylene ether-based polymer is used in combination, because not only the moldability becomes insufficient but also the mechanical performance becomes insufficient. Furthermore, when the content of the polyphenylene ether polymer (C) is less than 1% by weight, the effect of improving the dispersibility of the vinyl polymer (B) in the polyester is insufficient, and conversely, 30% by weight is reduced. When exceeding, it is not preferable because the effect of improving the dispersibility is saturated and no further effect can be expected.
以上に説明した成分を含有してなる本発明のポリエステル組成物は、温度300℃、剪断速度1000(1/sec)における溶融粘度が100〜800Pa・sの範囲、好ましくは200〜400Pa・sの範囲にあることが望ましい。溶融粘度がこの範囲にある場合には、ビニル系重合体(B)がポリエステル中に微分散されやすく、また、成形時の成形性も良好となり、得られる成形物の斑も抑制される。 The polyester composition of the present invention containing the components described above has a melt viscosity in the range of 100 to 800 Pa · s, preferably 200 to 400 Pa · s at a temperature of 300 ° C. and a shear rate of 1000 (1 / sec). It is desirable to be in range. When the melt viscosity is in this range, the vinyl polymer (B) is easily finely dispersed in the polyester, the moldability at the time of molding is good, and the spots of the resulting molded product are also suppressed.
本発明の組成物の製造方法は特に限定されず、上記の成分を従来公知の方法でそれぞれの成分を溶融混合すればよく、例えば二軸混練押出機を用いて溶融混練すればよい。また、ポリエステルの重縮合反応が終了した時点で、シンジオタクチック構造を有するビニル系重合体(B)とポリフェニレンエーテル系重合体(C)とを添加し、溶融混合後に押出しても構わない。 The method for producing the composition of the present invention is not particularly limited, and the above components may be melt-mixed with each other by a conventionally known method. For example, the components may be melt-kneaded using a twin-screw kneading extruder. Further, when the polycondensation reaction of the polyester is completed, the vinyl polymer (B) having a syndiotactic structure and the polyphenylene ether polymer (C) may be added and extruded after melt mixing.
このようにして得られた本発明のポリエステル組成物は、一旦ペレット状に成形した後に再度溶融して、あるいはペレット状に成形することなく連続して種々の成形品に成形することができる。例えば、Tダイ法や共押出法などにより延伸されたまたは無延伸のシート類、これを深絞り加工した深絞り容器、ブロー成形された成形体などとして用いることができる。 The polyester composition of the present invention thus obtained can be once molded into a pellet and then melted again or continuously into various molded products without molding into a pellet. For example, it can be used as a stretched or non-stretched sheet by a T-die method or a co-extrusion method, a deep-drawn container obtained by deep-drawing the sheet, a blow-molded molded body, and the like.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例により限定されるものではない。なお、本発明における各種特性は、以下の測定方法にしたがった。
(1)固有粘度
ポリエステルは、フェノール/トリクロロエタン=6/4(重量比)を溶媒に用いて35℃恒温下オストワルト型粘度計を用いて測定した。一方、ポリフェニレンエーテル系重合体は、クロロホルムを溶媒に用いて25℃恒温下オストワルト型粘度計を用いて測定した。
(2)溶融粘度
測定装置として島津製作所製フローテスターCF−500を用い、測定温度:300℃、予熱時間:1分、ノズル径:1mm、ノズル長:10mmで測定し、回帰式より剪断速度1000(1/秒)における溶融粘度を求めた。
(3)機械的特性(ヤング率)
ポリエステル組成物からなるペレットを、170℃で5時間乾燥した後、1軸の溶融混練押出機に供給し、290℃まで加熱して溶融状態でダイから回転冷却ドラムの上にシート状に押出し、急冷固化した後に、ポリエステルがポリエチレンナフタレートの場合には125℃、ポリエチレンテレフタレートニテの場合には90℃にて製膜方向および幅方向にそれぞれ3.5倍に延伸して厚み75μmの二軸配向フィルムを得る。
得られたフィルムから幅10mm、長さ15cmの試料を切り出し、インストロンタイプの万能引張試験機を用いて、チャック間100mm、引張速度10mm/分、チャート速度500mm/分で荷重−伸び曲線を測定し、その立上り部の接線よりヤング率を計算する。なお、測定方向は試料の長手方向とし、10回測定してその平均値を求めた。
(4)絶縁破壊電圧
上記のとおり作成したフィルムを用い、JIS C2151記載の平板電極法に準拠して、東京精電株式会社製ITS−6003を用い、直流電圧の昇圧速度を160V/秒として絶縁破壊電圧を測定した。
(5)湿度膨張係数(αh)
上記のとおり作成したフィルムから、幅方向が測定方向となるように長さ15mm、幅5mmの試料を切り出し、真空理工製TMA3000にセットし、温度30℃、湿度30%RHの窒素雰囲気下で1時間保持した後の長さ(L30)、次いで、温度30℃、湿度70%RHの窒素雰囲気下で1時間保持した後の長さ(L70)を測定し、次式にて湿度膨張係数を算出した。なお、10個の試料について行いその平均値を求めた。
αh=(L70−L30)/40
(6)耐湿熱性
上記のとおり作成したフィルムから、縦、横100mmの試料を切り出し、温度130℃湿度100%RHのオーブン内で100時間湿熱処理し、その処理前の固有粘度に対する処理後の固有粘度保持率(%)を測定した。この値が70%以上であれば湿熱下での耐水性良好とした。
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples. In addition, the various characteristics in this invention followed the following measuring methods.
(1) Intrinsic viscosity Polyester was measured using an Ostwald viscometer at a constant temperature of 35 ° C. using phenol / trichloroethane = 6/4 (weight ratio) as a solvent. On the other hand, the polyphenylene ether polymer was measured using an Ostwald viscometer at a constant temperature of 25 ° C. using chloroform as a solvent.
(2) Melt Viscosity Using a flow tester CF-500 manufactured by Shimadzu Corporation as a measuring device, the measurement temperature is 300 ° C., the preheating time is 1 minute, the nozzle diameter is 1 mm, the nozzle length is 10 mm, and the shear rate is 1000 from the regression equation. The melt viscosity at (1 / second) was determined.
(3) Mechanical properties (Young's modulus)
Pellets made of the polyester composition were dried at 170 ° C. for 5 hours, then supplied to a uniaxial melt-kneading extruder, heated to 290 ° C. and extruded from a die onto a rotating cooling drum in a molten state, After quenching and solidification, when the polyester is polyethylene naphthalate, the film is stretched 3.5 times in the film forming direction and the width direction at 90 ° C. when the polyester is polyethylene terephthalate and biaxially oriented with a thickness of 75 μm. Get a film.
A sample with a width of 10 mm and a length of 15 cm was cut out from the obtained film, and a load-elongation curve was measured using an Instron type universal tensile testing machine at a chuck distance of 100 mm, a tensile speed of 10 mm / min, and a chart speed of 500 mm / min. The Young's modulus is calculated from the tangent line of the rising portion. The measurement direction was the longitudinal direction of the sample, and the average value was obtained by measuring 10 times.
(4) Dielectric breakdown voltage Using the film prepared as described above, in accordance with the plate electrode method described in JIS C2151, using ITS-6003 manufactured by Tokyo Seiden Co., Ltd., the DC voltage boosting rate was set to 160 V / sec. The breakdown voltage was measured.
(5) Humidity expansion coefficient (αh)
From the film prepared as described above, a sample having a length of 15 mm and a width of 5 mm was cut out so that the width direction was the measurement direction, set in TMA3000 manufactured by Vacuum Riko, and 1 in a nitrogen atmosphere at a temperature of 30 ° C. and a humidity of 30% RH. The length after holding for a time (L30), then the length after holding for 1 hour in a nitrogen atmosphere at a temperature of 30 ° C. and a humidity of 70% RH (L70) is measured, and the humidity expansion coefficient is calculated by the following equation did. In addition, it carried out about 10 samples and calculated | required the average value.
αh = (L70−L30) / 40
(6) Moisture and heat resistance A sample of 100 mm in length and width is cut out from the film prepared as described above, subjected to wet heat treatment in an oven at a temperature of 130 ° C. and a humidity of 100% RH for 100 hours, and the inherent viscosity after the treatment with respect to the intrinsic viscosity before the treatment. Viscosity retention (%) was measured. If this value was 70% or more, the water resistance under wet heat was considered good.
[製造例1:シンジオタクチックポリスチレン(SPS)の製造]
2リットルの反応容器に、精製スチレン1.0リットル、トリエチルアルミニウム1ミリモルを加え、80℃に加熱したのち、予備混合触媒〔ペンタメチルシクロペンタジエニルチタントリメトキシド90マイクロモル、ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート90マイクロモル、トルエン29.1ミリモル、トリイソブチルアルミニウム1.8ミリモル〕16.5ミリリットルを添加し、80℃で5時間重合を行った。反応終了後、生成物をメタノールで繰返し洗浄し、乾燥して重合体380gを得た。この重合体の重量平均分子量を、1,2,4−トリクロロベンゼンを溶媒とし、130℃でゲルパーミエーションクロマトグラフィーにて測定したところ、150000であった。また、重量平均分子量/数平均分子量は2.70であった。さらに、融点及び13C−NMR測定により、この重合体はSPSであることを確認した。
[Production Example 1: Production of syndiotactic polystyrene (SPS)]
After adding 1.0 liter of purified styrene and 1 mmol of triethylaluminum to a reaction vessel of 2 liters and heating to 80 ° C., premixed catalyst [pentamethylcyclopentadienyl titanium trimethoxide 90 μmol, dimethylanilinium tetrakis (Pentafluorophenyl) borate 90 micromol, toluene 29.1 mmol, triisobutylaluminum 1.8 mmol] 16.5 ml was added and polymerization was carried out at 80 ° C. for 5 hours. After completion of the reaction, the product was repeatedly washed with methanol and dried to obtain 380 g of a polymer. When the weight average molecular weight of this polymer was measured by gel permeation chromatography at 130 ° C. using 1,2,4-trichlorobenzene as a solvent, it was 150,000. The weight average molecular weight / number average molecular weight was 2.70. Furthermore, this polymer was confirmed to be SPS by melting point and 13 C-NMR measurement.
[製造例2:フマル酸変性ポリフェニレンエーテルの製造]
ポリフェニレンエーテル(固有粘度0.45dl/g)1kg、フマル酸30g、ラジカル発生剤として2,3−ジメチル−2,3−ジフェニルブタン〔日本油脂(株)製,ノフマーBC,商品名〕20gをドライブレンドし、30mm二軸押出機を用いてスクリュー回転数200rpm、設定温度300℃で溶融混練を行った。この際樹脂温度は約330℃であった。ストランドを冷却後ペレット化し、フマル酸変性ポリフェニレンエーテルを得た。得られた変性ポリフェニレンエーテル1gをエチルベンゼンに溶解後、メタノールに再沈し、回収したポリマーをメタノールでソックスレー抽出し、乾燥後IRスペクトルのカルボニル吸収の強度および滴定により変性率を求めたところ、フェニレンエーテル単位に対して1.7モル%(変性率は1.6重量%)であった。
[Production Example 2: Production of fumaric acid-modified polyphenylene ether]
1 kg of polyphenylene ether (inherent viscosity 0.45 dl / g), 30 g of fumaric acid, 20 g of 2,3-dimethyl-2,3-diphenylbutane [manufactured by NOF Corporation, NOFMER BC, trade name] as a radical generator Blending was performed, and melt kneading was performed using a 30 mm twin screw extruder at a screw rotation speed of 200 rpm and a set temperature of 300 ° C. At this time, the resin temperature was about 330.degree. The strand was cooled and pelletized to obtain fumaric acid-modified polyphenylene ether. 1 g of the obtained modified polyphenylene ether was dissolved in ethylbenzene, reprecipitated in methanol, the recovered polymer was subjected to Soxhlet extraction with methanol, dried, and the degree of modification was determined by IR spectrum carbonyl absorption intensity and titration. The amount was 1.7 mol% relative to the unit (modification rate was 1.6% by weight).
[実施例1]
固有粘度が0.62dl/gのポリエチレンナフタレート70重量部、製造例1で得た重量平均分子量が15万のシンジオタクチックポリスチレン20重量部、および、製造例2で得たフマル酸変性ポリフェニレンエーテル10重量部をヘンシェルミキサーでドライブレンドした後、神戸製鋼製2軸押出機KTX−46を用いて温度245℃、回転数400rpmにて溶融混練して押出し、ついでペレット化した。得られたペレットを用いて評価した結果を表2に示す。
[Example 1]
70 parts by weight of polyethylene naphthalate having an intrinsic viscosity of 0.62 dl / g, 20 parts by weight of syndiotactic polystyrene having a weight average molecular weight of 150,000 obtained in Production Example 1, and fumaric acid-modified polyphenylene ether obtained in Production Example 2 10 parts by weight were dry blended with a Henschel mixer, then melt-kneaded and extruded at a temperature of 245 ° C. and a rotational speed of 400 rpm using a Kobe Steel twin screw extruder KTX-46, and then pelletized. The results of evaluation using the obtained pellets are shown in Table 2.
[実施例2、4、比較例1〜4]
表1記載のポリエステル、ビニル系重合体およびポリフェニレンエーテル系重合体を表1記載の割合で溶融混練する以外は実施例1と同様にした。結果を表2にあわせて示す。
[Examples 2 and 4 and Comparative Examples 1 to 4 ]
The same procedure as in Example 1 was conducted except that the polyester, vinyl polymer and polyphenylene ether polymer shown in Table 1 were melt-kneaded at the ratio shown in Table 1. The results are shown in Table 2.
表中、各略号は下記を表す。
PEN:固有粘度が0.62dl/gのポリエチレンナフタレート
PET:固有粘度が0.76dl/gのポリエチレンテレフタレート
SPS1:重量平均分子量が15万、分子量分布が2.7のシンジオタクチック構造を有するポリスチレン
SPS2:重量平均分子量が30万、分子量分布が2.9のシンジオタクチック構造を有するポリスチレン
SPS3:重量平均分子量が5万、分子量分布が2.6のシンジオタクチック構造を有するポリスチレン
SPS4:α−メチルスチレンを10モル%共重合した、重量平均分子量が15万、分子量分布が2.49のシンジオタクチック構造を有するポリスチレン
In the table, each abbreviation represents the following.
PEN: Polyethylene naphthalate PET having an intrinsic viscosity of 0.62 dl / g PET: Polyethylene terephthalate SPS having an intrinsic viscosity of 0.76 dl / g 1: Polystyrene having a syndiotactic structure having a weight average molecular weight of 150,000 and a molecular weight distribution of 2.7 SPS2: Polystyrene SPS3 having a syndiotactic structure having a weight average molecular weight of 300,000 and a molecular weight distribution of 2.9: Polystyrene SPS4 having a syndiotactic structure having a weight average molecular weight of 50,000 and a molecular weight distribution of 2.6: α- Polystyrene having a syndiotactic structure having a weight average molecular weight of 150,000 and a molecular weight distribution of 2.49, copolymerized with 10 mol% of methylstyrene
以上に説明した本発明のポリエステル組成物によれば、ビニル系重合体がポリエステル中に安定して分散されると共にこれらの界面の親和性が向上してミクロボイドの形成が抑制されるため、機械的性能や透明性を損なうことなく、湿熱下における耐水性や寸法安定性が改善された種々の成形品を安定して製造することができる。 According to the polyester composition of the present invention described above, the vinyl polymer is stably dispersed in the polyester and the affinity of these interfaces is improved to suppress the formation of microvoids. Various molded products with improved water resistance and dimensional stability under wet heat can be stably produced without impairing performance and transparency.
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