JP2009035709A - Film obtained by extruding and foaming modified polyphenylene ether resin and laminated composite material using the same - Google Patents

Film obtained by extruding and foaming modified polyphenylene ether resin and laminated composite material using the same Download PDF

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JP2009035709A
JP2009035709A JP2008040293A JP2008040293A JP2009035709A JP 2009035709 A JP2009035709 A JP 2009035709A JP 2008040293 A JP2008040293 A JP 2008040293A JP 2008040293 A JP2008040293 A JP 2008040293A JP 2009035709 A JP2009035709 A JP 2009035709A
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polyphenylene ether
modified polyphenylene
ether resin
thickness
average cell
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Tetsuo Okura
徹雄 大倉
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Kaneka Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated composite material which is lightweight and has high rigidity and the rigidity of which is hardly changed even at high temperature and consequently which can be used suitably as a member of a diaphragm of a dynamic planar speaker to be used in a cellular phone or the like. <P>SOLUTION: A film obtained by extruding and foaming a modified polyphenylene ether resin comprises a modified polyphenylene ether resin consisting of 10-60 wt.% polyphenylene ether resin and 40-90 wt.% polystyrene resin, has 60-300 kg/m<SP>3</SP>density and 0.1-0.5 mm thickness, and is characterized in that either of the ratio A/B (wherein A is the average cell diameter in the thickness direction; and B is the average cell diameter in the extrusion direction) and the ratio A/C (wherein C is the average cell diameter in the width direction) is 0.2-1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、変性ポリフェニレンエーテル系樹脂押出発泡フィルム及びそれを用いた積層複合材に関する。更に詳しくは、携帯電話などに使用するダイナミック型平面スピーカーの振動膜の部材として好適に使用しうる変性ポリフェニレンエーテル系樹脂発泡フィルム及びそれを用いた積層複合材に関する。   The present invention relates to a modified polyphenylene ether resin extruded foam film and a laminated composite using the same. More specifically, the present invention relates to a modified polyphenylene ether-based resin foam film that can be suitably used as a vibration membrane member of a dynamic flat speaker used in a mobile phone and a laminated composite material using the same.

近年、携帯電話などの移動通信端末の小型化、高機能化に伴い、搭載されるスピーカーに対しても、小型化、省電力化、音質改良に対する要求が高まっている。   In recent years, as mobile communication terminals such as mobile phones have become smaller and more functional, there have been increasing demands for smaller speakers, lower power consumption, and better sound quality for the speakers installed.

スピーカーを小型化する技術として、従来同様、磁石とコイルを用いて振動膜を振動させるダイナミック型以外に、セラミックなどの圧電材料を用いた圧電型スピーカーが挙げられ、小型化、特に薄肉化に関しては、圧電型の方が有利とされている。しかしながら、音質の観点、特に低音域の音の再現性に関してはダイナミック型の方が優れており、音質を重視する場合にはダイナミック型が採用される傾向にある。   In addition to the dynamic type that vibrates the vibration film using magnets and coils as in the past, piezoelectric speakers using a piezoelectric material such as ceramic can be cited as a technology for downsizing the speaker. The piezoelectric type is advantageous. However, the dynamic type is superior in terms of sound quality, particularly the reproducibility of low-frequency sounds, and the dynamic type tends to be employed when sound quality is important.

しかしながら、圧電型に比べ音質に優れるダイナミック型においても、小型のものは振動膜が平面である場合が多く、振動膜がコーン形状の場合に比べ中音域の音質が劣る傾向にあり、まだ改良の余地が残されていた。   However, even in the dynamic type, which is superior in sound quality compared to the piezoelectric type, the diaphragm is often flat, and the sound quality in the mid-range tends to be inferior compared to the case where the diaphragm is cone-shaped. There was room left.

ダイナミック型平面スピーカーの音質を改良する試みとしては、特許文献1では、振動膜における、低次の振動モードに基づく振動の振幅を抑えて中音領域の音質を改良する目的で、振動膜にPET(ポリエチレンテレフタレート)やPEN(ポリエチレンナフタレート)などの発泡体を貼付する試みが提案されている。また特許文献2では、独立気泡の低発泡ポリエチレンの両面にアルミニウムの面材を積相した複合板を振動板とすることが提案されている。しかしながら、ポリエチレンは耐熱性が低く、80℃程度の温度下では剛性が大きく低下し、音質が変化することから携帯電話などへの適用は好ましくない。また、ポリエチレンテレフタレートもガラス転移温度が高くないため耐熱性は充分ではない。一方、ポリエチレンナフタレートは耐熱性が高く、80℃程度では剛性低下が小さいため好ましいが、樹脂が高価であるため、汎用性に欠ける。更には、ポリエチレンテレフタレートやポリエチレンナフタレートは、押出発泡性に乏しいため、高圧容器中で炭酸ガスなどの不活性ガスを浸透させ、圧力開放した後加熱発泡するなどの煩雑なバッチプロセスを適用せざるを得ず、製造コストが高いなどの欠点があった。   As an attempt to improve the sound quality of a dynamic flat speaker, Patent Document 1 discloses that the diaphragm is made of PET for the purpose of improving the sound quality of the middle sound region by suppressing the amplitude of vibration based on the low-order vibration mode. Attempts have been made to affix foams such as (polyethylene terephthalate) and PEN (polyethylene naphthalate). Patent Document 2 proposes that a diaphragm is a composite plate in which aluminum face materials are stacked on both sides of closed-cell low-foam polyethylene. However, polyethylene has low heat resistance, and its rigidity is greatly reduced at a temperature of about 80 ° C., and the sound quality changes. In addition, polyethylene terephthalate is not high in heat resistance because its glass transition temperature is not high. On the other hand, polyethylene naphthalate is preferable because it has high heat resistance and a stiffness reduction of about 80 ° C. is small, but lacks versatility because the resin is expensive. Furthermore, since polyethylene terephthalate and polyethylene naphthalate are poor in extrusion foaming properties, it is necessary to apply a complicated batch process such as infiltration of an inert gas such as carbon dioxide gas in a high-pressure vessel, heating and foaming after releasing the pressure. There were drawbacks such as high manufacturing costs.

更には、市場において、ポリフェニレンエーテル系樹脂とポリスチレン系樹脂からなる変性ポリフェニレンエーテル系樹脂の予備発泡粒子を型内成型し、薄くスライスした発泡フィルムの両面にアルミニウム箔を積層した複合積層材を振動板に貼付したスピーカーが使用されている。しかしながら、予備発泡粒子のセル径のばらつきが大きい上に、粒子の融着面は粒子中央部よりも高密度となるため、得られる複合積層材が均一性に欠けるなどの欠点があった。   In addition, in the market, pre-expanded particles of modified polyphenylene ether resin made of polyphenylene ether resin and polystyrene resin are molded in-mold, and a composite laminate with aluminum foil laminated on both sides of a thin sliced foam film is used as a diaphragm. The speaker affixed to is used. However, since the cell diameter of the pre-expanded particles is large and the fused surface of the particles has a higher density than the center portion of the particles, the resulting composite laminate material lacks uniformity.

一方、特許文献3では、ポリフェニレンエーテル系樹脂とポリスチレン系樹脂からなる、特定方向への加熱収縮率が大きな積層発泡シートが提案されており、ここで厚み0.25〜0.5mmの発泡フィルムが開示されている。しかしながら、この発泡フィルムは加熱収縮率を大きくする目的で押出方向に強く延伸して得るため、セルが厚み方向に大きく扁平しており、剛性に欠けるものであった。
WO2003/073787号公報 特開2004−64726号公報 特開平2−151429号公報
On the other hand, Patent Document 3 proposes a laminated foamed sheet composed of a polyphenylene ether resin and a polystyrene resin and having a large heat shrinkage rate in a specific direction. Here, a foamed film having a thickness of 0.25 to 0.5 mm is proposed. It is disclosed. However, since this foamed film is obtained by strongly stretching in the extrusion direction for the purpose of increasing the heat shrinkage rate, the cell is greatly flattened in the thickness direction and lacks rigidity.
WO2003 / 073787 JP 2004-64726 A JP-A-2-151429

本発明の目的は、軽量で剛性が高く、かつ、高温下であっても、剛性の変化が少ないことから、携帯電話などに使用するダイナミック型平面スピーカーの振動膜の部材に好適に使用しうる押出発泡フィルム、および、該押出発泡フィルムから作製される積層複合材を提供することにある。   An object of the present invention is lightweight, highly rigid, and has little change in rigidity even at high temperatures. Therefore, it can be suitably used as a vibration membrane member of a dynamic flat speaker used for a mobile phone or the like. An object is to provide an extruded foam film and a laminated composite material produced from the extruded foam film.

本発明者らは前記課題を解決すべく鋭意研究を重ねた結果、特定の変性ポリフェニレンエーテル系樹脂からなる、セルの扁平の少ない押出発泡フィルムが、軽量かつ剛性に優れ、かつ80℃の高温下においても剛性の変化が小さいことを見出し、該押出発泡フィルムの両側にアルミニウム箔を積層してなる積層複合材がスピーカーの振動膜として好適に使用しうることを見出し、本発明の完成に至った。   As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an extruded foam film made of a specific modified polyphenylene ether resin and having a small cell flatness is lightweight and excellent in rigidity and at a high temperature of 80 ° C. Also found that a laminated composite material obtained by laminating aluminum foil on both sides of the extruded foam film can be suitably used as a vibration film of a speaker, and completed the present invention. .

即ち、本発明の第1は、ポリフェニレンエーテル系樹脂10〜60重量%とポリスチレン系樹脂40〜90重量%からなる変性ポリフェニレンエーテル系樹脂からなる、密度60〜300kg/m、厚み0.1〜0.5mm、厚み方向の平均セル径Aと押出方向の平均セル径B、幅方向平均セル径Cの比A/BおよびA/Cがいずれも0.2〜1であることを特徴とする変性ポリフェニレンエーテル系樹脂押出発泡フィルムに関する。 That is, the first aspect of the present invention is a density of 60 to 300 kg / m 3 , a thickness of 0.1 to 0.1, which is made of a modified polyphenylene ether resin comprising 10 to 60% by weight of polyphenylene ether resin and 40 to 90% by weight of polystyrene resin. The ratios A / B and A / C of 0.5 mm, average cell diameter A in the thickness direction, average cell diameter B in the extrusion direction, and average cell diameter C in the width direction are 0.2 to 1, respectively. The present invention relates to a modified polyphenylene ether resin extruded foam film.

本発明の第2は、前記記載の変性ポリフェニレンエーテル系樹脂発泡フィルムの両面にアルミニウム箔を積層することを特徴とする積層複合材に関し、本発明の第3は、前記記載の積層複合材を用いてなるスピーカーに関する。   2nd of this invention is related with the laminated composite material characterized by laminating | stacking aluminum foil on both surfaces of the modified polyphenylene ether-type resin foam film of the said description, 3rd of this invention uses the said laminated composite material. Related to the speaker.

本発明の変性ポリフェニレンエーテル系樹脂押出発泡フィルムは、軽量かつ剛性に優れ、80℃の高温下においても剛性の変化が小さい。   The modified polyphenylene ether resin extruded foam film of the present invention is lightweight and excellent in rigidity, and the change in rigidity is small even at a high temperature of 80 ° C.

従って、本発明の変性ポリフェニレンエーテル系樹脂押出発泡フィルムの両面にアルミニウム箔を積層した積層複合材は、軽量で剛性に優れ、80℃の高温下においても剛性の変化が小さいことから、平面スピーカーの振動膜の剛性を改良する部材に好適に利用可能である。   Accordingly, the laminated composite material in which the aluminum foil is laminated on both sides of the modified polyphenylene ether resin extruded foam film of the present invention is lightweight and excellent in rigidity, and the change in rigidity is small even at a high temperature of 80 ° C. It can be suitably used for a member that improves the rigidity of the diaphragm.

本発明における変性ポリフェニレンエーテル系樹脂押出発泡フィルムの基材樹脂である変性ポリフェニレンエーテル系樹脂は、ポリフェニレンエーテル系樹脂10〜60重量%とポリスチレン系樹脂40〜90重量%からなる。   The modified polyphenylene ether resin which is the base resin of the modified polyphenylene ether resin extruded foam film in the present invention comprises 10 to 60% by weight of polyphenylene ether resin and 40 to 90% by weight of polystyrene resin.

前記ポリフェニレンエーテル系樹脂の具体例としては、例えば、ポリ(2,6−ジメチルフェニレン−1,4−エーテル)、ポリ(2−メチル−6−エチルフェニレン−4−エーテル)、ポリ(2,6−ジエチルフェニレン−1,4−エーテル)、ポリ(2,6−ジエチルフェニレン−1,4−エーテル)、ポリ(2−メチル−6−n−プロピルフェニレン−1,4−エーテル)、ポリ(2−メチル−6−n−ブチルフェニレン−1,4−エーテル)、ポリ(2−メチル−6−クロルフェニレン−1,4−エーテル)、ポリ(2−メチル−6−ブロムフェニレン−1,4−エーテル)、ポリ(2−エチル−6−クロルフェニレン−1,4−エーテル)などがあげられ、これらは単独または2種以上を組み合わせて用いることができる。   Specific examples of the polyphenylene ether resin include poly (2,6-dimethylphenylene-1,4-ether), poly (2-methyl-6-ethylphenylene-4-ether), and poly (2,6 -Diethylphenylene-1,4-ether), poly (2,6-diethylphenylene-1,4-ether), poly (2-methyl-6-n-propylphenylene-1,4-ether), poly (2 -Methyl-6-n-butylphenylene-1,4-ether), poly (2-methyl-6-chlorophenylene-1,4-ether), poly (2-methyl-6-bromophenylene-1,4-ether) Ether), poly (2-ethyl-6-chlorophenylene-1,4-ether) and the like, and these can be used alone or in combination of two or more.

また前記ポリスチレン系樹脂としては、スチレンまたはその誘導体、例えばα−メチルスチレン、2,4−ジメチルスチレン、モノクロルスチレン、ジクロルスチレン、p−メチルスチレン、エチルスチレンなどを主成分とする樹脂があげられる。したがって、ポリスチレン系樹脂はスチレンまたはスチレン誘導体だけからなる単独重合体に限らず他の単量体と共重合することによって作られた共重合体であってもよい。   Examples of the polystyrene resin include resins mainly composed of styrene or a derivative thereof such as α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, dichlorostyrene, p-methylstyrene, ethylstyrene, and the like. . Accordingly, the polystyrene-based resin is not limited to a homopolymer composed of only styrene or a styrene derivative, but may be a copolymer made by copolymerizing with another monomer.

本発明において、両樹脂の配合割合は、ポリフェニレンエーテル系樹脂10〜60重量%およびポリスチレン系樹脂40〜90重量%であり、好ましくはポリフェニレンエーテル系樹脂30〜50重量%およびポリスチレン系樹脂50〜70重量%である。変性ポリフェニレンエーテル系樹脂中のポリフェニレンエーテル系樹脂が10重量%より少ないと、耐熱性が劣り、ポリフェニレンエーテル系樹脂が60重量%を超えると、加熱流動時の粘度が上昇し発泡成形が困難になる。   In the present invention, the blending ratio of both resins is 10 to 60% by weight of polyphenylene ether resin and 40 to 90% by weight of polystyrene resin, preferably 30 to 50% by weight of polyphenylene ether resin and 50 to 70 polystyrene resin. % By weight. If the polyphenylene ether-based resin in the modified polyphenylene ether-based resin is less than 10% by weight, the heat resistance is poor, and if the polyphenylene ether-based resin exceeds 60% by weight, the viscosity at the time of heat flow increases and foam molding becomes difficult. .

なお、市販の変性ポリフェニレンエーテル系樹脂は、ポリフェニレンエーテル系樹脂に少量のポリスチレン系樹脂が配合されている場合があるが、所望の配合比率でない場合、別途ポリスチレン系樹脂を配合して前記配合割合になるように調整してもよい。   In addition, a commercially available modified polyphenylene ether resin may contain a small amount of polystyrene resin in the polyphenylene ether resin, but if it is not the desired blending ratio, separately blend the polystyrene resin to the blending ratio. You may adjust so that it may become.

本発明における変性ポリフェニレンエーテル系樹脂押出発泡フィルムの密度としては、60〜300kg/mであり、好ましくは70〜250kg/mである。密度が60kg/mを下回ると剛性が低下するため、スピーカーの振動膜に貼付した際の音質改良効果が低下する。一方、密度が300kg/mを超えると、軽量性が損なわれ消費電力が増加する。 The density of the modified polyphenylene ether resin extruded foam film in the present invention is 60 to 300 kg / m 3 , preferably 70 to 250 kg / m 3 . When the density is less than 60 kg / m 3 , the rigidity is lowered, so that the sound quality improving effect when pasted on the diaphragm of the speaker is lowered. On the other hand, if the density exceeds 300 kg / m 3 , the lightness is impaired and the power consumption increases.

本発明における変性ポリフェニレンエーテル系樹脂押出発泡フィルムの厚みとしては、0.1〜0.5mmであり、好ましくは0.2〜0.4mmである。厚みが0.1mmを下回ると剛性が低下し、平面スピーカーの振動膜に貼付した際の音質改良効果が低下する。一方、厚みが0.5mmを超えると、平面スピーカーの振動膜に貼付した場合に振動膜からの突出が大きくなりスピーカーの容積が増大する。   The thickness of the modified polyphenylene ether resin extruded foam film in the present invention is 0.1 to 0.5 mm, preferably 0.2 to 0.4 mm. When the thickness is less than 0.1 mm, the rigidity is lowered, and the sound quality improving effect when pasted on the vibration membrane of a flat speaker is lowered. On the other hand, when the thickness exceeds 0.5 mm, the protrusion from the vibrating membrane becomes large when pasted on the vibrating membrane of a flat speaker, and the volume of the speaker increases.

本発明における変性ポリフェニレンエーテル系樹脂押出発泡フィルムの厚み方向の平均セル径Aと押出方向の平均セル径B、幅方向平均セル径Cの比A/BおよびA/Cがいずれも0.2〜1であり、好ましくは0.4〜1である。A/BまたはA/Cが0.2を下回ると剛性が低下するだけでなく、厚み方向と垂直な方向のセル径が大きくアルミニウム箔を積層した場合に複合材の表面平滑性が損なわれる。一方、A/BまたはA/Cが1を越えるセルとするには、押出後に発泡フィルムの上下面の面積が増加しないよう拘束しつつ、加熱により体積を増加させるなどの特殊な処理が必要となり、プロセスが複雑になるだけでなく、表面平滑性も損なわれる。   The ratio A / B and A / C of the average cell diameter A in the thickness direction, the average cell diameter B in the extrusion direction, and the average cell diameter C in the width direction of the modified polyphenylene ether-based resin extruded foam film in the present invention are both 0.2 to 1, preferably 0.4-1. When A / B or A / C is less than 0.2, not only the rigidity is lowered, but also the surface smoothness of the composite material is impaired when an aluminum foil is laminated with a large cell diameter in a direction perpendicular to the thickness direction. On the other hand, in order to make a cell with A / B or A / C exceeding 1, special treatments such as increasing the volume by heating while restraining the area of the upper and lower surfaces of the foamed film from increasing after extrusion are required. Not only is the process complicated, but surface smoothness is also impaired.

また、本発明における変性ポリフェニレンエーテル系樹脂押出発泡フィルムの厚み方向の平均セル径Aは、押出発泡フィルムの厚みを超えなければ特に限定は無いが、0.02〜0.2mmの範囲であることが好ましい。Aが0.02mmを下回ると剛性が低下する傾向にあり、0.2mmを超えると厚み方向のセル数が減少し、アルミニウム箔との積層複合材とした場合に部位によって物性のばらつきが大きくなる傾向にある。   In addition, the average cell diameter A in the thickness direction of the modified polyphenylene ether-based resin extruded foam film in the present invention is not particularly limited as long as it does not exceed the thickness of the extruded foam film, but is in the range of 0.02 to 0.2 mm. Is preferred. When A is less than 0.02 mm, the rigidity tends to decrease, and when it exceeds 0.2 mm, the number of cells in the thickness direction decreases, and when a laminated composite material with aluminum foil is used, variation in physical properties increases depending on the part. There is a tendency.

なお、本発明における押出発泡フィルムの厚み方向の平均セル径Aと押出方向の平均セル径B、幅方向平均セル径Cは、発泡フィルムの押出方向に平行な断面と幅方向に平行な断面を顕微鏡にて150倍に拡大し、顕微鏡に付属のスケールを用い、各断面で20個のセルについて厚み方向および押出方向、幅方向のセル径を読み取り、算術平均により算出する。   In the present invention, the average cell diameter A in the thickness direction of the extruded foam film, the average cell diameter B in the extrusion direction, and the average cell diameter C in the width direction are a cross section parallel to the extrusion direction of the foam film and a cross section parallel to the width direction. Using a scale attached to the microscope, the cell diameter in the thickness direction, the extrusion direction, and the width direction is read for 20 cells in each cross section and calculated by arithmetic average.

本発明における変性ポリフェニレンエーテル系樹脂押出発泡フィルムは、例えば、押出機内(150〜300℃)で前記変性ポリフェニレンエーテル系樹脂および発泡剤を溶融混練後、押出機内において発泡温度(130〜200℃)に調節し、環状のリップを有するサーキュラーダイスを用い、そのダイスのリップから大気圧中に押し出して円筒状の発泡体を得、次いで、その円筒状発泡体を引き取りながら、冷却筒(マンドレル)による成形加工によって冷却後、切り開く方法によって製造される。またサーキュラーダイスの代わりにTダイを用いてフィルム状に発泡体を得、ロールなどで引き取る方法によっても製造される。   The modified polyphenylene ether-based resin extruded foam film in the present invention is, for example, melt-kneaded the modified polyphenylene ether-based resin and the foaming agent in an extruder (150 to 300 ° C.) and then the foaming temperature (130 to 200 ° C.) in the extruder. Adjust and use a circular die with an annular lip, extrude into the atmospheric pressure from the lip of the die to obtain a cylindrical foam, then mold with a cooling cylinder (mandrel) while taking the cylindrical foam Manufactured by a slitting method after cooling by processing. Further, it is also produced by a method in which a foam is obtained in the form of a film using a T die instead of a circular die and taken up with a roll or the like.

本発明における発泡フィルムは厚みが薄いが、厚く吐出された発泡体を速く引き取ることで厚みを薄くすると、厚み方向の平均セル径Aと厚み方向と垂直な方向の平均セル径Bの比A/Bが小さくなる傾向がある。速く引き取ることなく所望の厚みの発泡フィルムを得るには、ダイギャップを所望の発泡フィルム厚みの0.1〜0.5倍程度にするのが好ましい。   Although the foamed film in the present invention is thin, if the thickness is reduced by quickly taking out the foam discharged thickly, the ratio of the average cell diameter A in the thickness direction and the average cell diameter B in the direction perpendicular to the thickness direction A / B tends to be small. In order to obtain a foam film having a desired thickness without being taken up quickly, the die gap is preferably about 0.1 to 0.5 times the thickness of the desired foam film.

本発明における変性ポリフェニレンエーテル系押出発泡フィルムの製造に使用される発泡剤としては、例えば、プロパン、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタン、などの脂肪族炭化水素類、シクロブタン、シクロペンタン、シクロヘキサンなどの脂環式炭化水素類、窒素、炭酸ガス、空気などの無機ガスがあげられる。これらは単独または2種以上混合して使用してよい。   Examples of the foaming agent used in the production of the modified polyphenylene ether-based extruded foam film in the present invention include aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, and isopentane, cyclobutane, cyclopentane, and cyclohexane. Inorganic gases such as alicyclic hydrocarbons, nitrogen, carbon dioxide and air. You may use these individually or in mixture of 2 or more types.

前記発泡剤の添加量(混練量)は、発泡剤の種類および目標密度により異なるが、変性ポリフェニレンエーテル系樹脂100重量部に対して、1〜5重量部の範囲内にあることが好ましい。   The addition amount (kneading amount) of the foaming agent varies depending on the type of foaming agent and the target density, but is preferably in the range of 1 to 5 parts by weight with respect to 100 parts by weight of the modified polyphenylene ether resin.

本発明においては、変性ポリフェニレンエーテル系樹脂押出発泡フィルムの厚み方向のセル数を前記範囲にコントロールするために、必要に応じて、タルクなどの造核剤を併用してもよい。必要に応じて用いられる該造核剤の添加量は、特に制限はないが、通常、変性ポリフェニレンエーテル系樹脂100重量部に対して、0.01〜1重量部であることが好ましい。   In the present invention, in order to control the number of cells in the thickness direction of the modified polyphenylene ether-based resin extruded foam film within the above range, a nucleating agent such as talc may be used in combination as necessary. Although there is no restriction | limiting in particular in the addition amount of this nucleating agent used as needed, Usually, it is preferable that it is 0.01-1 weight part with respect to 100 weight part of modified polyphenylene ether-type resin.

さらに本発明においては、変性ポリフェニレンエーテル系樹脂押出発泡フィルムの製造において、変性ポリフェニレンエーテル系樹脂の発泡性を損なわない範囲で、熱可塑性樹脂や、酸化防止剤、金属不活性剤、燐系加工安定剤、紫外線吸収剤、紫外線安定剤、蛍光増白剤、金属石鹸、制酸吸着剤などの安定剤、または架橋剤、連鎖移動剤、造核剤、滑剤、可塑剤、充填材、強化材、顔料、染料、難燃剤、帯電防止剤などの添加剤を添加してもよい。   Further, in the present invention, in the production of a modified polyphenylene ether resin extruded foam film, a thermoplastic resin, an antioxidant, a metal deactivator, and a phosphorus-based processing stability are within the range that does not impair the foamability of the modified polyphenylene ether resin. Stabilizers, UV absorbers, UV stabilizers, optical brighteners, metal soaps, antacid adsorbents, etc., or crosslinking agents, chain transfer agents, nucleating agents, lubricants, plasticizers, fillers, reinforcing materials, Additives such as pigments, dyes, flame retardants and antistatic agents may be added.

また本発明の変性ポリフェニレンエーテル系押出発泡フィルムの製造において、発泡フィルムの厚みや厚みムラを調整する目的で、厚み方向と垂直な面でスライスを行ってもよい。   In the production of the modified polyphenylene ether-based extruded foam film of the present invention, slicing may be performed on a plane perpendicular to the thickness direction for the purpose of adjusting the thickness and thickness unevenness of the foam film.

本発明における変性ポリフェニレンエーテル系押出発泡フィルムはこの様にして得ることができる。   The modified polyphenylene ether-based extruded foam film in the present invention can be obtained in this manner.

以上のようにして得られた変性ポリフェニレンエーテル系押出発泡フィルムの両面にアルミニウム箔を積層することにより本発明の積層複合材が得られる。   The laminated composite material of the present invention is obtained by laminating aluminum foil on both surfaces of the modified polyphenylene ether-based extruded foam film obtained as described above.

本発明において変性ポリフェニレンエーテル系樹脂押出発泡フィルムに積層されるアルミニウム箔は、厚さが0.005〜0.12mmであることがより好ましく、厚さが0.03〜0.1mmであることがより好ましい。厚みが0.005mmを下回ると剛性が低下するため、平面スピーカーの振動膜として使用した際の音質改良効果が低下する傾向にある。一方、厚さが0.12mmを超えると、軽量性が損なわれ消費電力が増加する傾向にある。   In the present invention, the aluminum foil laminated on the modified polyphenylene ether resin extruded foam film has a thickness of more preferably 0.005 to 0.12 mm, and a thickness of 0.03 to 0.1 mm. More preferred. When the thickness is less than 0.005 mm, the rigidity is lowered, so that the sound quality improvement effect when used as a vibration film of a flat speaker tends to be lowered. On the other hand, if the thickness exceeds 0.12 mm, the lightness tends to be impaired and the power consumption tends to increase.

本発明において変性ポリフェニレンエーテル系樹脂押出発泡フィルムにアルミニウム箔を積層する方法に特に制限は無く、接着剤や熱融着などの方法が採用可能だが、生産性や積層複合材の厚み精度の観点から、接着剤による積層が好ましい。   In the present invention, there is no particular limitation on the method of laminating the aluminum foil on the modified polyphenylene ether resin extruded foam film, and methods such as adhesives and heat fusion can be adopted, but from the viewpoint of productivity and thickness accuracy of the laminated composite material Lamination with an adhesive is preferred.

前記積層に使用する接着剤としては、無溶剤系で収縮が小さいことが好ましく、エポキシ系接着剤、アクリル系接着剤、シアノアクリレート系接着剤、ウレタン系接着剤、ホットメルト接着剤などが例示される。   The adhesive used for the lamination is preferably solventless and has a small shrinkage, and examples thereof include an epoxy adhesive, an acrylic adhesive, a cyanoacrylate adhesive, a urethane adhesive, and a hot melt adhesive. The

次に、本発明を実施例に基づいて更に詳細に説明するが、本発明はこれら実施例のみに限定されるものではない。   EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples.

〈押出発泡フィルムの密度測定〉
JIS−K6767に準拠し、測定した。
<Measurement of density of extruded foam film>
Measurement was performed in accordance with JIS-K6767.

〈押出発泡フィルムの厚み測定〉
厚みゲージを用いて、幅方向に20mm間隔で厚みを測定し、算術平均により算出した。
<Measurement of thickness of extruded foam film>
Using a thickness gauge, the thickness was measured at intervals of 20 mm in the width direction and calculated by arithmetic average.

〈押出発泡フィルムのセル構造評価〉
押出発泡フィルムの厚み方向の平均セル径Aと押出方向の平均セル径B、幅方向平均セル径Cは、発泡フィルムの押出方向に平行な断面と幅方向に平行な断面を顕微鏡にて150倍に拡大し、顕微鏡に付属のスケールを用い、各断面で20個のセルについて厚み方向および押出方向、幅方向のセル径を読み取り、算術平均により算出した。
<Evaluation of cell structure of extruded foam film>
The average cell diameter A in the thickness direction of the extruded foam film, the average cell diameter B in the extrusion direction, and the average cell diameter C in the width direction are 150 times the cross section parallel to the extrusion direction of the foam film and the cross section parallel to the width direction using a microscope. Using the scale attached to the microscope, the cell diameters in the thickness direction, the extrusion direction, and the width direction were read for 20 cells in each cross section and calculated by arithmetic average.

〈押出発泡フィルムの圧縮剛性評価〉
押出発泡フィルムを3cm×3cmに10枚切り出して重ねて測定試料とし、23℃雰囲気下、オートグラフを用いて2mm/minの速度で圧縮し、測定試料厚みをD(cm)、測定試料厚みの10%圧縮時の応力W10(kg)と、20%圧縮時の応力W20(kg)から、以下の式に基づき初期圧縮反発力(kg/cm/cm)を算出し、以下の基準にて圧縮剛性を評価した。
(初期圧縮反発力)=(W20−W10)/(0.1×D×3×3)
○:初期圧縮反発力が50kg/cm/cm以上
×:初期圧縮反発力が50kg/cm/cm未満
<Evaluation of compression rigidity of extruded foam film>
Ten sheets of extruded foam film were cut out into 3 cm × 3 cm and stacked to form a measurement sample, and compressed at a rate of 2 mm / min using an autograph in a 23 ° C. atmosphere, and the measurement sample thickness was D (cm). From the stress W10 (kg) at the time of 10% compression and the stress W20 (kg) at the time of 20% compression, the initial compression repulsive force (kg / cm / cm 2 ) is calculated based on the following formula, and the following criteria are used: The compression stiffness was evaluated.
(Initial compression repulsion force) = (W20−W10) / (0.1 × D × 3 × 3)
○: Initial compression repulsion force is 50 kg / cm / cm 2 or more ×: Initial compression repulsion force is less than 50 kg / cm / cm 2

〈押出発泡フィルムの耐熱性評価〉
オートグラフの付帯設備である高温槽を用いて、80℃雰囲気下にて上記初期圧縮反発力を評価し、以下の基準にて耐熱性を評価した。
○:初期圧縮反発力が25kg/cm/cm以上
×:初期圧縮反発力が25kg/cm/cm未満
<Evaluation of heat resistance of extruded foam film>
The initial compression repulsion force was evaluated in an 80 ° C. atmosphere using a high-temperature tank which is an auxiliary facility of the autograph, and the heat resistance was evaluated according to the following criteria.
○: Initial compression repulsion force is 25 kg / cm / cm 2 or more ×: Initial compression repulsion force is less than 25 kg / cm / cm 2

(実施例1)
ポリフェニレンエーテル70重量%とポリスチレン30重量%からなる変性ポリフェニレンエーテル樹脂(日本GEプラスチックス(株)製、ノリルEFN−4230)57.1重量部およびポリスチレン(A&Mスチレン(株)製、G8102)42.9重量部とを混合し、ポリフェニレンエーテル樹脂成分40重量%およびポリスチレン樹脂成分60重量%となるように調整した混合樹脂100重量部に対して、気泡核形成剤としてタルク0.32重量部を添加しリボンブレンダーにて撹拌混合した配合物を、65−90mmφタンデム型押出機に供給し、シリンダー温度270℃に設定した第1段押出機(65mmφ)中にて溶融させた後、iso−ブタンを主成分とする炭化水素系発泡剤(iso−ブタン/n−ブタン=85/15重量%)1.2重量部を圧入混合し、196℃に設定した第2段押出機(90mmφ)中で冷却し、ダイギャップを0.1mmに設定したサーキュラーダイ(75mmφ)より大気圧下に吐出し、外径200mmおよび本体長さ400mmの冷却筒にて成形しながら13m/minで引き取りつつ延伸・冷却し円筒型発泡体を得、これをカッターで切り開くことにより、厚み0.3mm、密度200kg/m、厚み方向の平均セル径Aが0.3mm、Aと押出方向平均セル径との比A/Bが0.6、Aと幅方向平均セル径との比A/Cが0.5の押出発泡フィルムを得た。なお、吐出量は30kg/hであった。この押出発泡フィルムの初期圧縮反発力を測定したところ、23℃雰囲気下で61kg/cm/cm、80℃雰囲気下で44kg/cm/cmであり、圧縮剛性評価、耐熱性評価いずれも○であった。評価結果を表1に示す。
Example 1
Modified polyphenylene ether resin comprising 70% by weight of polyphenylene ether and 30% by weight of polystyrene (Nippon GE Plastics Co., Ltd., Noryl EFN-4230) 57.1 parts by weight and polystyrene (A & M Styrene Co., Ltd., G8102) 42. 9 parts by weight is mixed, and 0.32 part by weight of talc is added as a cell nucleating agent to 100 parts by weight of the mixed resin adjusted to be 40% by weight of the polyphenylene ether resin component and 60% by weight of the polystyrene resin component The mixture stirred and mixed in the ribbon blender was supplied to a 65-90 mmφ tandem type extruder and melted in a first stage extruder (65 mmφ) set at a cylinder temperature of 270 ° C., and then iso-butane was added. Hydrocarbon blowing agent as the main component (iso-butane / n-butane = 85/15 weight) 1.2% by weight) was injected and mixed, cooled in a second stage extruder (90 mmφ) set at 196 ° C., and under atmospheric pressure from a circular die (75 mmφ) set at a die gap of 0.1 mm. While discharging and forming in a cooling cylinder having an outer diameter of 200 mm and a main body length of 400 mm, drawing and cooling at 13 m / min to obtain a cylindrical foam, which is cut with a cutter, thickness 0.3 mm, density 200 kg / m 3 , average cell diameter A in the thickness direction is 0.3 mm, ratio A / B between A and extrusion direction average cell diameter is 0.6, and ratio A / C between A and width direction average cell diameter is 0 An extruded foam film of .5 was obtained. The discharge rate was 30 kg / h. Measurement of the initial compression repulsive force of the extruded foamed film is 44kg / cm / cm 2 under 61kg / cm / cm 2, 80 ℃ atmosphere under 23 ° C. atmosphere, compressive stiffness evaluation, both heat resistance evaluation ○ Met. The evaluation results are shown in Table 1.

Figure 2009035709
(比較例1)
円筒型発泡体の引き取り速度を48m/minに変更した以外は、実施例1と同様な方法により、厚み0.08mm、密度220kg/m、厚み方向の平均セル径Aが0.06mm、Aと押出方向平均セル径との比A/Bが0.1、Aと幅方向平均セル径との比A/Cが0.3の押出発泡フィルムを得た。この押出発泡フィルムの初期圧縮反発力を測定したところ、23℃雰囲気下で47kg/cm/cm、80℃雰囲気下で20kg/cm/cmであり、圧縮剛性評価、耐熱性評価いずれも×であった。
Figure 2009035709
(Comparative Example 1)
Except that the take-up speed of the cylindrical foam was changed to 48 m / min, the thickness was 0.08 mm, the density was 220 kg / m 3 , and the average cell diameter A in the thickness direction was 0.06 mm. An extruded foam film having a ratio A / B of 0.1 to the average cell diameter in the extrusion direction was 0.1 and a ratio A / C of A to the average cell diameter in the width direction of 0.3 was obtained. When the initial compression repulsion force of this extruded foam film was measured, it was 47 kg / cm / cm 2 in an atmosphere at 23 ° C. and 20 kg / cm / cm 2 in an atmosphere at 80 ° C. Both compression rigidity evaluation and heat resistance evaluation were × Met.

(実施例2)
炭化水素系発泡剤圧入量を1.8重量部に変更し、第2段押出機の設定温度を194℃に変更した以外は、実施例1と同様な方法により、厚み0.5mm、密度130kg/m、厚み方向の平均セル径Aが0.2mm、Aと押出方向平均セル径との比A/Bが0.7、Aと幅方向平均セル径との比A/Cが0.6の押出発泡フィルムを得た。この押出発泡フィルムの初期圧縮反発力を測定したところ、23℃雰囲気下で58kg/cm/cm、80℃雰囲気下で35kg/cm/cmであり、圧縮剛性評価、耐熱性評価いずれも○であった。
(Example 2)
A thickness of 0.5 mm and a density of 130 kg were obtained in the same manner as in Example 1 except that the amount of injection of the hydrocarbon-based foaming agent was changed to 1.8 parts by weight and the set temperature of the second stage extruder was changed to 194 ° C. / M 3 , the average cell diameter A in the thickness direction is 0.2 mm, the ratio A / B between A and the average cell diameter in the extrusion direction is 0.7, and the ratio A / C between A and the average cell diameter in the width direction is 0. 6 extruded foam film was obtained. Measurement of the initial compression repulsive force of the extruded foamed film is 35kg / cm / cm 2 under 58kg / cm / cm 2, 80 ℃ atmosphere under 23 ° C. atmosphere, compressive stiffness evaluation, both heat resistance evaluation ○ Met.

(比較例2)
変性ポリフェニレンエーテル樹脂を配合せず、ポリスチレン(A&Mスチレン(株)製、G8102)100重量部を使用し、第1段押出機の設定温度を220℃、第2段押出機の設定温度を150℃に変更した以外は、実施例1と同様な方法により、厚み0.3mm、密度190kg/m、厚み方向の平均セル径Aが0.1mm、Aと押出方向平均セル径との比A/Bが0.6、Aと幅方向平均セル径との比A/Cが0.6の押出発泡フィルムを得た。この押出発泡フィルムの初期圧縮反発力を測定したところ、23℃雰囲気下で55kg/cm/cm、80℃雰囲気下で21kg/cm/cmであり、圧縮剛性評価は○だが、耐熱性評価は×であった。
(Comparative Example 2)
The modified polyphenylene ether resin is not blended and 100 parts by weight of polystyrene (A & M Styrene Co., Ltd., G8102) is used, the first stage extruder set temperature is 220 ° C, and the second stage extruder set temperature is 150 ° C. In the same manner as in Example 1 except that the thickness was changed to, the thickness was 0.3 mm, the density was 190 kg / m 3 , the average cell diameter A in the thickness direction was 0.1 mm, and the ratio A / A to the average cell diameter in the extrusion direction was A / An extruded foam film having B of 0.6 and a ratio A / C between A and the average cell diameter in the width direction of 0.6 was obtained. Measurement of the initial compression repulsive force of the extruded foamed film is 21kg / cm / cm 2 under 55kg / cm / cm 2, 80 ℃ atmosphere under 23 ° C. atmosphere, compressive stiffness evaluation ○ However, heat resistance evaluation Was x.

(比較例3)
炭化水素系発泡剤圧入量を5.1重量部に変更し、第2段押出機の設定温度を191℃に変更し、円筒型発泡体の引き取り速度を48m/minに変更した以外は、実施例1と同様な方法により、厚み0.5mm、密度45kg/m、厚み方向の平均セル径Aが0.2mm、Aと押出方向平均セル径との比A/Bが0.5、Aと幅方向平均セル径との比A/Cが0.7の押出発泡フィルムを得た。この押出発泡フィルムの初期圧縮反発力を測定したところ、23℃雰囲気下で41kg/cm/cm、80℃雰囲気下で18kg/cm/cmであり、圧縮剛性評価、耐熱性評価いずれも×であった。
(Comparative Example 3)
Except for changing the injection amount of hydrocarbon-based foaming agent to 5.1 parts by weight, changing the set temperature of the second stage extruder to 191 ° C, and changing the take-up speed of the cylindrical foam to 48 m / min. In the same manner as in Example 1, the thickness was 0.5 mm, the density was 45 kg / m 3 , the average cell diameter A in the thickness direction was 0.2 mm, and the ratio A / B between A and the average cell diameter in the extrusion direction was 0.5, A And an extruded foam film having a ratio A / C of 0.7 to the average cell diameter in the width direction was 0.7. Measurement of the initial compression repulsive force of the extruded foamed film is 18kg / cm / cm 2 under 41kg / cm / cm 2, 80 ℃ atmosphere under 23 ° C. atmosphere, compressive stiffness evaluation, both heat resistance evaluation × Met.

(実施例3)
実施例1の押出発泡フィルムの両面に、厚さ0.07mmのアルミニウム箔をエポキシ型接着剤(セメダイン(株)製、EP001)を用いて接着した。この積層複合材の初期圧縮反発力を測定したところ、23℃雰囲気下で68kg/cm/cm、80℃雰囲気下で45kg/cm/cmであり、圧縮剛性評価、耐熱性評価いずれも○であった。
(Example 3)
An aluminum foil having a thickness of 0.07 mm was bonded to both surfaces of the extruded foam film of Example 1 using an epoxy type adhesive (EP001 manufactured by Cemedine Co., Ltd.). Measurement of the initial compression repulsive force of the laminate composite is 45kg / cm / cm 2 under 68kg / cm / cm 2, 80 ℃ atmosphere under 23 ° C. atmosphere, compressive stiffness evaluation, both heat resistance evaluation ○ Met.

(実施例4)
実施例2の押出発泡フィルムの両面に、厚さ0.007mmのアルミニウム箔をホットメルト接着剤(倉敷紡績(株)製、クランベターX−2200)を用いて110℃にて接着した。この積層複合材の初期圧縮反発力を測定したところ、23℃雰囲気下で53kg/cm/cm、80℃雰囲気下で31kg/cm/cmであり、圧縮剛性評価、耐熱性評価いずれも○であった。
Example 4
Aluminum foil having a thickness of 0.007 mm was bonded to both sides of the extruded foam film of Example 2 at 110 ° C. using a hot melt adhesive (Kurashita Boseki Co., Ltd., Clanbetter X-2200). When the initial compression repulsion force of this laminated composite was measured, it was 53 kg / cm / cm 2 in an atmosphere at 23 ° C. and 31 kg / cm / cm 2 in an atmosphere at 80 ° C. Both compression rigidity evaluation and heat resistance evaluation were ○ Met.

Claims (3)

ポリフェニレンエーテル系樹脂10〜60重量%とポリスチレン系樹脂40〜90重量%からなる変性ポリフェニレンエーテル系樹脂からなる、密度60〜300kg/m、厚み0.1〜0.5mm、厚み方向の平均セル径Aと押出方向の平均セル径B、幅方向平均セル径Cの比A/BおよびA/Cがいずれも0.2〜1であることを特徴とする変性ポリフェニレンエーテル系樹脂押出発泡フィルム。 An average cell in the thickness direction having a density of 60 to 300 kg / m 3 , a thickness of 0.1 to 0.5 mm, and a modified polyphenylene ether resin comprising 10 to 60% by weight of a polyphenylene ether resin and 40 to 90% by weight of a polystyrene resin. A modified polyphenylene ether resin extruded foam film characterized in that the ratio A / B and A / C of the diameter A and the average cell diameter B in the extrusion direction and the average cell diameter C in the width direction are 0.2 to 1. 請求項1記載の変性ポリフェニレンエーテル系樹脂発泡フィルムの両面にアルミニウム箔を積層することを特徴とする積層複合材。   An aluminum foil is laminated on both surfaces of the modified polyphenylene ether-based resin foam film according to claim 1. 請求項2記載の積層複合材を用いてなるスピーカー。   A speaker using the laminated composite material according to claim 2.
JP2008040293A 2007-07-10 2008-02-21 Film obtained by extruding and foaming modified polyphenylene ether resin and laminated composite material using the same Pending JP2009035709A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
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JP2012010268A (en) * 2010-06-28 2012-01-12 Kaneka Corp Diaphragm for loudspeaker
JP2012045910A (en) * 2010-08-30 2012-03-08 Sekisui Plastics Co Ltd Composite panel, and method for manufacturing the same
JP2012077165A (en) * 2010-09-30 2012-04-19 Sekisui Plastics Co Ltd Polystyrenic resin expanded sheet, molded article, and method for producing polystyrenic resin expanded sheet
JP2012206457A (en) * 2011-03-30 2012-10-25 Sekisui Plastics Co Ltd Composite plate
KR20200069297A (en) 2017-10-10 2020-06-16 유니티카 가부시끼가이샤 Porous polyimide film and method for manufacturing same
JP2020164731A (en) * 2019-03-29 2020-10-08 株式会社カネカ Styrene-based resin flaky foam and method for producing the same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012010268A (en) * 2010-06-28 2012-01-12 Kaneka Corp Diaphragm for loudspeaker
JP2012045910A (en) * 2010-08-30 2012-03-08 Sekisui Plastics Co Ltd Composite panel, and method for manufacturing the same
JP2012077165A (en) * 2010-09-30 2012-04-19 Sekisui Plastics Co Ltd Polystyrenic resin expanded sheet, molded article, and method for producing polystyrenic resin expanded sheet
JP2012206457A (en) * 2011-03-30 2012-10-25 Sekisui Plastics Co Ltd Composite plate
KR20200069297A (en) 2017-10-10 2020-06-16 유니티카 가부시끼가이샤 Porous polyimide film and method for manufacturing same
JP2020164731A (en) * 2019-03-29 2020-10-08 株式会社カネカ Styrene-based resin flaky foam and method for producing the same
JP7353779B2 (en) 2019-03-29 2023-10-02 株式会社カネカ Styrenic resin flake foam and method for producing the same

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