JPH08174780A - Polycarbonate resin extruded expanded laminated sheet - Google Patents
Polycarbonate resin extruded expanded laminated sheetInfo
- Publication number
- JPH08174780A JPH08174780A JP7061623A JP6162395A JPH08174780A JP H08174780 A JPH08174780 A JP H08174780A JP 7061623 A JP7061623 A JP 7061623A JP 6162395 A JP6162395 A JP 6162395A JP H08174780 A JPH08174780 A JP H08174780A
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- polycarbonate resin
- foam
- foamed
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Molding Of Porous Articles (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリカーボネート樹脂
押出発泡積層シートに関するものであり、更に詳しく
は、金型再現性、深絞り性等加熱成形性に優れたポリカ
ーボネート樹脂押出発泡積層シートに関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin extruded foam laminated sheet, and more particularly to a polycarbonate resin extruded foam laminated sheet having excellent heat moldability such as mold reproducibility and deep drawability. is there.
【０００２】[0002]
【従来の技術】ポリカーボネート樹脂発泡体は、耐熱
性、耐老化性、耐水性等が高く、電気的及び機械的性質
も良いから、自動車や建造物の内装材、包装材、各種容
器等への用途展開が期待されている。また、耐熱性が要
求される電子レンジ用やレトルト食品用の容器材料とし
ては特に有望である。このように利点は多いが、ポリカ
ーボネート樹脂の流動開始点がポリスチレン等のそれよ
り大幅に高い上に、溶融粘度が低く加熱シートの伸びが
少ないから、通常の押出発泡法で所望の発泡シートを得
るのは困難である。そのため、溶解度係数６．５以上の
有機物を発泡剤とする方法（特開平２−２６１８３６号
公報）、沸点５０〜１５０℃のイソパラフィンを発泡剤
とする方法（特公昭４７−４３１８３号公報）等が提案
されている。しかし、これらの発泡剤を使っても加熱成
形加工時に寸法安定性の良い発泡シートが得られず、そ
のため加工時にシートが破れたり波打つ等の問題があ
る。2. Description of the Related Art Polycarbonate resin foams have high heat resistance, aging resistance, water resistance and the like and have good electrical and mechanical properties. Therefore, polycarbonate resin foams can be used for interior materials of automobiles and constructions, packaging materials, various containers, etc. Applications are expected to expand. Further, it is particularly promising as a container material for microwave ovens and retort foods, which requires heat resistance. Although there are many advantages as described above, the flow starting point of the polycarbonate resin is significantly higher than that of polystyrene and the like, and since the melt viscosity is low and the elongation of the heating sheet is small, the desired foamed sheet is obtained by the usual extrusion foaming method. Is difficult. Therefore, a method of using an organic substance having a solubility coefficient of 6.5 or more as a foaming agent (JP-A-2-261836), a method of using isoparaffin having a boiling point of 50 to 150 ° C. as a foaming agent (JP-B-47-43183) and the like are available. Proposed. However, even if these foaming agents are used, a foamed sheet having good dimensional stability cannot be obtained during the heat-molding process, so that there is a problem that the sheet is broken or corrugated during the process.
【０００３】また、本発明者らは、先にポリカーボネー
ト樹脂と発泡剤とを溶融混練して得られる特定気泡のポ
リカーボネート樹脂押出発泡シートを提案した。しかし
この発泡シートも深絞り性等の加熱成形加工性の点で充
分満足しうるものではない。更に、前記した押出発泡法
のほか、シート状のポリカーボネートに発泡剤を含浸さ
せて加熱発泡させる方法（特開平６−７９８１６号公
報）、低級アルキルベンゼンと低沸点溶剤でゲル化した
ポリカーボネートを加熱発泡させる方法（特公昭４６−
３１４６８号公報）等も提案されている。しかし、これ
らの方法で製造される発泡シートは、押出発泡シートよ
りコスト高となる上に加熱成形加工時の寸法安定性が向
上することもなく、深絞り成形性も良好なものとは言え
ないから、特別な場合を除いて有利な発泡シートとは云
えない。Further, the present inventors have previously proposed a polycarbonate resin extruded foam sheet having specific cells obtained by melt-kneading a polycarbonate resin and a foaming agent. However, this foamed sheet is also not sufficiently satisfactory in terms of heat molding processability such as deep drawing. Further, in addition to the above-mentioned extrusion foaming method, a method of impregnating a sheet-shaped polycarbonate with a foaming agent to heat-foam it (JP-A-6-79816), heat-foaming a polycarbonate gelled with a lower alkylbenzene and a low boiling point solvent. Method (Japanese Patent Publication No. 46-
31468 gazette) etc. are also proposed. However, the foamed sheet produced by these methods is more expensive than the extruded foamed sheet, and the dimensional stability at the time of heat molding is not improved, and the deep drawability is not good. Therefore, it cannot be said that it is an advantageous foamed sheet except in special cases.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、金型再現
性、深絞り成形性等の加熱成形性に優れ、しかも発泡倍
率の高いポリカーボネート樹脂発泡積層シートを提供す
ることを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a polycarbonate resin foam laminated sheet which has excellent moldability, heat drawability such as deep drawability, and high expansion ratio.
【０００５】[0005]
【課題を解決するための手段】本発明らは、押出発泡で
得られたポリカーボネート樹脂発泡シートの、金型再現
性、深絞り成形性等の加熱成形性の向上、また加熱下に
成形加工する際の伸びによる波打ち（以下、あばれとい
う）、それによる加熱ムラが原因で発生する成形品の破
れ等の防止について詳細に検討した結果、該発泡シート
の表面にポリカーボネート樹脂シートを積層することに
より、好ましくは更に該発泡シート内の気泡を押出方向
に多少扁平の球状に形成することによって、これらの目
的を達成しうることを見い出し、本発明を完成するに至
った。MEANS FOR SOLVING THE PROBLEMS The present invention improves the heat moldability of a polycarbonate resin foam sheet obtained by extrusion foaming, such as mold reproducibility and deep drawing moldability, and performs molding under heating. Rippling due to stretching at the time (hereinafter, referred to as "bare"), as a result of detailed study on prevention of breakage of a molded product caused by uneven heating, by laminating a polycarbonate resin sheet on the surface of the foamed sheet, It has been found that these objects can be achieved by preferably forming the air bubbles in the foamed sheet into a slightly flattened spherical shape in the extrusion direction, and completed the present invention.
【０００６】すなわち、ポリカーボネート樹脂押出発泡
シートを芯層とし、少なくとも片面にポリカーボネート
樹脂フィルムよりなる表層を積層したことを特徴とする
ポリカーボネート樹脂押出発泡積層シートが提供され
る。また、前記芯層が、下記式を満足するポリカーボネ
ート樹脂押出発泡シートであることを特徴とする前記ポ
リカーボネート樹脂押出発泡積層シートが提供される。 １＜Ｘ／Ｚ≦３ １＜Ｙ／Ｚ≦５ （Ｘ＋Ｙ＋Ｚ）／３≧０．１ｍｍ 〔但し、式中、Ｘはシート幅方向断面の厚み方向と直交
する方向の平均気泡径（ｍｍ）を、Ｙはシート押し出し
方向断面の厚み方向と直交する方向の平均気泡径（ｍ
ｍ）を、Ｚはシート断面の厚み方向の平均気泡径（ｍ
ｍ）を表す〕 更にまた、前記芯層を構成するポリカーボネート樹脂の
粘度平均分子量が２５０００以上であり、前記表層を構
成するポリカーボネート樹脂の粘度平均分子量が２００
００未満であることを特徴とするポリカーボネート樹脂
押出発泡積層シートが提供される。That is, there is provided a polycarbonate resin extruded foamed laminated sheet comprising a polycarbonate resin extruded foamed sheet as a core layer and a surface layer made of a polycarbonate resin film laminated on at least one surface thereof. Further, there is provided the polycarbonate resin extruded foamed laminated sheet, wherein the core layer is a polycarbonate resin extruded foamed sheet satisfying the following formula. 1 <X / Z ≦ 3 1 <Y / Z ≦ 5 (X + Y + Z) /3≧0.1 mm [where X is the average cell diameter (mm) in the direction orthogonal to the thickness direction of the cross section in the sheet width direction] , Y is the average bubble diameter (m
m), Z is the average cell diameter in the thickness direction of the sheet cross section (m
m)] Furthermore, the viscosity average molecular weight of the polycarbonate resin forming the core layer is 25,000 or more, and the viscosity average molecular weight of the polycarbonate resin forming the surface layer is 200 or more.
A polycarbonate resin extruded foam laminated sheet is provided, which is characterized in that it is less than 00.
【０００７】本発明によるポリカーボネート樹脂押出発
泡積層シートの特徴を説明するために、押出発泡による
発泡シートの一般的製造方法を以下に記述する。 押し出し機内に樹脂と気泡調整剤等の添加剤とを仕込
み、該機内で加熱・溶融・混練する工程 混練物に所望量の発泡剤を圧入して混練物に発泡剤を
練り込む工程 発泡剤が練り込まれている混練物を、所定温度で押出
機先端のサーキュラダイから低圧部に押出し、これを円
柱形状の樹脂発泡体冷却装置（マンドレル）の表面上に
引取って円筒状発泡体を形成させてから、押出方向に切
り開いてシート状発泡体とする工程 が含まれる。In order to explain the characteristics of the polycarbonate resin extruded foam laminated sheet according to the present invention, a general method for producing a foam sheet by extrusion foaming will be described below. A step of charging a resin and additives such as a cell regulator into an extruder and heating / melting / kneading in the machine A step of pressing a desired amount of a foaming agent into a kneaded product and kneading the foaming agent into the kneaded product The kneaded mixture is extruded at a predetermined temperature from the circular die at the tip of the extruder to the low pressure part, and this is taken up on the surface of the cylindrical resin foam cooling device (mandrel) to form a cylindrical foam. Then, the step of cutting in the extrusion direction to form a sheet-like foam is included.
【０００８】さらにシートの加熱成形についても以下に
記載する。 １．発泡シートをそれが軟化するまで予熱し、モールド
に位置決めする工程 ２．予熱されたシートをモールド表面に、真空引き等に
より密着させる成形工程 ３．賦型された発泡シートを冷却する工程 ４．成形品をモールドのキャビティーから取り出す工程 が含まれる。上記２．成形工程の具体的な例示として
は、ストレート成形、ドレープ成形、リバースドロー成
形、エアスリップ成形、チャンバブロー方式によるエア
スリップ成形、プラグアシスト成形、ドレープアンドプ
ラグアシスト成形、プラグアシストリバースドロー成
形、エアクッション成形、プラグアシストエアスリップ
成形、接触加熱式圧空成形等の真空成形、及び／又は圧
空成形や単純なプレス成形等が挙げられる。Further, the heat forming of the sheet will be described below. 1. 1. Preheat the foam sheet until it softens and position it in the mold. 2. A molding step in which the preheated sheet is brought into close contact with the mold surface by evacuation or the like. 3. Step of cooling the shaped foamed sheet 4. The process includes removing the molded product from the mold cavity. The above 2. Specific examples of the molding process include straight molding, drape molding, reverse draw molding, air slip molding, air slip molding by a chamber blow method, plug assist molding, drape and plug assist molding, plug assist reverse draw molding, and air cushion. Molding, plug-assisted air slip molding, vacuum molding such as contact heating type pressure molding, and / or pressure molding or simple press molding may be used.
【０００９】押出発泡法で発泡シートを製造する場合、
ポリスチレン発泡シート等の一般的樹脂発泡シート作製
時は、樹脂押し出し速度より多少高速で円筒状発泡体が
引取られるから、円筒状発泡体に引取り方向の張力がか
かって該発泡体内の押し出し方向断面の気泡が偏平に形
成される。そして、該シートを成形するために成形機内
加熱部で加熱軟化させると、シート内気泡が偏平状から
球状になろうとしてシートが収縮し、ピンと張った状態
となる。その結果、加熱ムラが無く形の良い成形品が得
られ、曲げ強度や機械的強度も向上すると考えられる。When a foamed sheet is produced by the extrusion foaming method,
When a general resin foam sheet such as a polystyrene foam sheet is manufactured, since the cylindrical foam is taken off at a speed slightly higher than the resin extrusion speed, tension in the take-out direction is applied to the cylindrical foam and the cross-section in the extruding direction inside the foam. Bubbles are formed flat. Then, when the sheet is heated and softened by the heating unit in the molding machine, the air bubbles in the sheet tend to become spherical and contract, and the sheet contracts. As a result, it is considered that a molded product with good shape without heating unevenness can be obtained, and bending strength and mechanical strength are also improved.
【００１０】一方、ポリカーボネート樹脂押出発泡シー
トでは、ダイス出口から押し出される樹脂の伸びが極め
て小さいから、該樹脂がダイスから押し出される速度よ
り速い速度でマンドレルに引取るのが困難である。そこ
で、実際には円筒状発泡体を多少だぶつかせながらマン
ドレルに引取っており、気泡が形成されるダイス出口近
付では円筒状発泡体が弛んでいる。このような方法で形
成される気泡の形状は厚み方向に多少縦長の球状にな
る。このように気泡が形成されているために、該発泡シ
ートを成形機内加熱部で加熱軟化させて成形加工する場
合には、軟化温度で気泡が真球状になろうとするために
発泡シートが伸びてしまう。しかし、成形機内ではシー
ト端部が押えられているから伸びたシートの逃げ場がな
く、成形機内加熱部でシートが波打ってあばれて加熱ム
ラが発生し、その様なシートを成形することによりナキ
や破れ等の不具合が生じて成形品の品質が低下してしま
う。なお、前記したナキは発泡シート表面に形成される
スキン層に亀裂が入っている状態を意味している。On the other hand, in the case of a polycarbonate resin extruded foam sheet, since the resin extruded from the die outlet has a very small elongation, it is difficult to take it into the mandrel at a speed higher than the speed at which the resin is extruded from the die. Therefore, in actuality, the cylindrical foam is taken over by a mandrel while being slightly slackened, and the cylindrical foam is slack when approaching the die outlet where bubbles are formed. The shape of the bubbles formed by such a method is a sphere that is somewhat elongated in the thickness direction. Since the foamed sheet is formed in this way, when the foamed sheet is heated and softened in the heating unit in the molding machine and molded, the foamed sheet stretches because the bubbles tend to become spherical at the softening temperature. I will end up. However, since the edges of the sheet are pressed inside the molding machine, there is no escape area for the stretched sheet, and the heating section inside the molding machine causes the sheet to undulate and generate heating unevenness. Defects such as cracks and tears occur and the quality of the molded product deteriorates. The naki mentioned above means that the skin layer formed on the surface of the foamed sheet has cracks.
【００１１】以上のほか、従来のポリカーボネート樹脂
押出発泡シートの製造では、シート幅５００ｍｍを超え
実用的な発泡シート製造が困難なことも欠点の一つであ
る。これは、円筒状発泡体の伸びが小さいために、サー
キュラダイ直径より２５０％程度以上直径が大きいマン
ドレルでは、押し出された円筒状発泡体を円滑に引取る
のが難かしいために起る問題である。そして、シート幅
が狭いと一般に包装用容器等の連続加熱成形機は、作業
効率面から最低でも５００ｍｍを超える幅のシートを使
うように設計されているから、５００ｍｍ幅以下のシー
トでは使用可能な成形機の機種が限定される。これらを
解決するために、例えば強引に直径の大きいマンドレル
で円筒状発泡体を引取る方法を採用しても、この方法で
はシートが破れてしまったりシート厚が薄くなったり表
面状態が悪くなる等の問題が起り、高品質の発泡シート
を得ることができない。そこで、サーキュラダイの直径
を大きくして幅広のシートを得ることも試みられたが、
この場合はサーキュラダイ直径が大きいから押し出し機
先端のダイス圧力を保持するのが難かしく、そのために
ダイス内部で発泡現象が起こって得られる発泡シートの
表面状態や機械的物性等の品質が低下する。In addition to the above, one of the drawbacks of the conventional production of extruded polycarbonate resin foamed sheets is that it is difficult to produce a practical foamed sheet with a sheet width exceeding 500 mm. This is a problem that occurs because it is difficult to smoothly take out the extruded cylindrical foam with a mandrel whose diameter is 250% or more larger than the circular die diameter because the expansion of the cylindrical foam is small. is there. When the sheet width is narrow, generally, a continuous thermoforming machine such as a packaging container is designed to use a sheet having a width of at least 500 mm or more in terms of work efficiency, so that a sheet having a width of 500 mm or less can be used. The type of molding machine is limited. In order to solve these problems, for example, even if a method of forcibly pulling out the cylindrical foam with a mandrel having a large diameter is adopted, the sheet will be torn or the sheet thickness will become thin, or the surface condition will deteriorate, etc. However, a high quality foamed sheet cannot be obtained. Therefore, it was attempted to increase the diameter of the circular die to obtain a wide sheet,
In this case, since the circular die diameter is large, it is difficult to maintain the die pressure at the tip of the extruder, and as a result, the foaming phenomenon occurs inside the die and the quality of the surface state and mechanical properties of the resulting foamed sheet deteriorates. .
【００１２】本発明のポリカーボネート樹脂押出発泡積
層シートは、加熱下に成形加工する際の寸法安定性が良
いからシートが破れたり波打ったりせず、高品質成形品
を歩留り良く製造できる発泡シートである。また、幅５
００ｍｍを超える場合でも優れた発泡シートである。本
発明積層シートを構成する芯層の発泡シートは独立気泡
率が高いものであることが断熱性、機械的強度等の面か
ら好ましいが、独立気泡率が低いものであってもポリカ
ーボネート樹脂フィルムを芯層の少なくとも片面に積層
している為、実用的なものとなりうる。例えば独立気泡
率が７５％未満の発泡シートは真空成形等に使用した場
合、気泡が連通している為に真空引きが難しく成形体の
角などがシャープに成形できないという金型再現性不良
の問題が起こるのに対し、ポリカーボネート樹脂フィル
ムを積層することでその様な問題も解決できるのであ
る。又、驚くべきことに、シートの断熱性も樹脂フィル
ムを積層したものは、独立気泡率の高いものに比べてさ
ほど劣らない。更に、独立気泡率の高い発泡シートはシ
ートの厚み、幅等のコントロールが難しいのに対し、独
立気泡率の低いものは比較的に厚み、幅、倍率等のコン
トロールが容易である為、このことを利用することによ
り本発明の積層発泡シートの生産性も良好となる。ま
た、発泡シートを構成する気泡形状においては、Ｘをシ
ート幅方向断面の厚み方向と直交する方向の平均気泡径
（ｍｍ）、Ｙをシート押し出し方向断面の厚み方向と直
交する方向の平均気泡径（ｍｍ）、Ｚをシート断面の厚
み方向の平均気泡径（ｍｍ）とした場合、好ましくは１
＜Ｘ／Ｚ≦３、更に好ましくは１．５＜Ｘ／Ｚ≦３で、
好ましくは１＜Ｙ／Ｚ≦５、更に好ましくは１．５＜Ｙ
／Ｚ≦５、しかも（Ｘ＋Ｙ＋Ｚ）／３≧０．１ｍｍの形
状を持つ気泡発泡シートである。気泡の大きさは、（Ｘ
＋Ｙ＋Ｚ）／３≧０．１ｍｍから分るように好ましくは
平均直径０．１ｍｍ以上、更に好ましくは０．２〜０．
５ｍｍに形成されている発泡シートである。この押出発
泡シートを図１に示すが、図１の（ａ）は該発泡シート
の斜視図、（ｂ）は（ａ）のＡで示される部分の拡大断
面図、（ｃ）は（ａ）のＢで示される部分の拡大断面図
である。また、図１のＸ方向、Ｙ方向、Ｚ方向はそれぞ
れシート幅方向、シート押し出し方向及びシート厚み方
向を表し、Ｘ1、Ｘ2、Ｙ1、Ｙ2、Ｚ1、Ｚ2は個々の気泡
のそれぞれの方向における径を表している。The polycarbonate resin extruded foamed laminated sheet of the present invention is a foamed sheet which has good dimensional stability when being molded under heating and therefore does not break or wavy and can produce high quality molded articles with good yield. is there. Also, width 5
It is an excellent foamed sheet even when it exceeds 00 mm. It is preferable that the foamed sheet of the core layer constituting the laminated sheet of the present invention has a high closed cell rate in terms of heat insulation, mechanical strength, etc., but even if the closed cell rate is low, a polycarbonate resin film is used. Since it is laminated on at least one side of the core layer, it can be practical. For example, when a foamed sheet with a closed cell ratio of less than 75% is used for vacuum forming, etc., it is difficult to evacuate because the cells are connected to each other and the corners of the formed body cannot be formed sharply. However, such problems can be solved by laminating a polycarbonate resin film. Surprisingly, the heat insulating property of the sheet is not so inferior to that obtained by laminating the resin films, as compared with the sheet having a high closed cell rate. Furthermore, it is difficult to control the thickness, width, etc. of a foamed sheet with a high closed cell ratio, whereas it is relatively easy to control the thickness, width, magnification, etc. for a foamed sheet with a low closed cell ratio. By utilizing, the productivity of the laminated foam sheet of the present invention is improved. Further, in the shape of bubbles forming the foamed sheet, X is an average bubble diameter (mm) in a direction orthogonal to the thickness direction of the sheet width direction cross section, and Y is an average bubble diameter in a direction orthogonal to the thickness direction of the sheet extrusion direction cross section. (Mm) and Z are average cell diameters (mm) in the thickness direction of the sheet cross section, preferably 1
<X / Z ≦ 3, more preferably 1.5 <X / Z ≦ 3,
Preferably 1 <Y / Z ≦ 5, more preferably 1.5 <Y
It is a foamed foam sheet having a shape of / Z ≦ 5 and (X + Y + Z) /3≧0.1 mm. The size of the bubble is (X
+ Y + Z) /3≧0.1 mm, the average diameter is preferably 0.1 mm or more, more preferably 0.2 to 0.
It is a foamed sheet formed to 5 mm. This extruded foam sheet is shown in Fig. 1. (a) of Fig. 1 is a perspective view of the foam sheet, (b) is an enlarged cross-sectional view of the portion indicated by A in (a), and (c) is (a). It is an expanded sectional view of the part shown by B of FIG. Further, the X direction, the Y direction, and the Z direction in FIG. 1 respectively represent the sheet width direction, the sheet pushing direction, and the sheet thickness direction, and X 1 , X 2 , Y 1 , Y 2 , Z 1 , and Z 2 are individual bubbles. Represents the diameter in each direction.
【００１３】発泡シートは前記形状の気泡で形成されて
いる場合、発泡シートで構成される積層前の芯層を１７
０℃で３０秒間加熱した際の寸法変化が樹脂押出方向で
−３０〜０％、特に好ましくは−３０〜−３％の範囲に
あり、加熱成形時には積層されるポリカーボネート樹脂
フィルムによらず多少縮むから、シートの弛みがないた
め加熱ムラがなく形の良い成形品を得ることができる。
更に、上記加熱条件における該芯層の幅方向の寸法変化
は、−１０〜−１％、特に−７〜−３％の範囲であるこ
とが加熱ムラ防止の点で好ましい。なお、加熱寸法変化
の測定は以下のようにして求める。１７０×１７０ｍｍ
の試験片を作製し、その中央部分に押し出し方向（ＭＤ
方向）と幅方向（ＴＤ方向）に沿って長さ１００ｍｍの
直線を十字に引く。この試験片を、１７０±２℃のオー
ブン内で３０秒間熱処理してから前記直線の長さを測定
し、下式によって加熱寸法変化を求める。 加熱寸法変化＝〔（加熱後の長さｍｍ−１００ｍｍ）／
１００ｍｍ〕×１００ この試験を３回行って平均値を各々ＭＤ方向及びＴＤ方
向の加熱寸法変化とする。尚、上述の通り、発泡シート
は前記形状の気泡で形成されていればポリカーボネート
樹脂フィルムによらず、前述のシートのあばれ、ドロー
ダウンや成形品のナキ等が発生せず良好な成形性を示す
が、厚みが異常に厚いフィルム等のように芯層の収縮し
ようとする力を阻む特異なものでは、この効果の実現は
難しく、通常２０〜５００μｍの厚みの延伸又は無延伸
フィルムが好適である。一方、発泡シートの気泡形状が
１≧Ｘ／Ｚ、１≧Ｙ／Ｚの場合であっても、表層のポリ
カーボネート樹脂フィルムを厚み５０μｍ以上のものを
使用することにより、ポリカーボネート樹脂発泡積層シ
ートの加熱成形時のシートの自重によるシート中央部の
垂れ下がり（ドローダウン）はみられるものの、シート
の大きな伸びによって発生するあばれが引き起こす加熱
ムラによるナキや破れの問題をある程度解決することが
でき、更に表層の該フィルムとして延伸フィルムを使用
する事により、ナキや破れはもとよりドローダウンを防
止することが可能であり、１＜Ｘ／Ｚ≦３、１＜Ｙ／Ｚ
≦５の気泡形状を有する発泡シートを使用した時の効果
に近づけることができる。尚、Ｘ／Ｚ＞３、Ｙ／Ｚ＞５
の場合は、上述の成形品のナキ、シートのあばれやドロ
ーダウンは防止できるが、加熱成形品のシートの伸びが
悪くなる恐れがある。本発明において、加熱成形の際に
ポリカーボネート樹脂発泡積層シートが発泡シート単独
の場合と同様に上式により求められる加熱寸法変化がＭ
Ｄ方向において０〜−３０％、ＴＤ方向においては−１
〜−１０％の範囲であることが好ましく、上述の様に芯
層の気泡形状や表層の延伸度等によって調整することが
できる。尚、ＴＤ方向、ＭＤ方向の加熱時の収縮、成形
時の伸びのバランスを考慮すると、表層は二軸延伸フィ
ルムであることが更に好ましい。このことにより１＜Ｘ
／Ｚ≦３、１＜Ｙ／Ｚ≦５の発泡シートを芯層とする時
と同様、本発明積層シートの加熱成形時に深絞り成形及
び多数個取り成形が容易になる。When the foamed sheet is formed of air bubbles having the above-mentioned shape, the core layer before lamination composed of the foamed sheet is
The dimensional change when heated at 0 ° C. for 30 seconds is in the range of −30 to 0%, particularly preferably −30 to −3% in the resin extrusion direction, and shrinks somewhat during heat molding regardless of the laminated polycarbonate resin film. Therefore, since there is no slack in the sheet, it is possible to obtain a molded article with good shape without heating unevenness.
Further, the dimensional change in the width direction of the core layer under the above heating conditions is preferably in the range of -10 to -1%, particularly -7 to -3% from the viewpoint of preventing heating unevenness. The measurement of the change in heating dimension is obtained as follows. 170 x 170 mm
The test piece of is prepared, and the extrusion direction (MD
Direction) and a width direction (TD direction), a straight line having a length of 100 mm is drawn in a cross shape. This test piece is heat-treated in an oven at 170 ± 2 ° C. for 30 seconds, the length of the straight line is measured, and the change in heating dimension is determined by the following formula. Change in heating dimension = [(length after heating mm-100 mm) /
100 mm] × 100 This test is carried out three times, and the average value is taken as the heating dimension change in the MD direction and the TD direction, respectively. As described above, if the foamed sheet is formed of air bubbles having the above-mentioned shape, regardless of the polycarbonate resin film, the above-mentioned sheet flaking, drawdown, naki of a molded product, etc. do not occur, and good moldability is exhibited. However, it is difficult to realize this effect with a peculiar material that prevents the force of the core layer from shrinking, such as an abnormally thick film, and a stretched or unstretched film having a thickness of 20 to 500 μm is usually suitable. . On the other hand, even when the bubble shape of the foamed sheet is 1 ≧ X / Z and 1 ≧ Y / Z, heating of the polycarbonate resin foamed laminated sheet is performed by using a polycarbonate resin film having a thickness of 50 μm or more as the surface layer. Although the center of the sheet hangs down (drawdown) due to the weight of the sheet during molding, it is possible to solve the problem of plucking and tearing due to uneven heating caused by the large elongation of the sheet to a certain extent, and further to the surface layer. By using a stretched film as the film, it is possible to prevent drawdown as well as pear breakage, and 1 <X / Z ≦ 3, 1 <Y / Z.
The effect when using a foamed sheet having a cell shape of ≦ 5 can be approximated. Incidentally, X / Z> 3, Y / Z> 5
In such a case, the above-mentioned pucker of the molded product, the burrs of the sheet, and the drawdown can be prevented, but the elongation of the sheet of the heat-molded product may be deteriorated. In the present invention, when the polycarbonate resin foam laminated sheet is formed by heat molding, the heating dimensional change obtained by the above formula is M as in the case of using the foam sheet alone.
0 to -30% in D direction, -1 in TD direction
It is preferably in the range of -10%, and as described above, it can be adjusted by the bubble shape of the core layer, the degree of stretching of the surface layer, and the like. In consideration of the balance between shrinkage during heating in the TD direction and MD direction and elongation during molding, the surface layer is more preferably a biaxially stretched film. By this, 1 <X
As in the case where a foamed sheet of / Z ≦ 3, 1 <Y / Z ≦ 5 is used as the core layer, deep drawing and multi-cavity molding are facilitated during heat molding of the laminated sheet of the present invention.
【００１４】以上に詳記した本発明の積層シートで構成
する芯層のポリカーボネート樹脂押出発泡シートは、種
々の方法で製造することができる。例えば、原料のポリ
カーボネートに粘度平均分子量が２５０００以上で、２
５０℃における溶融張力が２．３ｇ以上のものを使うこ
とで達成可能である。このようなポリカーボネートとし
ては、三菱ガス化学社製ユーピロンＳ−１０００〔粘度
平均分子量２６０００、溶融張力２．４ｇ（２５０
℃）〕、ユーピロンＥ−１０００〔粘度平均分子量３２
０００、溶融張力６．４ｇ（２５０℃）〕、ユーピロン
Ｅ−２０００〔粘度平均分子量２９０００、溶融張力
２．６ｇ（２５０℃）〕等が例示される。このほか、上
記以外のポリカーボネートと特定の発泡剤とを組合せる
ことによって達成可能な場合もある。尚、上記溶融張力
は東洋精機製作所社製メルトテンションテスターII型を
使用しオリフィスとその真下に位置するロードセルと連
結しているプーリーとの間隔を２５０ｍｍとし捲き取り
速度１０ｍ／ｍｉｎ、樹脂押出ピストン押出速度１０ｍ
ｍ／ｍｉｎで１２０℃で３時間乾燥させたポリカーボネ
ート樹脂を測定し、ロードセルに検出される値の平均値
を採用した。The polycarbonate resin extruded foam sheet for the core layer, which is composed of the laminated sheet of the present invention described in detail above, can be manufactured by various methods. For example, if the raw material polycarbonate has a viscosity average molecular weight of 25,000 or more,
It can be achieved by using a melt tension at 50 ° C. of 2.3 g or more. As such a polycarbonate, Iupilon S-1000 manufactured by Mitsubishi Gas Chemical Co., Inc. [viscosity average molecular weight 26000, melt tension 2.4 g (250
° C)], Iupilon E-1000 [viscosity average molecular weight 32
000, melt tension 6.4 g (250 ° C.)], Iupilon E-2000 [viscosity average molecular weight 29000, melt tension 2.6 g (250 ° C.)] and the like. In addition, it may be achievable by combining a polycarbonate other than the above with a specific foaming agent. For the melt tension, a melt tension tester type II manufactured by Toyo Seiki Seisaku-sho, Ltd. was used, and the distance between the orifice and the pulley connected directly to the load cell was 250 mm, the winding speed was 10 m / min, and the resin extrusion piston extrusion. Speed 10m
The polycarbonate resin dried at 120 ° C. for 3 hours at m / min was measured, and the average value of the values detected by the load cell was adopted.
【００１５】又、１＜Ｘ／Ｚ≦３、１＜Ｙ／Ｚ≦５の気
泡形状の芯層を得る為には以上に加えて、押出機から出
る樹脂温度の制御、或いは円筒状発泡体の引取り方法改
善等で該発泡シートが得られる。すなわち、以下の通り
である。一般に押し出し機のダイス先端から低圧域に押
し出された円筒状発泡体は、内部から空気によって膨ら
ませられながらバルーン（円筒状発泡体の径がダイス径
からマンドレル径まで拡大される部分）を形成した後
に、マンドレルの円柱側面上に引き取られる。そして、
ポリスチレン系樹脂発泡体やポリエチレン系樹脂発泡体
の製造時には、前記の空気として常温のコンプレッサー
の空気を使えば良いが、本発明の発泡シートの基材樹脂
はポリカーボネート樹脂であり、ガラス転移点が１５０
℃と高温なために、常温のコンプレッサーの空気ではす
ぐに円筒状発泡体が固化して引き取り操作がむずかしく
なる。しかし、該空気の温度を１５１〜２００℃の範囲
内で調整すれば引き取り操作を容易にすることができ
る。また、引取り操作の際に引取り速度が遅いと、発泡
シートを構成する気泡の押出方向への配向が不充分とな
るから、引取り速度は下記式によって求められる速度よ
り大きくすることが好ましく、この方法によって本発明
の目的とする良好なポリカーボネート樹脂押出発泡シー
トが得られる。In order to obtain a cell-shaped core layer with 1 <X / Z ≦ 3, 1 <Y / Z ≦ 5, in addition to the above, control of the resin temperature discharged from the extruder or cylindrical foam The foamed sheet can be obtained by, for example, improving the take-up method. That is, it is as follows. Generally, the cylindrical foam extruded from the die end of the extruder into the low pressure area is inflated by air from the inside to form a balloon (a portion where the diameter of the cylindrical foam is expanded from the die diameter to the mandrel diameter). , Pulled onto the cylindrical side of the mandrel. And
At the time of manufacturing a polystyrene resin foam or a polyethylene resin foam, air of a compressor at room temperature may be used as the air, but the base resin of the foamed sheet of the present invention is a polycarbonate resin and has a glass transition point of 150.
Due to the high temperature of ℃, the air in the compressor at room temperature immediately solidifies the cylindrical foam, which makes the take-up operation difficult. However, if the temperature of the air is adjusted within the range of 151 to 200 ° C., the take-up operation can be facilitated. Further, if the take-up speed is slow during the take-up operation, the orientation of the cells forming the foamed sheet in the extrusion direction will be insufficient, so the take-up speed is preferably higher than the speed obtained by the following formula. By this method, a good polycarbonate resin extruded foam sheet intended for the present invention can be obtained.
【数１】 [Equation 1]
【００１６】上記のように、芯層を構成するポリカーボ
ネート樹脂押出発泡シートを製造する場合の原料や発泡
剤は限定される場合もあるが、選択使用可能な原料や発
泡剤等の範囲について記述すると以下の通りである。該
発泡シート原料として使用されるポリカーボネートは、
炭酸とグリコール又はビスフェノールから形成されるポ
リエステルである。そして、分子鎖にジフェニルアルカ
ンを有する芳香族ポリカーボネートは、結晶性が高く高
融点の上に、耐熱性、耐候性及び耐酸性に優れているか
ら好適である。このようなポリカーボネートとしては、
２，２−ビス（４−オキシフェニル）プロパン（別名ビ
スフェノールＡ）、２，２−ビス（４−オキシフェニ
ル）ブタン、１，１−ビス（４−オキシフェニル）シク
ロヘキサン、１，１−ビス（４−オキシフェニル）イソ
ブタン、１，１−ビス（４−オキシフェニル）エタン等
のビスフェノールから誘導されるポリカーボネートが例
示される。As described above, the raw materials and foaming agents for producing the extruded polycarbonate resin foam sheet constituting the core layer may be limited, but the range of raw materials and foaming agents that can be selectively used will be described. It is as follows. Polycarbonate used as the foam sheet material,
It is a polyester formed from carbonic acid and glycol or bisphenol. An aromatic polycarbonate having diphenylalkane in its molecular chain is preferable because it has high crystallinity, a high melting point, and excellent heat resistance, weather resistance, and acid resistance. As such a polycarbonate,
2,2-bis (4-oxyphenyl) propane (also known as bisphenol A), 2,2-bis (4-oxyphenyl) butane, 1,1-bis (4-oxyphenyl) cyclohexane, 1,1-bis ( Examples include polycarbonates derived from bisphenols such as 4-oxyphenyl) isobutane and 1,1-bis (4-oxyphenyl) ethane.
【００１７】本発明の積層シートに係る芯層を構成する
発泡シート製造の際に使われる発泡剤は、無機発泡剤、
揮発性発泡剤、分解型発泡剤のいずれも使用可能である
が、押出発泡法の場合は分解型発泡剤のみを使うと発泡
倍率の高い発泡体が得られにくいので、揮発性発泡剤を
使用するのが好ましい。又、無機発泡剤としては、二酸
化炭素、窒素等が用いられる。揮発性発泡剤としては、
プロパン、ｎ−ブタン、ｉ−ブタン、ｎ−ペンタン、ｉ
−ペンタン、ヘキサン等の低級脂肪族炭化水素；シクロ
ブタン、シクロペンタン等の低級脂環式炭化水素；ベン
ゼン、トルエン、キシレン等の低級芳香族炭化水素；メ
タノール、エタノール等の脂肪族低級一価アルコール；
アセトン、メチルエチルケトン等の低級脂肪族ケトン；
１−クロロ−１，１−ジフルオロエタン、ペンタフルオ
ロエタン、１，１，１，２−テトラフルオロエタン、
１，１−ジフルオロエタン等の低沸点ハロゲン化炭化水
素；等が用いられる。以上に詳記した発泡剤は、単独又
は２種以上混合して使用可能であり、例えば無機発泡剤
と揮発性発泡剤のように異なった型の発泡剤の併用も可
能である。又、気泡径調節の為に分解型発泡剤の併用も
可能である。The foaming agent used in the production of the foamed sheet constituting the core layer of the laminated sheet of the present invention is an inorganic foaming agent,
Both volatile foaming agents and decomposable foaming agents can be used, but in the case of the extrusion foaming method, it is difficult to obtain foams with a high expansion ratio when using only decomposing foaming agents, so use volatile foaming agents. Preferably. Moreover, carbon dioxide, nitrogen, etc. are used as an inorganic foaming agent. As a volatile foaming agent,
Propane, n-butane, i-butane, n-pentane, i
-Lower aliphatic hydrocarbons such as pentane and hexane; lower alicyclic hydrocarbons such as cyclobutane and cyclopentane; lower aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic lower monohydric alcohols such as methanol and ethanol;
Lower aliphatic ketones such as acetone and methyl ethyl ketone;
1-chloro-1,1-difluoroethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane,
A low-boiling halogenated hydrocarbon such as 1,1-difluoroethane is used. The foaming agents described in detail above can be used alone or as a mixture of two or more kinds. For example, different types of foaming agents such as an inorganic foaming agent and a volatile foaming agent can be used together. In addition, a decomposable foaming agent may be used in combination for controlling the cell diameter.
【００１８】発泡剤使用量は発泡剤の種類や所望する発
泡倍率によっても異なり、発泡倍率によって該発泡シー
トの密度が定まるから、主に所望する発泡シートの密度
で発泡剤の使用量が定まると云える。そして、本発明の
発泡シートは密度０．０３〜０．６ｇ／ｃｍ3、好まし
くは０．０６〜０．２４ｇ／ｃｍ3とするのが望ましい
から、この範囲となるように発泡剤を使えばよい。な
お、本発明の発泡シート密度が０．０３ｇ／ｃｍ3未満
では成形品の強度が小さすぎるし、密度が０．６ｇ／ｃ
ｍ3を超えると断熱性低下や重量増加の上に製造原価も
増加する。発泡シートの密度は０．０６〜０．２４ｇ／
ｃｍ3とするのが好ましく、そのために必要な発泡剤量
は樹脂１００重量部当り揮発性発泡剤では０．５〜１０
重量部（ブタンを使用した場合）、無機発泡剤では０．
２〜３．０重量部（二酸化炭素を使用した場合）程度で
ある。尚、上記発泡シートの密度とは本発明積層シート
に係る芯層の密度のことである。The amount of the foaming agent used varies depending on the type of the foaming agent and the desired expansion ratio, and the density of the foamed sheet is determined by the expansion ratio. Therefore, the amount of the foaming agent used is mainly determined by the desired density of the foamed sheet. Can say The foamed sheet of the present invention preferably has a density of 0.03 to 0.6 g / cm 3 , and preferably 0.06 to 0.24 g / cm 3 , so if a foaming agent is used in this range, Good. When the density of the foamed sheet of the present invention is less than 0.03 g / cm 3 , the strength of the molded product is too small and the density is 0.6 g / c.
When it exceeds m 3 , the heat insulating property is lowered, the weight is increased, and the manufacturing cost is increased. The density of the foam sheet is 0.06-0.24 g /
it is preferable to be cm 3, the blowing agent amount required for the resin 100 parts by weight per volatile blowing agent is 0.5 to 10
In parts by weight (when butane is used), it is 0.
It is about 2 to 3.0 parts by weight (when carbon dioxide is used). The density of the foamed sheet is the density of the core layer of the laminated sheet of the present invention.
【００１９】本発明の芯層を構成する発泡シートでは、
ポリカーボネート樹脂を円滑に発泡させるために、樹脂
と発泡剤との溶融混練物中に必要に応じて気泡調整剤を
添加することができる。この場合の気泡調整剤として
は、タルクやシリカ等の無機粉末、多価カルボン酸の酸
性塩、多価カルボン酸と炭酸ナトリウム又は重炭酸ナト
リウムとの混合物等が好ましい。その添加量は、樹脂１
００重量部当り０．０１〜５．０重量部、好ましくは
０．０５〜０．５重量部とするのが良い。０．０１重量
部より少ないとポリカーボネート樹脂を事実上発泡せし
めることが困難となり、一方５．０重量部よりも多いと
得られた発泡成形品の物性が低下し、好ましくない。In the foamed sheet constituting the core layer of the present invention,
In order to smoothly foam the polycarbonate resin, a cell regulator may be added to the melt-kneaded product of the resin and the foaming agent, if necessary. In this case, the air bubble modifier is preferably an inorganic powder such as talc or silica, an acid salt of polyvalent carboxylic acid, a mixture of polyvalent carboxylic acid and sodium carbonate or sodium bicarbonate, and the like. The addition amount is resin 1
0.01 to 5.0 parts by weight, and preferably 0.05 to 0.5 parts by weight, per 100 parts by weight. If it is less than 0.01 part by weight, it becomes difficult to actually foam the polycarbonate resin, while if it is more than 5.0 parts by weight, the physical properties of the obtained foamed molded article deteriorate, which is not preferable.
【００２０】本発明の発泡積層シートの表層を構成する
ポリカーボネート樹脂としては、前記発泡シートを構成
するポリカーボネート樹脂と同様の原料から製造される
ものが用いられる。本発明のポリカーボネート樹脂押出
発泡積層シートは、押出しラミネート法、ポリカーボネ
ートフィルムの熱ラミネート法、接着材によるフィルム
の接着、共押出し法等により製造することができる。ラ
ミネート用樹脂、特に共押出押出ラミネートに用いられ
るポリカーボネート樹脂の分子量は２００００未満であ
ることが好ましい。２００００以上では共押出又押出ラ
ミネート用としては流動性が悪く、積層体の厚みが不均
一になりやすい。本発明におけるポリカーボネート樹脂
の粘度平均分子量はＳｃｈｎｅｌｌによって与えられた
粘度式As the polycarbonate resin constituting the surface layer of the foamed laminated sheet of the present invention, those produced from the same raw material as the polycarbonate resin constituting the foamed sheet are used. The polycarbonate resin extruded foam laminated sheet of the present invention can be produced by an extrusion laminating method, a thermal laminating method of a polycarbonate film, a film bonding with an adhesive, a coextrusion method, or the like. The molecular weight of the laminating resin, particularly the polycarbonate resin used for coextrusion extrusion lamination, is preferably less than 20,000. When it is 20,000 or more, the fluidity is poor for coextrusion or extrusion lamination, and the thickness of the laminate tends to be nonuniform. The viscosity average molecular weight of the polycarbonate resin in the present invention is the viscosity formula given by Schnell.
【数２】 （但し、〔η〕は極限粘度であり、Ｍは粘度平均分子量
である。）を基に塩化メチレン（２０℃）を溶媒として
浸透圧法によって求められる値である。尚、〔η〕はオ
ストワールド粘度計で比粘度ηspを樹脂濃度を変えて測
定し各濃度Ｃ〔ｇ／１００ｃｍ3〕とηsp／Ｃとをグラ
フにプロットし、下記の値を求める。[Equation 2] (However, [η] is the intrinsic viscosity and M is the viscosity average molecular weight.) Based on the value, it is a value determined by the osmotic pressure method using methylene chloride (20 ° C.) as a solvent. [Η] is measured by an Ostworld viscometer by measuring the specific viscosity ηsp while changing the resin concentration, and the respective concentrations C [g / 100 cm 3 ] and ηsp / C are plotted on a graph to obtain the following values.
【数３】〔η〕＝ｌｉｍηsp／Ｃ Ｃ→Ｏ 熱ラミネート用フィルムとしては、前述の通り、二軸延
伸、一軸延伸、無延伸のどれを用いても良く成形性の面
から好ましくは延伸フィルム特に二軸延伸フィルムが良
い。[Η] = lim ηsp / C C → O As the film for heat lamination, any of biaxially stretched, uniaxially stretched and unstretched may be used as described above, and a stretched film is preferable from the viewpoint of moldability. A biaxially stretched film is particularly preferable.
【００２１】ラミネート又は共押出しするポリカーボネ
ート層の厚さは、２０μｍ〜５００μｍとすることが好
ましく、５０〜２００μｍが特に好ましい。ポリカーボ
ネート層の厚さが２０μｍ未満の場合、ピンホールが発
生したり、サージング（吐出の微妙な変動）による厚み
むらが発生したりして、安定したラミネート又は共押出
し層が得られにくく、又、加熱成形時、独立気泡率の低
い発泡シートに積層した時には、真空成形時穴があいて
しまう等の問題があり、一方５００μｍをこえるとシー
トの柔軟性に欠ける。また、発泡積層シートの全体の厚
みは０．５ｍｍ〜１０ｍｍの範囲が好ましく、更に１ｍ
ｍ〜５ｍｍの範囲が好ましい。シート厚みが０．５ｍｍ
よりも薄いと成形品に強度がなく、１０ｍｍを超えると
金型成形時、加熱シート内部まで平均に加熱する為に強
力な遠赤外線加熱ヒーター等を使用する等の工夫が必要
である。The thickness of the polycarbonate layer to be laminated or coextruded is preferably 20 μm to 500 μm, particularly preferably 50 to 200 μm. When the thickness of the polycarbonate layer is less than 20 μm, pinholes are generated or thickness unevenness is caused by surging (subtle fluctuations in ejection), and it is difficult to obtain a stable laminate or coextrusion layer. At the time of heat molding, when laminated on a foamed sheet having a low closed cell rate, there is a problem that holes are formed at the time of vacuum molding, while if it exceeds 500 μm, the sheet lacks flexibility. The total thickness of the foam laminated sheet is preferably in the range of 0.5 mm to 10 mm, further 1 m.
The range of m to 5 mm is preferable. Sheet thickness is 0.5 mm
If it is thinner than 10 mm, the strength of the molded article will be low. If it exceeds 10 mm, it is necessary to devise such as using a powerful far-infrared heating heater to heat the inside of the heating sheet evenly during die molding.
【００２２】本発明の積層シートを構成する芯層及び／
又は表層には、難燃剤、熱安定剤、耐候性向上剤、着色
剤等のように、通常の発泡シート等に添加される公知の
添加剤を添加することができる。また、水酸化アルミニ
ウム、水酸化カルシウム、水酸化マグネシウム等の無機
水酸化物、炭酸カルシウム、炭酸マグネシウム、炭酸バ
リウム等の無機炭酸塩、亜硫酸カルシウム、亜硫酸マグ
ネシウム等の無機亜硫酸塩、硫酸カルシウム、硫酸マグ
ネシウム、硫酸アルミニウム等の無機硫酸塩、酸化カル
シウム、酸化アルミニウム、酸化ケイ素等の無機酸化
物、タルク、クレー、カオリン、ゼオライト等の粘度又
は天然鉱物等の無機充填剤を５〜３０重量％添加しても
よい。Core layer constituting the laminated sheet of the present invention and /
Alternatively, known additives, such as flame retardants, heat stabilizers, weather resistance improvers, and colorants, which are commonly added to foamed sheets and the like can be added to the surface layer. Further, inorganic hydroxides such as aluminum hydroxide, calcium hydroxide and magnesium hydroxide, inorganic carbonates such as calcium carbonate, magnesium carbonate and barium carbonate, inorganic sulfites such as calcium sulfite and magnesium sulfite, calcium sulfate and magnesium sulfate. , 5 to 30% by weight of inorganic sulfate such as aluminum sulfate, inorganic oxide such as calcium oxide, aluminum oxide and silicon oxide, viscosity such as talc, clay, kaolin and zeolite or inorganic filler such as natural mineral Good.
【００２３】以上のようにして得られたポリカーボネー
ト樹脂発泡積層シートは、ポリカーボネート樹脂本来の
優れた特性を有する発泡積層シートである。そしてその
芯層の発泡シートの両面又は一方の面に、該発泡シート
との接着性が良いポリカーボネート樹脂からなる表層を
積層したものであるから、機械的強度は極めて優れたも
のである上、加熱成形に際して芯材の発泡シートの独立
気泡率に左右されず真空引きが可能であり、金型再現
性、成形性が良好で、特に深絞り加工性が優れている。The foamed polycarbonate resin laminated sheet obtained as described above is a foamed laminated sheet having the excellent characteristics inherent to the polycarbonate resin. Then, on both surfaces or one surface of the foamed sheet of the core layer, a surface layer made of a polycarbonate resin having good adhesiveness with the foamed sheet is laminated, so that the mechanical strength is extremely excellent, and the heating is performed. During molding, vacuuming is possible without being affected by the closed cell rate of the foamed sheet of the core material, mold reproducibility and moldability are good, and particularly deep drawability is excellent.
【００２４】[0024]
【実施例】次に、本発明を実施例によって更に具体的に
説明するが、本発明はこの実施例によって限定されるも
のではない。EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.
【００２５】実施例１ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機中
で、加熱、溶融、混練した後、発泡剤としてイソペンタ
ンを０．５３モル／ｋｇ樹脂、押出機中より圧入し、樹
脂温度２００度で押出し、円筒状発泡体の内部及び外部
を８０℃の熱風で加熱しながらバルーンを形成させ、こ
れを直径２００ｍｍのマンドレルで引き取ってから押出
方向に沿って切り開いてシート状発泡体を得た。なおサ
ーキュラダイ直径は６５ｍｍ、ダイスクリアーは、０．
７ｍｍである。また円筒状発泡体の吐出量は５０ｋｇ／
ｈｒ、該発泡体の引取速度は６．５ｍ／分とした。この
発泡シートは、独立気泡率８０％、芯層密度０．１２ｇ
／ｃｍ3、平均セル径０．３４ｍｍ、シート厚み２．１
ｍｍ、シート幅６４０ｍｍとなり、このシートの片面に
厚さ８０μｍとなるようにビスフェノールＡよりなるポ
リカーボネート樹脂（粘度平均分子量１８０００）を押
出ラミネートし、表１に示す発泡積層シートを得た。そ
のシートを多数個取りの熱成形機を用いて上面直径１５
０ｍｍ、下面直径１１０ｍｍ、深さ９０ｍｍの丼型成形
物に真空成形し、成形加熱時の、シートのあばれ、深絞
り性、金型再現性、ドローダウン性を評価した。結果を
表１に示す。Example 1 A raw material resin prepared by adding 0.05 part by weight of talc as a nucleating agent to 100 parts by weight of a polycarbonate resin (viscosity average molecular weight 29000) made of bisphenol A was heated, melted and kneaded in an extruder. After that, isopentane as a foaming agent, 0.53 mol / kg resin, was pressed into the extruder and extruded at a resin temperature of 200 ° C. to form a balloon while heating the inside and outside of the cylindrical foam with hot air at 80 ° C. Then, this was taken out with a mandrel having a diameter of 200 mm and then cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm and the die clear is 0.
7 mm. The discharge rate of the cylindrical foam is 50 kg /
hr, the take-up speed of the foam was 6.5 m / min. This foam sheet has a closed cell rate of 80% and a core layer density of 0.12 g.
/ Cm 3 , average cell diameter 0.34 mm, sheet thickness 2.1
mm, the sheet width was 640 mm, and a polycarbonate resin (viscosity average molecular weight 18000) made of bisphenol A was extrusion-laminated on one surface of the sheet to a thickness of 80 μm to obtain a foamed laminated sheet shown in Table 1. Using a thermoforming machine that takes multiple sheets of the sheet, the upper surface diameter is 15
Vacuum molding was performed on a bowl-shaped molded product having a diameter of 0 mm, a lower surface diameter of 110 mm, and a depth of 90 mm, and during the heating for molding, the sheet was exposed, the deep drawability, the mold reproducibility, and the drawdown property were evaluated. The results are shown in Table 1.
【００２６】実施例２ 実施例１と同様な発泡シートを芯層に、厚さ１００μｍ
の二軸延伸ポリカーボネート樹脂フィルム（粘度平均分
子量３００００）を熱ラミネートし、実施例１と同様に
成形評価を行った。結果を表１に示す。Example 2 The same foamed sheet as in Example 1 was used as the core layer, and the thickness was 100 μm.
The biaxially stretched polycarbonate resin film of (No. 30000, viscosity average molecular weight) was heat laminated, and the molding evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
【００２７】実施例３ 実施例１と同様な発泡シートを芯層に、厚さ１２０μｍ
の無延伸ポリカーボネート樹脂フィルム（粘度平均分子
量２５０００）を熱ラミネートし、実施例１と同様に成
形評価を行った。結果を表１に示す。Example 3 A foamed sheet similar to that in Example 1 was used as the core layer with a thickness of 120 μm.
The unstretched polycarbonate resin film (having a viscosity average molecular weight of 25,000) was heat-laminated, and the molding evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
【００２８】実施例４ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機に供
給し押出機中で、加熱、溶融、混練した後、発泡剤とし
てイソペンタンを０．５５モル／ｋｇ樹脂、押出機中よ
り圧入し、樹脂温度１９６℃で押出し、円筒状発泡体の
内部及び外部を８０℃の熱風で加熱しながらバルーンを
形成させ、これを直径２００ｍｍのマンドレルで引き取
ってから押出方向に沿って切り開いてシート状発泡体を
得た。なおサーキュラダイ直径は６５ｍｍ、ダイスクリ
アーは１．２ｍｍである。また円筒状発泡体の吐出量は
５１ｋｇ／ｈｒ、該発泡体の引取速度は６．３ｍ／分と
した。この発泡シートは、独立気泡率１５％、芯層密度
０．０８ｇ／ｃｍ3、平均セル径０．６１ｍｍ、シート
厚み４．０ｍｍ、シート幅６４０ｍｍとなり、このシー
トの任意の片面に厚さ１５０μｍの二軸延伸ポリカーボ
ネート樹脂フィルム（粘度平均分子量３００００）を熱
ラミネートし、実施例１と同様に成形評価を行った。結
果を表１に示す。Example 4 A raw material resin prepared by adding 0.05 part by weight of talc as a nucleating agent to 100 parts by weight of a polycarbonate resin made of bisphenol A (viscosity average molecular weight 29000) was fed to the extruder and heated in the extruder. After melting and kneading, isopentane 0.55 mol / kg resin as a foaming agent was pressed into the extruder and extruded at a resin temperature of 196 ° C., and the inside and outside of the cylindrical foam was heated with hot air of 80 ° C. While forming a balloon, the balloon was formed, and the balloon was taken up by a mandrel having a diameter of 200 mm and cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm, and the die clear is 1.2 mm. The discharge rate of the cylindrical foam was 51 kg / hr, and the take-up speed of the foam was 6.3 m / min. This foamed sheet had a closed cell rate of 15%, a core layer density of 0.08 g / cm 3 , an average cell diameter of 0.61 mm, a sheet thickness of 4.0 mm and a sheet width of 640 mm, and a thickness of 150 μm on any one side of the sheet. A biaxially stretched polycarbonate resin film (viscosity average molecular weight 30,000) was heat laminated, and molding evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
【００２９】実施例５ 実施例４と同様な発泡シートを芯層に、厚さ１００μｍ
の無延伸ポリカーボネート樹脂フィルム（粘度平均分子
量２５０００）を熱ラミネートし、実施例１と同様に成
形評価を行った。結果を表１に示す。Example 5 The same foamed sheet as in Example 4 was used as the core layer, and the thickness was 100 μm.
The unstretched polycarbonate resin film (having a viscosity average molecular weight of 25,000) was heat-laminated, and the molding evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
【００３０】実施例６ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機に供
給し押出機中で、加熱、溶融、混練した後、発泡剤とし
てイソペンタンを０．５３モル／ｋｇ樹脂、押出機中よ
り圧入し樹脂温度２００℃で押出し、円筒状発泡体の内
部及び外部を８０℃の熱風で加熱しながらバルーンを形
成させ、これを直径２００ｍｍのマンドレルで引き取っ
てから押出方向に沿って切り開いてシート状発泡体を得
た。なお、サーキュラダイ直径は６５ｍｍ、ダイスクリ
アーは０．７ｍｍである。また円筒状発泡体の吐出量は
５０ｋｇ／ｈｒ、該発泡体の引取速度は６．４ｍ／分と
した。この発泡シートは、独立気泡率８０％、芯層密度
０．１２ｇ／ｃｍ3、平均セル径０．３０ｍｍ、シート
厚み２．０ｍｍ、シート幅６４０ｍｍとなり、このシー
トの任意の片面に厚さ４０μｍの二軸延伸ポリカーボネ
ート樹脂フィルム（粘度平均分子量３００００）を熱ラ
ミネートし、実施例１と同様に成形評価を行った。結果
を表１に示す。Example 6 To 100 parts by weight of a polycarbonate resin (viscosity average molecular weight 29000) made of bisphenol A, 0.05 parts by weight of talc was added as a nucleating agent, and the starting resin was fed to the extruder and heated in the extruder. After melting and kneading, 0.53 mol / kg resin as a foaming agent was pressed into the extruder and extruded at a resin temperature of 200 ° C., while heating the inside and outside of the cylindrical foam with hot air at 80 ° C. A balloon was formed, and this was taken up by a mandrel having a diameter of 200 mm and then cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm and the die clear is 0.7 mm. The discharge rate of the cylindrical foam was 50 kg / hr and the take-up speed of the foam was 6.4 m / min. This foamed sheet had a closed cell rate of 80%, a core layer density of 0.12 g / cm 3 , an average cell diameter of 0.30 mm, a sheet thickness of 2.0 mm, and a sheet width of 640 mm, and a thickness of 40 μm on any one side of the sheet. A biaxially stretched polycarbonate resin film (viscosity average molecular weight 30,000) was heat laminated, and molding evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
【００３１】実施例７ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機に供
給し押出機中で、加熱、溶融、混練した後、発泡剤とし
てイソペンタンを０．５３モル／ｋｇ樹脂、押出機中よ
り圧入し樹脂温度２０１℃で押出し、円筒状発泡体の内
部及び外部を８０℃の熱風で加熱しながらバルーンを形
成させ、これを直径２００ｍｍのマンドレルで引き取っ
てから押出方向に沿って切り開いてシート状発泡体を得
た。なお、サーキュラダイ直径は６５ｍｍ、ダイスクリ
アーは０．７ｍｍである。また円筒状発泡体の吐出量は
５３ｋｇ／ｈｒ、該発泡体の引取速度は６．８ｍ／分と
した。その際、ビスフェノールＡよりなるポリカーボネ
ート樹脂（粘度平均分子量１５０００）を共押出して、
厚さ４０μｍの表層を片面に設けた。この発泡シート
は、独立気泡率８５％、芯層密度０．１１ｇ／ｃｍ3、
平均セル径０．４７ｍｍ、シート厚み２．０ｍｍ、シー
ト幅６４０ｍｍとなり、実施例１と同様に成形評価を行
った。結果を表１に示す。Example 7 A raw material resin prepared by adding 0.05 part by weight of talc as a nucleating agent to 100 parts by weight of a polycarbonate resin (viscosity average molecular weight 29000) made of bisphenol A was heated in the extruder. After melting and kneading, isopentane 0.53 mol / kg resin as a foaming agent was pressed into the extruder and extruded at a resin temperature of 201 ° C, while heating the inside and outside of the cylindrical foam with hot air of 80 ° C. A balloon was formed, and this was taken up by a mandrel having a diameter of 200 mm and then cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm and the die clear is 0.7 mm. The discharge rate of the cylindrical foam was 53 kg / hr, and the take-up speed of the foam was 6.8 m / min. At that time, a polycarbonate resin composed of bisphenol A (viscosity average molecular weight 15,000) was coextruded,
A surface layer having a thickness of 40 μm was provided on one surface. This foamed sheet had a closed cell rate of 85%, a core layer density of 0.11 g / cm 3 ,
The average cell diameter was 0.47 mm, the sheet thickness was 2.0 mm, and the sheet width was 640 mm, and the molding evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
【００３２】実施例８ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機に供
給し押出機中で、加熱、溶融、混練した後、発泡剤とし
てイソペンタンを０．４３モル／ｋｇ樹脂、押出機中よ
り圧入し樹脂温度２０３℃で押出し、円筒状発泡体の内
部及び外部を８０℃の熱風で加熱しながらバルーンを形
成させ、これを直径２００ｍｍのマンドレルで引き取っ
てから押出方向に沿って切り開いてシート状発泡体を得
た。なお、サーキュラダイ直径は６５ｍｍ、ダイスクリ
アーは０．７ｍｍである。また円筒状発泡体の吐出量は
５０ｋｇ／ｈｒ、該発泡体の引取速度は５．０ｍ／分と
した。この発泡シートは、独立気泡率４０％、芯層密度
０．１５ｇ／ｃｍ3、平均セル径０．３１ｍｍ、シート
厚み４．０ｍｍ、シート幅６４０ｍｍとなり、このシー
トの任意の片面に厚さ７０μｍの二軸延伸ポリカーボネ
ート樹脂フィルム（粘度平均分子量３００００）を熱ラ
ミネートし、実施例１と同様に成形評価を行った。結果
を表１に示す。Example 8 A raw material resin prepared by adding 0.05 part by weight of talc as a nucleating agent to 100 parts by weight of a polycarbonate resin (viscosity average molecular weight 29000) made of bisphenol A was heated in the extruder. After melting and kneading, isopentane as a foaming agent was 0.43 mol / kg resin, which was pressed into the extruder and extruded at a resin temperature of 203 ° C. while heating the inside and outside of the cylindrical foam with hot air at 80 ° C. A balloon was formed, and this was taken up by a mandrel having a diameter of 200 mm and then cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm and the die clear is 0.7 mm. The discharge rate of the cylindrical foam was 50 kg / hr, and the take-up speed of the foam was 5.0 m / min. This foamed sheet had a closed cell rate of 40%, a core layer density of 0.15 g / cm 3 , an average cell diameter of 0.31 mm, a sheet thickness of 4.0 mm and a sheet width of 640 mm, and a sheet having a thickness of 70 μm on any one surface of the sheet. A biaxially stretched polycarbonate resin film (viscosity average molecular weight 30,000) was heat laminated, and molding evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
【００３３】実施例９ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機に供
給し押出機中で、加熱、溶融、混練した後、発泡剤とし
てイソペンタンを０．５０モル／ｋｇ樹脂、押出機中よ
り圧入し樹脂温度２０２℃で押出し、円筒状発泡体の内
部及び外部を８０℃の熱風で加熱しながらバルーンを形
成させ、これを直径２００ｍｍのマンドレルで引き取っ
てから押出方向に沿って切り開いてシート状発泡体を得
た。なお、サーキュラダイ直径は６５ｍｍ、ダイスクリ
アーは０．７ｍｍである。また円筒状発泡体の吐出量は
５５ｋｇ／ｈｒ、該発泡体の引取速度は６．７ｍ／分と
した。その際、ビスフェノールＡよりなるポリカーボネ
ート樹脂（粘度平均分子量１００００）を共押出して、
厚さ５０μｍの表層を両面に設けた。この発泡シート
は、独立気泡率８０％、芯層密度０．１０ｇ／ｃｍ3、
平均セル径０．５０ｍｍ、シート厚み２．０ｍｍ、シー
ト幅６４０ｍｍとなり、実施例１と同様に成形評価を行
った。結果を表１に示す。Example 9 To 100 parts by weight of a polycarbonate resin composed of bisphenol A (viscosity average molecular weight of 29000), 0.05 parts by weight of talc was added as a nucleating agent, and a raw material resin was supplied to the extruder and heated in the extruder. After melting and kneading, isopentane was added as a foaming agent at 0.50 mol / kg resin, which was pressed into the extruder and extruded at a resin temperature of 202 ° C., while heating the inside and outside of the cylindrical foam with hot air at 80 ° C. A balloon was formed, and this was taken up by a mandrel having a diameter of 200 mm and then cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm and the die clear is 0.7 mm. The discharge rate of the cylindrical foam was 55 kg / hr and the take-up speed of the foam was 6.7 m / min. At that time, a polycarbonate resin made of bisphenol A (viscosity average molecular weight 10000) was coextruded,
A surface layer having a thickness of 50 μm was provided on both surfaces. This foamed sheet has a closed cell ratio of 80%, a core layer density of 0.10 g / cm 3 ,
The average cell diameter was 0.50 mm, the sheet thickness was 2.0 mm, and the sheet width was 640 mm, and the molding evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
【００３４】実施例１０ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機に供
給し押出機中で、加熱、溶融、混練した後、発泡剤とし
てイソペンタンを１．１モル／ｋｇ樹脂、押出機中より
圧入し樹脂温度１９５℃で押出し、円筒状発泡体の内部
及び外部を８０℃の熱風で加熱しながらバルーンを形成
させ、これを直径２００ｍｍのマンドレルで引き取って
から押出方向に沿って切り開いてシート状発泡体を得
た。なお、サーキュラダイ直径は６５ｍｍ、ダイスクリ
アーは０．７ｍｍである。また円筒状発泡体の吐出量は
５０ｋｇ／ｈｒ、該発泡体の引取速度は６．０ｍ／分と
した。この発泡シートは、独立気泡率８０％、芯層密度
０．０６ｇ／ｃｍ3、平均セル径０．６５ｍｍ、シート
厚み５．０ｍｍ、シート幅６４０ｍｍとなり、このシー
トの任意の片面に厚さ８０μｍの二軸延伸ポリカーボネ
ート樹脂フィルム（粘度平均分子量２９０００）を熱ラ
ミネートし、実施例１と同様に成形評価を行った。結果
を表１に示す。Example 10 A raw material resin obtained by adding 0.05 part by weight of talc as a nucleating agent to 100 parts by weight of a polycarbonate resin (viscosity average molecular weight 29000) made of bisphenol A was heated in the extruder. After melting and kneading, isopentane as a foaming agent was 1.1 mol / kg resin, which was pressed into the extruder and extruded at a resin temperature of 195 ° C., while heating the inside and outside of the cylindrical foam with hot air of 80 ° C. A balloon was formed, and this was taken up by a mandrel having a diameter of 200 mm and then cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm and the die clear is 0.7 mm. The discharge rate of the cylindrical foam was 50 kg / hr and the take-up speed of the foam was 6.0 m / min. This foamed sheet had a closed cell rate of 80%, a core layer density of 0.06 g / cm 3 , an average cell diameter of 0.65 mm, a sheet thickness of 5.0 mm, and a sheet width of 640 mm, and a thickness of 80 μm on any one side of this sheet. A biaxially stretched polycarbonate resin film (viscosity average molecular weight 29000) was heat laminated, and the molding evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
【００３５】実施例１１ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機に供
給し押出機中で、加熱、溶融、混練した後、発泡剤とし
てイソペンタンを０．５０モル／ｋｇ樹脂、押出機中よ
り圧入し樹脂温度２１０℃で押出し、円筒状発泡体の内
部及び外部を８０℃の熱風で加熱しながらバルーンを形
成させ、これを直径２００ｍｍのマンドレルで引き取っ
てから押出方向に沿って切り開いてシート状発泡体を得
た。なお、サーキュラダイ直径は６５ｍｍ、ダイスクリ
アーは０．７ｍｍである。また円筒状発泡体の吐出量は
５０ｋｇ／ｈｒ、該発泡体の引取速度は６．４ｍ／分と
した。この発泡シートは、独立気泡率１０％、芯層密度
０．１０ｇ／ｃｍ3、平均セル径０．３０ｍｍ、シート
厚み２．２ｍｍ、シート幅６４０ｍｍとなり、このシー
トの任意の片面に厚さ８０μｍの二軸延伸ポリカーボネ
ート樹脂フィルム（粘度平均分子量２９０００）を熱ラ
ミネートし、実施例１と同様に成形評価を行った。結果
を表１に示す。Example 11 0.05 parts by weight of talc as a nucleating agent was added to 100 parts by weight of a polycarbonate resin made of bisphenol A (viscosity average molecular weight 29000), and the starting resin was fed to the extruder and heated in the extruder. After melting and kneading, isopentane as a foaming agent was added at 0.50 mol / kg resin under pressure from an extruder and extruded at a resin temperature of 210 ° C, while heating the inside and outside of the cylindrical foam with hot air at 80 ° C. A balloon was formed, and this was taken up by a mandrel having a diameter of 200 mm and then cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm and the die clear is 0.7 mm. The discharge rate of the cylindrical foam was 50 kg / hr and the take-up speed of the foam was 6.4 m / min. This foamed sheet had a closed cell rate of 10%, a core layer density of 0.10 g / cm 3 , an average cell diameter of 0.30 mm, a sheet thickness of 2.2 mm, and a sheet width of 640 mm, and a thickness of 80 μm on any one surface of the sheet. A biaxially stretched polycarbonate resin film (viscosity average molecular weight 29000) was heat laminated, and the molding evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
【００３６】実施例１２ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機に供
給し押出機中で、加熱、溶融、混練した後、発泡剤とし
てイソペンタンを０．５３モル／ｋｇ樹脂、押出機中よ
り圧入し樹脂温度２１０℃で押出し、円筒状発泡体の内
部及び外部を８０℃の熱風で加熱しながらバルーンを形
成させ、これを直径２００ｍｍのマンドレルで引き取っ
てから押出方向に沿って切り開いてシート状発泡体を得
た。なお、サーキュラダイ直径は６５ｍｍ、ダイスクリ
アーは０．７ｍｍである。また円筒状発泡体の吐出量は
５０ｋｇ／ｈｒ、該発泡体の引取速度は６．６ｍ／分と
した。この発泡シートは、独立気泡率１０％、芯層密度
０．１１ｇ／ｃｍ3、平均セル径０．５１ｍｍ、シート
厚み２．３ｍｍ、シート幅６４０ｍｍとなり、このシー
トの任意の片面に厚さ１５０μｍにビスフェノールＡよ
りなるポリカーボネート樹脂（粘度平均分子量１８００
０）を押出ラミネートし、実施例１と同様に成形評価を
行った。結果を表１に示す。Example 12 0.05 parts by weight of talc as a nucleating agent was added to 100 parts by weight of a polycarbonate resin (viscosity average molecular weight 29000) made of bisphenol A, and the starting resin was heated in the extruder. After melting and kneading, 0.53 mol / kg resin isopentane as a foaming agent was pressed into the extruder and extruded at a resin temperature of 210 ° C, while heating the inside and outside of the cylindrical foam with hot air at 80 ° C. A balloon was formed, and this was taken up by a mandrel having a diameter of 200 mm and then cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm and the die clear is 0.7 mm. The discharge rate of the cylindrical foam was 50 kg / hr, and the take-up speed of the foam was 6.6 m / min. This foamed sheet had a closed cell rate of 10%, a core layer density of 0.11 g / cm 3 , an average cell diameter of 0.51 mm, a sheet thickness of 2.3 mm and a sheet width of 640 mm, and a thickness of 150 μm on any one side of this sheet. Polycarbonate resin consisting of bisphenol A (viscosity average molecular weight 1800
0) was extrusion-laminated, and the molding evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
【００３７】実施例１３ 実施例１２と同様な発泡シートを芯層に、厚さ８０μｍ
の無延伸ポリカーボネート樹脂フィルム（粘度平均分子
量２５０００）を熱ラミネートし、実施例１と同様に成
形評価を行った。結果を表１に示す。Example 13 The same foamed sheet as in Example 12 was used as the core layer, and the thickness was 80 μm.
The unstretched polycarbonate resin film (having a viscosity average molecular weight of 25,000) was heat-laminated, and the molding evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
【００３８】比較例１ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機に供
給し押出機中で、加熱、溶融、混練した後、発泡剤とし
てイソペンタンを０．５３モル／ｋｇ樹脂、押出機中よ
り圧入し樹脂温度２００℃で押出し、円筒状発泡体の内
部及び外部を８０℃の熱風で加熱しながらバルーンを形
成させ、これを直径２００ｍｍのマンドレルで引き取っ
てから押出方向に沿って切り開いてシート状発泡体を得
た。なお、サーキュラダイ直径は６５ｍｍ、ダイスクリ
アーは０．７ｍｍである。また円筒状発泡体の吐出量は
５０ｋｇ／ｈｒ、該発泡体の引取速度は６．２ｍ／分と
した。この発泡シートは、独立気泡率８５％、芯層密度
０．１０ｇ／ｃｍ3、平均セル径０．５３ｍｍ、シート
厚み１．９ｍｍ、シート幅６４０ｍｍとなり、このシー
トに表層を設ける事なく、実施例１と同様に成形評価を
行った。結果を表１に示す。Comparative Example 1 A raw material resin prepared by adding 0.05 part by weight of talc as a nucleating agent to 100 parts by weight of a polycarbonate resin made of bisphenol A (viscosity average molecular weight 29000) was heated in the extruder. After melting and kneading, 0.53 mol / kg resin as a foaming agent was pressed into the extruder and extruded at a resin temperature of 200 ° C., while heating the inside and outside of the cylindrical foam with hot air at 80 ° C. A balloon was formed, and this was taken up by a mandrel having a diameter of 200 mm and then cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm and the die clear is 0.7 mm. The discharge rate of the cylindrical foam was 50 kg / hr and the take-up speed of the foam was 6.2 m / min. This foamed sheet had a closed cell rate of 85%, a core layer density of 0.10 g / cm 3 , an average cell diameter of 0.53 mm, a sheet thickness of 1.9 mm, and a sheet width of 640 mm. Molding evaluation was performed in the same manner as in 1. The results are shown in Table 1.
【００３９】比較例２ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機に供
給し押出機中で、加熱、溶融、混練した後、発泡剤とし
てイソペンタンを０．５３モル／ｋｇ樹脂、押出機中よ
り圧入し樹脂温度２００℃で押出し、円筒状発泡体の内
部及び外部を８０℃の熱風で加熱しながらバルーンを形
成させ、これを直径２００ｍｍのマンドレルで引き取っ
てから押出方向に沿って切り開いてシート状発泡体を得
た。なお、サーキュラダイ直径は６５ｍｍ、ダイスクリ
アーは０．７ｍｍである。また円筒状発泡体の吐出量は
５０ｋｇ／ｈｒ、該発泡体の引取速度は６．５ｍ／分と
した。この発泡シートは、独立気泡率８０％、芯層密度
０．１１ｇ／ｃｍ3、平均セル径０．３３ｍｍ、シート
厚み２．０ｍｍ、シート幅６４０ｍｍとなり、このシー
トに表層を設ける事なく、実施例１と同様に成形評価を
行った。結果を表１に示す。Comparative Example 2 A raw material resin prepared by adding 0.05 part by weight of talc as a nucleating agent to 100 parts by weight of a polycarbonate resin (viscosity average molecular weight 29000) made of bisphenol A was heated in the extruder. After melting and kneading, 0.53 mol / kg resin as a foaming agent was pressed into the extruder and extruded at a resin temperature of 200 ° C., while heating the inside and outside of the cylindrical foam with hot air at 80 ° C. A balloon was formed, and this was taken up by a mandrel having a diameter of 200 mm and then cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm and the die clear is 0.7 mm. The discharge rate of the cylindrical foam was 50 kg / hr and the take-up speed of the foam was 6.5 m / min. This foamed sheet had a closed cell rate of 80%, a core layer density of 0.11 g / cm 3 , an average cell diameter of 0.33 mm, a sheet thickness of 2.0 mm, and a sheet width of 640 mm. Molding evaluation was performed in the same manner as in 1. The results are shown in Table 1.
【００４０】比較例３ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機に供
給し押出機中で、加熱、溶融、混練した後、発泡剤とし
てイソペンタンを０．５５モル／ｋｇ樹脂、押出機中よ
り圧入し樹脂温度２１３℃で押出し、円筒状発泡体の内
部及び外部を８０℃の熱風で加熱しながらバルーンを形
成させ、これを直径２００ｍｍのマンドレルで引き取っ
てから押出方向に沿って切り開いてシート状発泡体を得
た。なお、サーキュラダイ直径は６５ｍｍ、ダイスクリ
アーは０．７ｍｍである。また円筒状発泡体の吐出量は
５０ｋｇ／ｈｒ、該発泡体の引取速度は６．０ｍ／分と
した。この発泡シートは、独立気泡率１５％、芯層密度
０．１３ｇ／ｃｍ3、平均セル径０．３４ｍｍ、シート
厚み１．７ｍｍ、シート幅６４０ｍｍとなり、このシー
トに表層を設ける事なく、実施例１と同様に成形評価を
行った。結果を表１に示す。Comparative Example 3 A raw material resin prepared by adding 0.05 part by weight of talc as a nucleating agent to 100 parts by weight of a polycarbonate resin made of bisphenol A (viscosity average molecular weight 29000) was heated in the extruder. After melting and kneading, isopentane 0.55 mol / kg resin as a foaming agent was press-fitted from the extruder and extruded at a resin temperature of 213 ° C. while heating the inside and outside of the cylindrical foam with hot air of 80 ° C. A balloon was formed, and this was taken up by a mandrel having a diameter of 200 mm and then cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm and the die clear is 0.7 mm. The discharge rate of the cylindrical foam was 50 kg / hr and the take-up speed of the foam was 6.0 m / min. This foamed sheet had a closed cell rate of 15%, a core layer density of 0.13 g / cm 3 , an average cell diameter of 0.34 mm, a sheet thickness of 1.7 mm, and a sheet width of 640 mm. Molding evaluation was performed in the same manner as in 1. The results are shown in Table 1.
【００４１】比較例４ ビスフェノールＡよりなるポリカーボネート樹脂（粘度
平均分子量２９０００）１００重量部に対し、核剤とし
てタルク０．０５重量部を加えた原料樹脂を押出機に供
給し押出機中で、加熱、溶融、混練した後、発泡剤とし
てイソペンタンを０．５５モル／ｋｇ樹脂、押出機中よ
り圧入し樹脂温度２１２℃で押出し、円筒状発泡体の内
部及び外部を８０℃の熱風で加熱しながらバルーンを形
成させ、これを直径２００ｍｍのマンドレルで引き取っ
てから押出方向に沿って切り開いてシート状発泡体を得
た。なお、サーキュラダイ直径は６５ｍｍ、ダイスクリ
アーは０．７ｍｍである。また円筒状発泡体の吐出量は
５０ｋｇ／ｈｒ、該発泡体の引取速度は６．０ｍ／分と
した。この発泡シートは、独立気泡率１５％、芯層密度
０．１３ｇ／ｃｍ3、平均セル径０．３５ｍｍ、シート
厚み１．８ｍｍ、シート幅６４０ｍｍとなり、このシー
トに表層を設ける事なく、実施例１と同様に成形評価を
行った。結果を表１に示す。Comparative Example 4 A raw material resin prepared by adding 0.05 part by weight of talc as a nucleating agent to 100 parts by weight of a polycarbonate resin (viscosity average molecular weight 29000) made of bisphenol A was heated in the extruder. After melting and kneading, isopentane 0.55 mol / kg resin as a foaming agent was pressed into the extruder and extruded at a resin temperature of 212 ° C, while heating the inside and outside of the cylindrical foam with hot air at 80 ° C. A balloon was formed, and this was taken up by a mandrel having a diameter of 200 mm and then cut open along the extrusion direction to obtain a sheet-like foam. The circular die diameter is 65 mm and the die clear is 0.7 mm. The discharge rate of the cylindrical foam was 50 kg / hr and the take-up speed of the foam was 6.0 m / min. This foamed sheet had a closed cell rate of 15%, a core layer density of 0.13 g / cm 3 , an average cell diameter of 0.35 mm, a sheet thickness of 1.8 mm, and a sheet width of 640 mm. Molding evaluation was performed in the same manner as in 1. The results are shown in Table 1.
【００４２】[0042]
【表１−（１）】 [Table 1- (1)]
【表１−（２）】 [Table 1- (2)]
【００４３】〔評価基準〕 ・成形加熱時のシートのあばれ ○ 良好 △ 少々あばれるが成形できる × 大きくあばれ、成形できない ・深絞り成形性 ○ 良好 △ 少々のナキ等があるが成形できる × やぶれて成形できない ・金型再現性 ○ 良好 △ 型の角が少々あまくなるが成形できる × ほとんど型が再現できない ・成形加熱時のシートのドローダウン ○ 良好 △ 少々ドローダウンするが成形に影響はない × 大きくドローダウンし成形できない[Evaluation Criteria] -Sheet exposure during molding heating ○ Good △ Slightly exposed but can be formed × Largely exposed and cannot be formed ・ Deep drawing formability ○ Good △ Slight naki etc. can be formed × Shaky forming No ・ Mold reproducibility ○ Good △ Mold corners are slightly rounded but molding is possible × Almost no mold can be reproduced ・ Sheet drawdown during molding heating ○ Good △ A little drawdown but molding is not affected × Large draw Can't mold down
【００４４】〔独立気泡率の測定方法〕独立気泡率Ｆc
（％）の測定は空気比較式比重計〔９３０型 東芝・ベ
ックマン（株）製〕を使用しＡＳＴＭ Ｄ２８５６に
（エアピクノメータ法）と同様の方法によりＶxを計測
して下式により求めることができる。但し、サンプルサ
イズ、見掛け容積Ｖa（ｃｍ3）は以下の通りとする。 ・サンプルサイズ：表層を除く芯層を２５ｍｍ角に切
り、積み重ねて約３０ｍｍになるようにする。 ・見掛け容積Ｖa（ｃｍ3）：上記積み重ねサンプルを構
成する各々の芯層をノギスにより１０μｍの単位まで測
定し容積を求める。 Ｆo＝〔（Ｖa−Ｖx）／Ｖa〕×１００ Ｆc＝１００−Ｆo Ｆo（％）：連続気泡率 Ｖx（ｃｍ3）：エアピクノメーター法により求められる
サンプルの実容積 〔加熱寸法変化の測定方法〕１７０×１７０ｍｍのポリ
カーボネート樹脂発泡積層シート試験片を作製し、その
中央部分に流れ方向（ＭＤ）と幅方向（ＴＤ）に沿って
長さ１００ｍｍの直線を十字に引く。この試験片を１７
０℃のオーブン内で３０秒間処理してから前記直線の長
さを測定し、下式によって加熱寸法変化を求める。加熱
寸法変化＝〔（加熱後の長さｍｍ−１００ｍｍ）／１０
０ｍｍ〕×１００この試験を３回行って平均値を各々Ｍ
Ｄ方向及びＴＤ方向の加熱寸法変化とする。 〔平均気泡径Ｘ、Ｙ、Ｚの測定方法〕発泡積層シート
（比較例においては発泡シート）の幅方向及び押し出し
方向断面を顕微鏡にて拡大し図１（ｂ）、（ｃ）に示す
ような拡大断面図を得る。次に該断面図上の全ての気泡
（少なくとも５０個以上の気泡）について図１（ｄ）に
示すように最大値をもって気泡径とし、Ｘ1…ｎ、Ｙ1…
ｎ、Ｚ1…ｎ（ｎは５０以上）の測定を行ない平均気泡
径Ｘ、Ｙ、Ｚを求める。但し、拡大断面図上に５０個以
上の気泡が存在しない場合は他の測定点で更に測定を行
ない併せて５０個以上の気泡におけるＸ、Ｙ、Ｚを求め
る。又、気泡が連通している場合、円または楕円の形状
を維持しているものについては気泡径を求め、その他の
ものについては除外するものとする。[Measurement Method of Closed Cell Rate] Closed Cell Rate Fc
(%) Can be obtained by the following formula by measuring Vx in the same method as ASTM D2856 (air pycnometer method) using an air comparison type hydrometer [manufactured by Toshiba Beckman Co., Ltd. model 930]. it can. However, the sample size and the apparent volume Va (cm 3 ) are as follows. -Sample size: The core layer excluding the surface layer is cut into 25 mm squares and stacked to have a size of about 30 mm. -Apparent volume Va (cm 3 ): Each core layer constituting the above-mentioned stacked sample is measured with a caliper to a unit of 10 μm to obtain the volume. Fo = [(Va-Vx) / Va] × 100 Fc = 100-Fo Fo (%): Open cell ratio Vx (cm 3 ): Actual volume of sample obtained by air pycnometer method [Method of measuring change in heating dimension] A 170 × 170 mm polycarbonate resin foam laminated sheet test piece is prepared, and a straight line having a length of 100 mm is drawn in a cross shape in the central portion along the flow direction (MD) and the width direction (TD). 17 this test piece
After being treated in an oven at 0 ° C. for 30 seconds, the length of the straight line is measured, and the heating dimensional change is obtained by the following formula. Change in heating dimension = [(length after heating mm-100 mm) / 10
0 mm] × 100 This test was performed 3 times and the average value was M
The heating dimension changes in the D direction and the TD direction. [Measurement Method of Average Cell Diameters X, Y, Z] Cross sections in the width direction and the extrusion direction of the foamed laminated sheet (foamed sheet in the comparative example) are enlarged by a microscope as shown in FIGS. Obtain an enlarged cross-sectional view. Next, for all the bubbles (at least 50 bubbles or more) on the cross-sectional view, as shown in FIG. 1D, the maximum value is taken as the bubble diameter, and X 1 ... N, Y 1 ...
n, Z 1 ... N (n is 50 or more) are measured to obtain average bubble diameters X, Y, Z. However, when 50 or more bubbles do not exist on the enlarged cross-sectional view, further measurement is performed at other measurement points, and X, Y, and Z in 50 or more bubbles are also obtained. When bubbles are communicating, the bubble diameter is determined for those that maintain a circular or elliptical shape, and the others are excluded.
【００４５】[0045]
【発明の効果】本発明のポリカーボネート樹脂発泡積層
シートは、ポリカーボネート樹脂本来の優れた特性を有
し、機械的強度、金型再現性及び深絞り加工性に優れた
ものであり、特に真空成形及び／又は圧空成形に好適な
ものである。また、本発明のポリカーボネート樹脂発泡
積層シートは、芯材の発泡シートの気泡を前記の如く、
特定のものとすることにより、発泡シートは成形時のド
ローダウンも防ぐことができ、均一加熱が容易で成形性
に特に優れたものとなる。更に本発明のポリカーボネー
ト樹脂発泡積層シートを構成する芯層及び表層のそれぞ
れのポリカーボネート樹脂を前記特定の分子量のものと
することによって、加熱加工性に優れ、積層シートの厚
みも均一となる他、積層作業性、特に共押出容易とな
り、又、ポリカーボネート樹脂のリサイクル原料を表層
又は芯層として使用する時の材料選択の幅も拡がる。EFFECT OF THE INVENTION The polycarbonate resin foam laminated sheet of the present invention has the original excellent properties of the polycarbonate resin and is excellent in mechanical strength, mold reproducibility and deep drawing workability. And / or is suitable for pressure forming. In addition, the polycarbonate resin foam laminated sheet of the present invention, the bubbles of the foam sheet of the core material, as described above,
By using a specific material, the foamed sheet can prevent drawdown at the time of molding, can be uniformly heated easily, and have excellent moldability. Furthermore, by making each of the polycarbonate resin of the core layer and the surface layer constituting the polycarbonate resin foamed laminated sheet of the present invention have the specific molecular weight, excellent heat processability is obtained, and the thickness of the laminated sheet becomes uniform, Workability, especially co-extrusion becomes easy, and the range of choice of materials when the recycled raw material of the polycarbonate resin is used as the surface layer or the core layer is expanded.
【図１】（ａ）、（ｂ）、（ｃ）、（ｄ）は各々本発明
の発泡積層シートにおける発泡層の気泡形状を説明する
図である。FIG. 1 (a), (b), (c), (d) is a diagram for explaining a bubble shape of a foam layer in a foam laminated sheet of the present invention.
Ｘ シート幅方向 Ｙ シート押し出し方向 Ｚ シート厚み方向 X sheet width direction Y sheet extrusion direction Z sheet thickness direction
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ２９Ｌ 7:00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location B29L 7:00
Claims (3)
芯層とし、少なくとも片面にポリカーボネート樹脂フィ
ルムよりなる表層を積層したことを特徴とするポリカー
ボネート樹脂押出発泡積層シート。1. A polycarbonate resin extruded and foamed laminated sheet, comprising a polycarbonate resin extruded and foamed sheet as a core layer, and a surface layer made of a polycarbonate resin film laminated on at least one surface thereof.
ボネート樹脂押出発泡シートであることを特徴とする請
求項１記載のポリカーボネート樹脂押出発泡積層シー
ト。 １＜Ｘ／Ｚ≦３ １＜Ｙ／Ｚ≦５ （Ｘ＋Ｙ＋Ｚ）／３≧０．１ｍｍ 〔但し、式中、Ｘはシート幅方向断面の厚み方向と直交
する方向の平均気泡径（ｍｍ）を、Ｙはシート押し出し
方向断面の厚み方向と直交する方向の平均気泡径（ｍ
ｍ）を、Ｚはシート断面の厚み方向の平均気泡径（ｍ
ｍ）を表す〕2. The polycarbonate resin extruded foam laminated sheet according to claim 1, wherein the core layer is a polycarbonate resin extruded foam sheet satisfying the following formula. 1 <X / Z ≦ 3 1 <Y / Z ≦ 5 (X + Y + Z) /3≧0.1 mm [where X is the average cell diameter (mm) in the direction orthogonal to the thickness direction of the cross section in the sheet width direction] , Y is the average bubble diameter (m in the direction perpendicular to the thickness direction of the cross section of the sheet extrusion direction).
m), Z is the average cell diameter in the thickness direction of the sheet cross section (m
represents m)]
脂の粘度平均分子量が２５０００以上であり、前記表層
を構成するポリカーボネート樹脂の粘度平均分子量が２
００００未満であることを特徴とする請求項１又は２記
載のポリカーボネート樹脂押出発泡積層シート。3. A polycarbonate resin constituting the core layer has a viscosity average molecular weight of 25,000 or more, and a polycarbonate resin constituting the surface layer has a viscosity average molecular weight of 2 or more.
It is less than 0000, The polycarbonate resin extrusion foaming laminated sheet according to claim 1 or 2, which is characterized in that.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06162395A JP3791699B2 (en) | 1994-10-27 | 1995-02-24 | Polycarbonate resin extruded foam laminated sheet |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-287407 | 1994-10-27 | ||
| JP28740794 | 1994-10-27 | ||
| JP06162395A JP3791699B2 (en) | 1994-10-27 | 1995-02-24 | Polycarbonate resin extruded foam laminated sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08174780A true JPH08174780A (en) | 1996-07-09 |
| JP3791699B2 JP3791699B2 (en) | 2006-06-28 |
Family
ID=26402674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06162395A Expired - Lifetime JP3791699B2 (en) | 1994-10-27 | 1995-02-24 | Polycarbonate resin extruded foam laminated sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3791699B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1090744A2 (en) * | 1999-10-06 | 2001-04-11 | Jsp Corporation | Composite sheet having foamed polycarbonate resin layer and non-foamed polycarbonate resin layer |
| US6543573B2 (en) | 1999-12-28 | 2003-04-08 | Jsp Corporation | Speaker unit, speaker system, and speaker diaphragm manufacturing method |
| WO2021209335A1 (en) * | 2020-04-15 | 2021-10-21 | Covestro Deutschland Ag | Polycarbonate composite article |
| WO2023188487A1 (en) | 2022-03-31 | 2023-10-05 | マクセル株式会社 | Coextruded sheet |
| WO2023189108A1 (en) | 2022-03-31 | 2023-10-05 | マクセル株式会社 | Co-extruded sheet and molded resin article |
| JP2023152225A (en) * | 2022-03-31 | 2023-10-16 | マクセル株式会社 | Co-extrusion sheet |
-
1995
- 1995-02-24 JP JP06162395A patent/JP3791699B2/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1090744A2 (en) * | 1999-10-06 | 2001-04-11 | Jsp Corporation | Composite sheet having foamed polycarbonate resin layer and non-foamed polycarbonate resin layer |
| EP1090744A3 (en) * | 1999-10-06 | 2002-04-17 | Jsp Corporation | Composite sheet having foamed polycarbonate resin layer and non-foamed polycarbonate resin layer |
| US6492015B1 (en) | 1999-10-06 | 2002-12-10 | Jsp Corporation | Composite sheet having foamed polycarbonate resin layer and non-foamed polycarbonate resin layer |
| US6543573B2 (en) | 1999-12-28 | 2003-04-08 | Jsp Corporation | Speaker unit, speaker system, and speaker diaphragm manufacturing method |
| WO2021209335A1 (en) * | 2020-04-15 | 2021-10-21 | Covestro Deutschland Ag | Polycarbonate composite article |
| CN115397668A (en) * | 2020-04-15 | 2022-11-25 | 科思创德国股份有限公司 | Polycarbonate composite article |
| WO2023188487A1 (en) | 2022-03-31 | 2023-10-05 | マクセル株式会社 | Coextruded sheet |
| WO2023190634A1 (en) | 2022-03-31 | 2023-10-05 | マクセル株式会社 | Co-extruded sheet |
| WO2023189108A1 (en) | 2022-03-31 | 2023-10-05 | マクセル株式会社 | Co-extruded sheet and molded resin article |
| JP2023152225A (en) * | 2022-03-31 | 2023-10-16 | マクセル株式会社 | Co-extrusion sheet |
| KR20240012497A (en) | 2022-03-31 | 2024-01-29 | 맥셀 주식회사 | coextruded sheet |
| KR20240012499A (en) | 2022-03-31 | 2024-01-29 | 맥셀 주식회사 | Coextruded sheets and resin molded products |
| KR20240012495A (en) | 2022-03-31 | 2024-01-29 | 맥셀 주식회사 | coextruded sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3791699B2 (en) | 2006-06-28 |
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