JPH0313059B2 - - Google Patents

Info

Publication number
JPH0313059B2
JPH0313059B2 JP54122125A JP12212579A JPH0313059B2 JP H0313059 B2 JPH0313059 B2 JP H0313059B2 JP 54122125 A JP54122125 A JP 54122125A JP 12212579 A JP12212579 A JP 12212579A JP H0313059 B2 JPH0313059 B2 JP H0313059B2
Authority
JP
Japan
Prior art keywords
pvf
polyalkyl methacrylate
acrylonitrile
butadiene
thermoplastic polymer
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.)
Expired - Lifetime
Application number
JP54122125A
Other languages
Japanese (ja)
Other versions
JPS5544898A (en
Inventor
Sutoratsuseru Aruberu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Atochem SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from KR1019790003305A external-priority patent/KR830000832B1/en
Application filed by Atochem SA filed Critical Atochem SA
Publication of JPS5544898A publication Critical patent/JPS5544898A/en
Publication of JPH0313059B2 publication Critical patent/JPH0313059B2/ja
Granted legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
    • B29C48/335—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Description

【発明の詳細な説明】[Detailed description of the invention]

本発明はポリ弗化ビニリデン（以下PVF2と略
称する）、及びアクリロニトリル−ブタジエン−
スチレン共重合体及びポリ塩化ビニルから選ばれ
た熱可塑性重合体からなる複合材に関する。この
複合材は同時押出法によつて製造される。 熱可塑性プラスチツクの同時押出法は当分野で
周知の技術であり、特に“Polymer Plastics
Technology and Engineering”第３巻、第49−
68頁に記載されている。 一般に、押出加工すべき重合体の数に等しい慣
用の押出機から熱可塑性プラスチツクを同時押出
する方法は３通り知られている。第１の方法は重
合体を別々に押出し、それらがダイから離れるに
つれて一緒にする方法である。第２の方法は少く
とも２基の押出機から、押出機（従つて押出され
る重合体）と同数の溝を有する単一のダイに供給
することからなり、この場合各重合体の流束はダ
イのリツプで（即ちダイを離れる直前で）合流さ
れる。第３の方法は所望数の押出機から流束分配
装置に供給するものであり、この分配装置で重合
体は一緒になつて単一流束を形成し、ダイに供給
される。これらの方法では押出機の各押出速度が
押出される重合体の相対的な厚みを調節する手段
を与える。 上記公知の方法により種々の重合体を同時押出
加工することができるが、PVF2を他の重合体と
組合せることはできなかつた。その理由は、
PVF2は他の重合体と不混和性であり、また周知
事実として弗素化樹旨は大部分の熱可塑性重合体
にたやすく接着しないからである。PVF2を他の
熱可塑性重合体と組合せる際の困難な問題は、一
方がPVF2からなり他方が任意所望の熱可塑性重
合体からなる二つの予備成形フイルムを加圧下で
相互に接着せんとする積層法を行なう場合にも遭
遇される。かかる積層の試みは、PVF2の予備成
形フイルムと押出機を去る（即ち実質的に溶融状
態の）ポリ塩化ビニル、ポリスチレン、ポリメタ
クリル酸メチル又はアクリロニトリル−ブタジエ
ン−スチレン共重合体のフイルムとを材料とする
場合にも成功を収めていない。かかる条件下でも
二種の重合体は冷却後容易に分離する。 従つて、PVF2をこれと不混和性の別の熱可塑
性プラスチツクと組合せることが所望される場合
には接着剤を使用せねばならないが、この方法は
次の三工程からなるという不都合を有する： −PVF2フイルムの形成 −熱可塑性プラスチツクフイルムの形成 −両フイルムの接着剤による結合及び加圧 これらの作業は実際的でなく、時間がかかり、
通常除去困難な溶剤に基づく接着剤の使用を必要
としかつ接着剤の乾燥に必要な時間のため形成さ
れた複合材を直ちに使用できない。更に、得られ
た複合材は一体化されず、中間面は離脱を惹起し
易いすべての現象に対してなお感受性である。従
つて、接着剤による結合は一体化された複合材を
与えず、単に熱可塑性プラスチツク材料を並置し
て不均質な構造体を与えるにすぎないといえる。 本発明は前述した欠点を解消して、材料が相互
に堅固に結合されている一体化された均質構造の
真の複合材を提供するものである。本発明の新規
な複合材は、少なくとも一つの外表面はPVF2か
らなり、もう一つの表面はアクリロニトリル−ブ
タジエン−スチレン共重合体及びポリ塩化ビニル
から選ばれた熱可塑性重合体からなるものであつ
て、これら２種の重合体がその表面全体に亘つて
ポリメタクリル酸アルキルにより相互に結合され
ておりかつ該ポリメタクリル酸アルキルがそれ自
体少くとも部分的に上記２種の重合体の全表面に
堅固に結合されていることを特徴とするものであ
る。PVF2とポリメタクリル酸アルキルとの界面
及びアクリロニトリル−ブタジエン−スチレン共
重合体及びポリ塩化ビニルから選ばれた熱可塑性
重合体とポリメタクリル酸アルキルとの界面は、
これら成分を溶融状態で一緒に混合した結果生ず
ると考えられるアロイ状であるが、この成分間の
結合状態から本発明の複合材は一体化された均質
構造のものとみなすことができる。これに対し、
例えば接着剤による結合によつて得られるいわゆ
る不均質構造の複合材においては、転移部を有し
ない界面が明確にみられ、損傷を受け易くなるで
あろう。本発明の複合材は、ポリメタクリル酸ア
ルキルとPVF2との結合及びポリメタクリル酸ア
ルキルとアクリロニトリル−ブタジエン−スチレ
ン共重合体及びポリ塩化ビニルから選ばれた熱可
塑性重合体との結合により形成された三成分から
なり、かつ少なくとも一つの外表面はPVF2から
なりもう一つの表面はアクリロニトリル−ブタジ
エン−スチレン共重合体がポリ塩化ビニルから選
ばれた熱可塑性重合体からなる複合材として定義
することもできる。複合材のPVF2からなる外面
は通常結合剤として作用するポリメタクリル酸ア
ルキルを含まない。これはPVF2の固有の性質を
すべて該表面上で保持させんとする場合にいえ
る。 単に経済的理由から、本発明の複合材は通常唯
一のPVF2外面及びアクリロニトリル−ブタジエ
ン−スチレン共重合体及びポリ塩化ビニルから選
ばれた熱可塑性重合体からなる他の外面を有す
る。しかしながら、アクリロニトリル−ブタジエ
ン−スチレン共重合体及びポリ塩化ビニルから選
ばれた熱可塑性重合体は別の材料に対する結合面
として作用し得る。従つて、本発明の複合材は両
方の外面がPVF2からなり、三成分間の結合配列
がPVF2−ポリメタクリル酸アルキル−アクリロ
ニトリル−ブタジエン−スチレン共重合体及びポ
リ塩化ビニルから選ばれた熱可塑性重合体−ポリ
メタクリル酸アルキル−PVF2からなるものであ
つてもよい。本発明において、アクリロニトリル
−ブタジエン−スチレン共重合体及びポリ塩化ビ
ニルから選ばれた熱可塑性重合体の表面″とは外
面及び内面のいずれをも意味し得る。 この種の複合材は、例えば管状、スリーブ状、
異形品状、フイルム状及びシート状の如き熱可塑
性プラスチツクを用いる場合に通常みられる任意
の形状をとり得るが、中でも例えば熱成形の如き
公知の方法により二次成形できるシート状がきわ
めて価値がある。シート状の複合材は、耐候性で
ありかつ通常PVF2に特有の性質をすべて有する
少くとも一外面及びアクリロニトリル−ブタジエ
ン−スチレン共重合体及びポリ塩化ビニルから選
ばれた熱可塑性重合体に特有の機械的性質（概し
てすべての性質）を有する別の表面をもつが、構
造上一体化されかつ均質なものになるので有利で
ある。 本発明の複合材は同時押出によりきわめて有利
に得られるが、このことはPVF2を熱可塑性重合
体に付着せしめる周知の困難性から考えて実に驚
くべきことである。本発明者は、ポリメタクリル
酸アルキルをアクリロニトリル−ブタジエン−ス
チレン共重合体及びポリ塩化ビニルから選ばれた
熱可塑性重合体と一緒に、ポリメタクリル酸アル
キルが両方の重合体の間に配置されるように同時
押出すると、異種の重合体層がすべて相互に堅固
に結合された直ちに使用できる複合材が一工程で
得られることを認めた。 従つて本発明によれば、ポリ弗化ビニリデン、
中間結合剤として作用するポリメタクリル酸アル
キル及びポリ弗化ビニリデンと不混和性の熱可塑
性重合体を同時押出すること及びその際、押出機
を去るポリ弗化ビニリデン、 ポリメタクリル酸アルキル及び熱可塑性重合体
の流束を遅くともダイのグリツプ位置で合流させ
ることを特徴とする、ポリメタクリル酸アルキル
とポリ弗化ビニリデンとの結合及びポリメタクリ
ル酸アルキルとポリ弗化ビニリデンと不混和性の
熱可塑性重合体との結合により形成された三成分
からなり、かつポリ弗化ビニリデンの少くとも一
外面及びポリ弗化ビニリデンと不混和性である熱
可塑性重合体の一表面を有する複合材の製造法が
提供される。 すべてのPVF2が満足できる結果を与えるが、
最良の結果は、下記の表における少くとも２つの
速度勾配値について表示される両極限値の範囲内
の見かけ粘度（200℃）を有するPVF2を用いた
場合に得られる。 The present invention uses polyvinylidene fluoride (hereinafter abbreviated as PVF 2 ) and acrylonitrile-butadiene-
The present invention relates to a composite material comprising a thermoplastic polymer selected from a styrene copolymer and polyvinyl chloride. This composite is manufactured by coextrusion. Co-extrusion of thermoplastic plastics is a well-known technique in the art, particularly the “Polymer Plastics
Technology and Engineering” Volume 3, No. 49-
It is described on page 68. Generally, three methods are known for coextruding thermoplastics from conventional extruders equal to the number of polymers to be extruded. The first method is to extrude the polymers separately and bring them together as they leave the die. A second method consists of feeding from at least two extruders to a single die having the same number of grooves as extruders (and thus the polymers being extruded), in which case the flux of each polymer are joined at the lip of the die (ie just before leaving the die). A third method is to feed the desired number of extruders to a flux distribution device where the polymers are combined to form a single flux and fed to a die. In these methods, each extrusion speed of the extruder provides a means to control the relative thickness of the extruded polymer. Although various polymers can be coextruded by the above-mentioned known methods, it has not been possible to combine PVF 2 with other polymers. The reason is,
This is because PVF 2 is immiscible with other polymers and it is well known that fluorinated resins do not readily adhere to most thermoplastic polymers. A difficult problem in combining PVF 2 with other thermoplastic polymers is that two preformed films, one of PVF 2 and the other of any desired thermoplastic polymer, must be bonded together under pressure. It is also encountered when carrying out the lamination method. Such lamination attempts have involved the use of a preformed film of PVF 2 and a film of polyvinyl chloride, polystyrene, polymethyl methacrylate or acrylonitrile-butadiene-styrene copolymer leaving the extruder (i.e. in substantially molten state). This has not been successful either. Even under such conditions, the two types of polymers are easily separated after cooling. Therefore, if it is desired to combine PVF 2 with another thermoplastic with which it is immiscible, adhesives must be used, but this method has the disadvantage of consisting of three steps: : - Formation of PVF 2 film - Formation of thermoplastic plastic film - Bonding and pressing of both films with adhesive These operations are impractical, time consuming and
It usually requires the use of solvent-based adhesives that are difficult to remove, and the time required for the adhesive to dry prevents the formed composite from being ready for immediate use. Moreover, the resulting composite is not integrated and the intermediate surface is still susceptible to all phenomena that tend to cause detachment. Therefore, adhesive bonding does not provide an integrated composite, but merely juxtaposes thermoplastic materials to provide a heterogeneous structure. The present invention overcomes the drawbacks mentioned above and provides a true composite material with an integrated homogeneous structure in which the materials are firmly bonded to each other. The novel composite material of the present invention is characterized in that at least one outer surface consists of PVF 2 and another surface consists of a thermoplastic polymer selected from acrylonitrile-butadiene-styrene copolymer and polyvinyl chloride. the two polymers are interconnected over their entire surfaces by polyalkyl methacrylates, and the polyalkyl methacrylates are themselves at least partially distributed over the entire surfaces of the two polymers. It is characterized by being firmly connected. The interface between PVF 2 and polyalkyl methacrylate and the interface between thermoplastic polymer selected from acrylonitrile-butadiene-styrene copolymer and polyvinyl chloride and polyalkyl methacrylate are:
Although the alloy-like shape is thought to result from mixing these components together in a molten state, the composite material of the present invention can be considered to have an integrated homogeneous structure due to the state of bonding between the components. In contrast,
In composites with a so-called heterogeneous structure obtained, for example, by adhesive bonding, interfaces without transitions are clearly visible and may be more susceptible to damage. The composite material of the present invention is formed by combining polyalkyl methacrylate with PVF 2 and combining polyalkyl methacrylate with a thermoplastic polymer selected from acrylonitrile-butadiene-styrene copolymer and polyvinyl chloride. It may also be defined as a composite material consisting of three components and at least one outer surface of PVF 2 and the other surface of a thermoplastic polymer selected from polyvinyl chloride, an acrylonitrile-butadiene-styrene copolymer. can. The PVF 2 outer surface of the composite is usually free of polyalkyl methacrylate, which acts as a binder. This is true if all the inherent properties of PVF 2 are to be retained on the surface. For purely economic reasons, the composites of the invention usually have only one PVF 2 outer surface and another outer surface consisting of a thermoplastic polymer chosen from acrylonitrile-butadiene-styrene copolymer and polyvinyl chloride. However, thermoplastic polymers selected from acrylonitrile-butadiene-styrene copolymers and polyvinyl chloride can act as a bonding surface for another material. Therefore, the composite of the present invention consists of PVF 2 on both outer surfaces and a ternary bond arrangement of thermoplastic selected from PVF 2 -polyalkyl methacrylate-acrylonitrile-butadiene-styrene copolymer and polyvinyl chloride. It may be composed of a polymer-polyalkyl methacrylate- PVF2 . In the present invention, the term "surface" of the thermoplastic polymer selected from acrylonitrile-butadiene-styrene copolymer and polyvinyl chloride can mean both the outer surface and the inner surface. sleeve shape,
It can take any shape that is commonly found when using thermoplastics, such as irregularly shaped articles, films, and sheets, but sheet shapes that can be secondary formed by known methods such as thermoforming are particularly valuable. . The sheet composite is weather resistant and typically has at least one exterior surface having all the properties characteristic of PVF 2 and a thermoplastic polymer selected from acrylonitrile-butadiene-styrene copolymer and polyvinyl chloride. Advantageously, it has a separate surface with mechanical properties (generally all properties) but is structurally integrated and homogeneous. The composites of the invention are very advantageously obtained by coextrusion, which is quite surprising in view of the known difficulties in attaching PVF 2 to thermoplastic polymers. The present inventor has developed a method of combining polyalkyl methacrylate with a thermoplastic polymer selected from acrylonitrile-butadiene-styrene copolymer and polyvinyl chloride such that the polyalkyl methacrylate is located between both polymers. It has been observed that when coextruded, a ready-to-use composite in which the dissimilar polymer layers are all firmly bonded to each other is obtained in one step. According to the invention, therefore, polyvinylidene fluoride,
coextrusion of a thermoplastic polymer immiscible with polyalkyl methacrylate and polyvinylidene fluoride, which acts as intermediate binder, and in which case the polyvinylidene fluoride, polyalkyl methacrylate and thermoplastic polymer leaving the extruder Bonding of polyalkyl methacrylate and polyvinylidene fluoride and thermoplastic polymer immiscible with polyalkyl methacrylate and polyvinylidene fluoride, characterized in that the fluxes of coalescence are merged at the grip position of the die at the latest. Provided is a method for producing a composite material having at least one outer surface of polyvinylidene fluoride and one surface of a thermoplastic polymer that is immiscible with the polyvinylidene fluoride. Ru. Although all PVF 2 gives satisfactory results,
The best results are obtained when using PVF 2 with an apparent viscosity (200° C.) within both extreme values indicated for at least two velocity slope values in the table below.

【表】 表示した見かけ粘度は非ニユートン流体に適用
されるラビノウイツチ（Rabinowitch）補正を考
慮して細管レオメーターを用いて公知の方法によ
り測定したものである。 一般的にPVF2の層厚は重要ではないが、経済
的理由からPVF2の層厚が10ミクロン〜数10mmで
ある複合材を形成させることが好ましい。本明細
書においてPVF2は単独重合体ばかりでなく、
PVF2を少くとも70重量％含む共重合体及び
PVF2と他の重合体との混合物をも意味する。 ポリメタクリル酸アルキルは好ましくはポリメ
タクリル酸メチル（PMMA）であり、その溶融
状態の粘度は市販のPMMAの粘度範囲内に選定
でき、その粘度を例えば少量の装填物又は別の重
合体との混合により（但しポリメタクリル酸アル
キルの重量を75％以上に保つ）調節する方法は当
業者には公知であろう。 ポリメタクリル酸アルキルの量及び場合により
PVF2の量は溶融状態の不混和性熱可塑性重合体
の粘度に従つて選定するのがよいことが認められ
た。良好な結果は下記の表に示される所与の速度
勾配値について両極限値の範囲内のPMMA粘度
（200℃で測定）を用いた場合に得られる。しかし
ながら、これらの値は限定的なものではなく、当
業者にはかかる粘度を押出温度の関数として変え
ることができよう。[Table] The indicated apparent viscosities were determined by known methods using a capillary rheometer, taking into account the Rabinowitch correction applied to non-Newtonian fluids. Generally, the layer thickness of PVF 2 is not critical, but for economic reasons it is preferable to form a composite with a PVF 2 layer thickness of 10 microns to several tens of mm. In this specification, PVF 2 is not only a homopolymer, but also a homopolymer.
Copolymers containing at least 70% by weight of PVF 2 and
It also refers to mixtures of PVF 2 and other polymers. The polyalkyl methacrylate is preferably polymethyl methacrylate (PMMA), the viscosity of which in the molten state can be selected within the viscosity range of commercially available PMMA, and whose viscosity can be adjusted, for example, by mixing with a small charge or with another polymer. Those skilled in the art will know how to adjust the weight of polyalkyl methacrylate (while keeping the weight of polyalkyl methacrylate above 75%). Amount of polyalkyl methacrylate and optionally
It has been found that the amount of PVF 2 is preferably selected according to the viscosity of the immiscible thermoplastic polymer in the molten state. Good results are obtained when using PMMA viscosities (measured at 200° C.) within both extreme values for the given velocity gradient values shown in the table below. However, these values are not limiting and one skilled in the art will be able to vary such viscosities as a function of extrusion temperature.

【表】 １／秒 極小値 極大値
[Table] 1/sec Local minimum value Local maximum value

Claims (1)

【特許請求の範囲】 １ 少なくとも一つの外表面はポリフツ化ビニリ
デンであり、もつ一つの表面はアクリロニトリル
−ブタジエン−スチレン共重合体及びポリ塩化ビ
ニルから選ばれた熱可塑性重合体である複合材に
おいて、ポリフツ化ビニリデン、中間結合成分と
してのポリメタクリル酸アルキル、及びアクリロ
ニトリル−ブタジエン−スチレン共重合体及びポ
リ塩化ビニルから選ばれた熱可塑性重合体の三成
分を同時押出しすることにより、その際押出器を
出る重合体の流速を遅くともダイのリツプ位置で
合流させることにより製造され、ポリメタクリル
酸アルキルとポリフツ化ビニリデンとの界面及び
ポリメタクリル酸アルキルとアクリロニトリル−
ブタジエン−スチレン共重合体及びポリ塩化ビニ
ルから選ばれた熱可塑性重合体との界面にアロイ
状の転移部を有し、全体として一体的構造を持つ
ことを特徴とする複合材。 ２ ポリメタクリル酸アルキルがポリメタクリル
酸メチルである特許請求の範囲第一項記載の複合
材。[Claims] 1. A composite material in which at least one outer surface is polyvinylidene fluoride and one surface is a thermoplastic polymer selected from acrylonitrile-butadiene-styrene copolymer and polyvinyl chloride, By coextruding the three components of polyvinylidene fluoride, polyalkyl methacrylate as an intermediate bonding component, and a thermoplastic polymer selected from acrylonitrile-butadiene-styrene copolymer and polyvinyl chloride, the extruder is It is produced by converging the flow rate of the exiting polymer at the lip position of the die at the latest, and the interface between polyalkyl methacrylate and polyvinylidene fluoride and the interface between polyalkyl methacrylate and acrylonitrile are produced.
A composite material characterized by having an alloy-like transition region at the interface with a thermoplastic polymer selected from a butadiene-styrene copolymer and polyvinyl chloride, and having an integral structure as a whole. 2. The composite material according to claim 1, wherein the polyalkyl methacrylate is polymethyl methacrylate.
JP12212579A 1978-09-25 1979-09-25 Compound material containing polyfluovinylidene and its preparation Granted JPS5544898A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7827361A FR2436676A1 (en) 1978-09-25 1978-09-25 Composite of polyvinylidene fluoride and incompatible thermoplastics - has intermediate layer of poly:alkyl methacrylate! and is useful for tube, film and sheet prodn.
KR1019790003305A KR830000832B1 (en) 1978-09-25 1979-09-24 Laminates of Polyvinylidene Fluoride and Incompatible Thermoplastics

Publications (2)

Publication Number Publication Date
JPS5544898A JPS5544898A (en) 1980-03-29
JPH0313059B2 true JPH0313059B2 (en) 1991-02-21

Family

ID=26220772

Family Applications (1)

Application Number Title Priority Date Filing Date
JP12212579A Granted JPS5544898A (en) 1978-09-25 1979-09-25 Compound material containing polyfluovinylidene and its preparation

Country Status (4)

Country Link
JP (1) JPS5544898A (en)
FR (1) FR2436676A1 (en)
SU (1) SU1071216A3 (en)
ZA (1) ZA795036B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2477463A1 (en) * 1980-03-07 1981-09-11 Ugine Kuhlmann PROCESS FOR PRODUCING VINYLIDENE POLYFLUORIDE COMPOSITE AND NON-COMPATIBLE POLYMER BY COEXTRUSION-MOLDING
JPS57187248A (en) * 1981-05-12 1982-11-17 Kureha Chemical Ind Co Ltd Laminate
JPS57142359A (en) * 1981-02-28 1982-09-03 Kureha Chemical Ind Co Ltd Extruded laminate
JPS58126154A (en) * 1982-01-25 1983-07-27 呉羽化学工業株式会社 Method of coating metallic base material with resin
JPS59140053A (en) * 1983-01-31 1984-08-11 カンボウプラス株式会社 Laminated cloth having excellent contamination resistance
EP0132583B1 (en) * 1983-08-01 1988-09-14 Ausimont, U.S.A., Inc. Coextrusion of thermoplastic fluoropolymers with thermoplastic polymers
JPH0671785B2 (en) * 1984-06-23 1994-09-14 電気化学工業株式会社 Method for producing vinylidene fluoride resin-based composite film
FR2711665B1 (en) * 1993-10-25 1995-12-08 Atochem Elf Sa PVDF adhesion binder, its application as a barrier material and materials obtained from it.
KR100900159B1 (en) * 2004-02-20 2009-06-02 생-고뱅 퍼포먼스 플라스틱스 코포레이션 Draw resonant resistant multilayer films
RU2443564C2 (en) * 2007-02-21 2012-02-27 Асахи Гласс Компани, Лимитед Laminated sheet
US7866348B2 (en) * 2008-05-01 2011-01-11 Saint-Gobain Performance Plastics Corporation Multi-layered fuel tubing
US8092881B2 (en) * 2008-05-01 2012-01-10 Saint-Gobain Performance Plastics Corporation Multi-layered fuel tubing
JP2022087831A (en) 2020-12-01 2022-06-13 サン－ゴバン パフォーマンス プラスティックス コーポレイション Multilayer tube for chemical transfer applications

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3451876A (en) * 1964-05-28 1969-06-24 Ksh Inc Plastic light-transmitting panel
US3565985A (en) * 1969-04-10 1971-02-23 Dow Chemical Co Method of preparing multilayer plastic articles
US3647612A (en) * 1969-06-06 1972-03-07 Dow Chemical Co Multilayer plastic articles
DE2246497B2 (en) * 1972-09-22 1976-04-08 Verfahren zum Coextrudieren von thermoplastischem Kunststoff Dynamit Nobel AG, 5210 Troisdorf PROCESS FOR COEXTRUDING THERMOPLASTIC PLASTIC
JPS5155381A (en) * 1974-11-12 1976-05-15 Kureha Chemical Ind Co Ltd SEKISOHORIMECHIRUMETAAKURIREETOBAN
JPS5159971A (en) * 1974-11-21 1976-05-25 Nippon Carbide Kogyo Kk TAIKOSEINOSUGURETAFUKUGOFUIRUMU
FR2366922A1 (en) * 1976-10-05 1978-05-05 Sumitomo Chemical Co Orientated thermoplastic film laminate - produced by compressing between pressure rollers below lowest softening temp. of constituent films

Also Published As

Publication number Publication date
SU1071216A3 (en) 1984-01-30
ZA795036B (en) 1980-09-24
FR2436676B1 (en) 1981-02-13
JPS5544898A (en) 1980-03-29
FR2436676A1 (en) 1980-04-18

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