JP2005096123A - Extrusion molding method - Google Patents

Extrusion molding method Download PDF

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JP2005096123A
JP2005096123A JP2003330084A JP2003330084A JP2005096123A JP 2005096123 A JP2005096123 A JP 2005096123A JP 2003330084 A JP2003330084 A JP 2003330084A JP 2003330084 A JP2003330084 A JP 2003330084A JP 2005096123 A JP2005096123 A JP 2005096123A
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raw material
kneading extruder
die
die plate
screw
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Takahiro Oshima
貴弘 大嶌
Seiji Kameoka
誠治 亀岡
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Japan Steel Works Ltd
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Japan Steel Works Ltd
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    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/362—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using static mixing devices
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/397—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using a single screw

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To mold a sheet having barrier properties by melting an HDPE raw material and a PA raw material different in melting point from each other separately in a screw type kneading extruder and a die plate. <P>SOLUTION: In this extrusion molding method, the screw type kneading extruder (1) and an extrusion molding apparatus (20) constituted of the screw type kneading extruder (1), the die plate (2) and a molding die (3) are used to subject a mixed raw material of the HDPE raw material (6) and the PA raw material (7) to kneading melting low in kneading degree for melting only the HDPE raw material in the screw type kneading extruder (1) not only to knead but also to gradually heat the same in the die plate (2) on the downstream side of the screw type kneading extruder (1) by a mixing device (4) to melt the PA raw material (7). Then, both molten raw materials are extruded in a sheetlike state from the leading end of the molding die (3). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、押出成形方法に関し、特に、互いに融点が異なるＨＤＰＥ原料とＰＡ原料を完全に混練溶融して押出すための新規な改良に関する。   The present invention relates to an extrusion molding method, and in particular, to a novel improvement for completely kneading and melting an HDPE raw material and a PA raw material having different melting points and extruding.

シート状あるいはフィルム状（以下において「シート」と記述する。）に押出成形された合成樹脂材料である高密度ポリエチレン（以下において「ＨＤＰＥ」と記述する。）のシートは、単一の材料では水、油等の液体に対する非透過性が無い。安価な材料であるＨＤＰＥに非透過性をもたせるため、従来、非透過性を有する同じく合成樹脂材料としてのナイロンであるポリアミド（以下において「ＰＡ」と記述する。）を加えて成形することが行われている。   A sheet of high-density polyethylene (hereinafter referred to as “HDPE”), which is a synthetic resin material extruded into a sheet or film (hereinafter referred to as “sheet”), is a water-soluble material as a single material. There is no impermeability to liquids such as oil. In order to make HDPE, which is an inexpensive material, impervious, conventionally, it has been performed by adding polyamide (hereinafter referred to as “PA”) which is non-permeable nylon, which is also a synthetic resin material. It has been broken.

図５において、符号１で示されるものはスクリュ式混練押出機であり、このスクリュ式混練押出機１はシリンダ１１を有すると共に、このスクリュ式混練押出機１にはダイプレート２を介してＴダイ３が接続され、前述のスクリュ式混練押出機１、ダイプレート２及びＴダイ３により押出成形装置２０が構成されている。   In FIG. 5, what is indicated by reference numeral 1 is a screw-type kneading and extruding machine. The screw-type kneading and extruding machine 1 has a cylinder 11. 3 is connected, and the above-described screw-type kneading extruder 1, die plate 2 and T die 3 constitute an extrusion molding apparatus 20.

以上のように構成された押出成形装置２０において、ＨＤＰＥ原料とＰＡ原料との混合原料がシリンダ１１内へ供給され、シリンダ１１の加熱とスクリュ１３の混練作用とにより混練溶融されながら、スクリュ１３の輸送作用により順次先端方向へ流動し、先端からダイプレート２を経てＴダイ３からシート状に押出される。なお、シリンダ１１、ダイプレート２およびＴダイ３は、図示しない周知の加熱装置により加熱され、混合原料の溶融状態が維持されている。   In the extrusion molding apparatus 20 configured as described above, the mixed raw material of the HDPE raw material and the PA raw material is supplied into the cylinder 11 and is kneaded and melted by the heating of the cylinder 11 and the kneading action of the screw 13. It flows in the direction of the tip sequentially by the transport action, and is extruded from the tip through the die plate 2 to the sheet from the T die 3. The cylinder 11, the die plate 2, and the T die 3 are heated by a well-known heating device (not shown), and the molten state of the mixed raw material is maintained.

また、複数の原料を混合するために、ダイプレート内にミキシングデバイスを用いることは、特許文献１及び２に開示されているが、従来、ＨＤＰＥ原料及びＰＡ原料の混合には採用されていなかった。   In addition, the use of a mixing device in a die plate for mixing a plurality of raw materials is disclosed in Patent Documents 1 and 2, but has not been conventionally used for mixing HDPE raw materials and PA raw materials. .

特開平５-４２５７８号公報JP-A-5-42578 実開昭５８−６９４１５号公報Japanese Utility Model Publication No. 58-69415

従来のＨＤＰＥとＰＡとの混合原料による押出成形方法は以上のように構成されていたため、次のような課題が存在していた。すなわち、スクリュ式混練押出機における混練溶融において、出来るだけ大きな粒子のＰＡ原料を残そうとして混練度を低くすると、ＰＡ原料が周辺部に偏る。その結果、スクリュ式混練押出機から押出されてダイプレートを流動する混合原料は、図６に示すように、円形断面の周辺部にＰＡ原料が偏って分布する。このような混合原料がＴダイへ流入すると、押出成形されたシートは、図７に示すようにＰＡ原料が疎らに分布し、バリア性としての非透過性が得られない。また、混練度を高めすぎると、図８のように、ＰＡ原料が分散されすぎ、バリア性が得られなくなる。   Since the conventional extrusion molding method using a mixed raw material of HDPE and PA is configured as described above, the following problems exist. That is, in the kneading and melting in the screw-type kneading extruder, if the degree of kneading is lowered so as to leave the PA raw material having as large particles as possible, the PA raw material is biased toward the periphery. As a result, in the mixed raw material that is extruded from the screw-type kneading extruder and flows through the die plate, the PA raw material is unevenly distributed in the periphery of the circular cross section as shown in FIG. When such a mixed raw material flows into the T-die, the extruded sheet has the PA raw material distributed sparsely as shown in FIG. 7, and the imperviousness as a barrier property cannot be obtained. If the degree of kneading is too high, the PA raw material is too dispersed as shown in FIG. 8, and the barrier property cannot be obtained.

本発明による押出成形方法は、スクリュ式混練押出機、ダイプレートおよび成形ダイからなり、前記ダイプレートにミキシングデバイスを有する押出成形装置を用い、ＨＤＰＥ原料とＰＡ原料とを混合した混合原料を前記スクリュ式混練押出機に供給し、前記スクリュ式混練押出機で前記ＨＤＰＥ原料のみの溶融混練を行い、その後、前記スクリュ式混練押出機よりも温度が高い状態の前記ダイプレート内で前記ＰＡ原料が溶融され、溶融状態の前記混合原料が前記ミキシングデバイスを経て前記成形ダイの先端より押出される方法であり、また、前記ＰＡ原料は、前記ダイプレートの後段において溶融される方法である。   The extrusion molding method according to the present invention comprises a screw-type kneading extruder, a die plate and a molding die, and uses an extrusion molding apparatus having a mixing device on the die plate, and mixes the raw material mixed with HDPE raw material and PA raw material with the screw. The kneading extruder is used to melt and knead only the HDPE raw material in the screw kneading extruder, and then the PA raw material is melted in the die plate at a higher temperature than the screw kneading extruder. In this method, the mixed raw material in a molten state is extruded from the tip of the molding die through the mixing device, and the PA raw material is melted at a subsequent stage of the die plate.

本発明による押出成形方法は以上のように構成されているため、次のような効果を得ることができる。すなわち、スクリュ式混練押出機において、ＨＤＰＥ原料のみが溶融し、ＰＡ原料はペレット状の大きな粒子のまま未溶融状態で混練され、ダイプレートにおいて、ミキシングデバイスにより、溶融状態のＨＤＰＥ原料と未溶融ペレット状態のＰＡ原料とが均一に混合され、ＰＡ原料が溶融状態に加熱される。
従って、Ｔダイの先端から押出されたシートは、ＰＡ原料が溶融して薄いフィルム状に大きく広がった状態で母材（ＨＤＰＥ原料）中に均一かつ多層に混入した状態となり、液体に対する非透過（バリア）性を発揮することができる。 Since the extrusion molding method according to the present invention is configured as described above, the following effects can be obtained. That is, in the screw-type kneading extruder, only the HDPE raw material is melted, and the PA raw material is kneaded in an unmelted state in the form of large pellet-like particles. The PA raw material in a state is uniformly mixed, and the PA raw material is heated to a molten state.
Therefore, the sheet extruded from the tip of the T die is uniformly mixed in the base material (HDPE raw material) in a state where the PA raw material is melted and spreads widely in a thin film, and is impervious to liquid ( (Barrier) property can be exhibited.

本発明は、融点が異なるＨＤＰＥ原料とＰＡ原料を溶融混練し、ミキシングデバイスを介して成形ダイに送り、バリア性を良好に有するシート等を作ることを目的とする。   An object of the present invention is to melt-knead an HDPE raw material and a PA raw material having different melting points, and send them to a forming die via a mixing device to produce a sheet having good barrier properties.

以下、図面と共に本発明による押出成形方法の好適な実施の形態について説明する。
図１において、符号１で示されるものはスクリュ式混練押出機であり、このスクリュ式混練押出機１はシリンダ１１とスクリュ１３により構成されている。シリンダ１１は図示しない加熱装置により温度制御可能に構成されている。前記スクリュ式混練押出機１の下流端にはダイプレート２を介してＴダイ（成形ダイ）３が連結されている。このダイプレート２の内孔２ａには静止型のミキシングデバイス４が挿入され、前記ダイプレート２および前記成形ダイ３は、図示しない加熱装置により内孔２ａ、流路３ａおよびスリット３ｂの内壁面が温度制御可能に構成されている。 Hereinafter, preferred embodiments of an extrusion molding method according to the present invention will be described with reference to the drawings.
In FIG. 1, what is indicated by reference numeral 1 is a screw-type kneading extruder, and this screw-type kneading extruder 1 includes a cylinder 11 and a screw 13. The cylinder 11 is configured to be temperature-controllable by a heating device (not shown). A T die (molding die) 3 is connected to the downstream end of the screw kneading extruder 1 via a die plate 2. A stationary mixing device 4 is inserted into the inner hole 2a of the die plate 2, and the die plate 2 and the forming die 3 have inner walls 2a, a flow path 3a, and slits 3b formed by a heating device (not shown). It is configured to be temperature controllable.

前記ミキシングデバイス４は、通称スタティックミキサと呼ばれる周知の装置であり、長方形の板が捩られた形状で複数個連結して構成されている。捩れの方向により右巻きに捩られた右部材と左巻きに捩られた左部材とが設けられている。   The mixing device 4 is a known device commonly called a static mixer, and is configured by connecting a plurality of rectangular plates in a twisted shape. A right member that is twisted clockwise and a left member that is twisted counterclockwise are provided depending on the direction of twist.

以上のように構成された押出成形装置２０において、ＨＤＰＥ原料６とＰＡ原料７との混合原料による押出成形は以下のように行われる。図示しない加熱装置によりシリンダ１１、ダイプレート２および成形ダイ３の各内壁面がそれぞれ所定の温度になるように加熱制御され、図示しない駆動装置によりスクリュ１３が回転駆動されている状態で、粉粒体状あるいはペレット状のＨＤＰＥ原料６とペレット状のＰＡ原料７とを混合した混合原料をシリンダ１１内に供給する。この混合原料は、混合溶融されつつ、スクリュ１３の輸送作用により順次先端方向へ流動し、先端からダイプレート２の内孔２ａへ押出される。このダイプレート２の内孔２ａへ押出された混合原料は周知のように、内孔２ａ内に挿入されたミキシングデバイス４の間を流動し成形ダイ３の流路３ａへ押出される。成形ダイ３の流路３ａへ押出された混合原料は流路３ａの横幅方向へ広がってシート状に押出される。   In the extrusion molding apparatus 20 configured as described above, extrusion molding using a mixed raw material of the HDPE raw material 6 and the PA raw material 7 is performed as follows. In a state where the heating is controlled so that the inner wall surfaces of the cylinder 11, the die plate 2 and the molding die 3 are at predetermined temperatures by a heating device (not shown), and the screw 13 is rotationally driven by a driving device (not shown). A mixed raw material obtained by mixing the body-like or pellet-like HDPE raw material 6 and the pellet-like PA raw material 7 is supplied into the cylinder 11. While this mixed raw material is mixed and melted, it flows in the direction of the tip by the transport action of the screw 13 and is extruded from the tip to the inner hole 2 a of the die plate 2. As is well known, the mixed raw material extruded into the inner hole 2 a of the die plate 2 flows between the mixing devices 4 inserted into the inner hole 2 a and is extruded into the flow path 3 a of the molding die 3. The mixed raw material extruded into the flow path 3a of the molding die 3 spreads in the width direction of the flow path 3a and is extruded into a sheet shape.

しかしながら、以上の押出成形において、前記混合原料は、スクリュ式混練押出機１では、シリンダ１１の内壁面温度とスクリュ１３の構成および回転数とが混練度を低くするように図示しない制御部により設定・制御されていることにより、融点の低いＨＤＰＥ原料６のみが先に混練溶融されると共にペレット状でＨＤＰＥ原料６よりも融点の高いＰＡ原料７が破砕されず未溶融状態でダイプレート２内へ押出される。ダイプレート２では、ＰＡ原料７がダイプレート２の下流端付近で溶融温度に加熱されるように、ダイプレート２の内壁面温度が設定され、加熱される。成形ダイ３では、内壁面温度がＰＡ原料７の溶融温度以上に設定され、流路３ａにおいて横幅方向へ広がると共に先端方向へ流動して徐々に厚みを薄くする（圧縮する）ことにより、ペレット形状で溶融状態のＰＡ原料７が押し潰されて薄いフィルム状になり、シート３０の面方向へ二次元的に広がる。成形ダイ３のスリット３ｂを通過し押出されたシート３０は、図３に示すように、シート３０の幅方向断面の全幅において、フィルム状に大きく広がったＰＡ原料７が均一に、また多層に分布している。   However, in the above-described extrusion molding, in the screw-type kneading extruder 1, the mixed raw material is set by a control unit (not shown) so that the inner wall surface temperature of the cylinder 11 and the configuration and rotation speed of the screw 13 are lowered. -By controlling, only the HDPE raw material 6 having a low melting point is kneaded and melted first, and the PA raw material 7 having a higher melting point than the HDPE raw material 6 is not crushed into the die plate 2 in an unmelted state. Extruded. In the die plate 2, the inner wall surface temperature of the die plate 2 is set and heated so that the PA raw material 7 is heated to the melting temperature in the vicinity of the downstream end of the die plate 2. In the molding die 3, the inner wall surface temperature is set to be equal to or higher than the melting temperature of the PA raw material 7, and spreads in the lateral width direction in the flow path 3 a and flows toward the tip to gradually reduce the thickness (compress), thereby forming a pellet shape The molten PA raw material 7 is crushed into a thin film and spreads two-dimensionally in the plane direction of the sheet 30. As shown in FIG. 3, the sheet 30 extruded through the slit 3b of the forming die 3 has the PA raw material 7 spread widely in a film shape uniformly and distributed in multiple layers over the entire width of the sheet 30 in the width direction. doing.

以上の記述における成形ダイ３はシート成形ダイあるいはフィルム成形ダイを代表的に表わしたものであり、また、Ｔ字型に限定されるものではなく、Ｌ字型等その他の形状のシート成形ダイあるいはフィルム成形ダイでも良い。   The forming die 3 in the above description represents a sheet forming die or a film forming die as a representative, and is not limited to the T-shape, and other shapes such as an L-shape or the like. A film forming die may be used.

次に、本出願人が行った実施例について説明する。
ＨＤＰＥ原料６に２０重量％の割合でペレット状ＰＡ原料７を加えた混合原料により、図１に示すミキシングデバイス４を装備した押出成形装置と図５に示すミキシングデバイス４を装備しない押出成形装置において、シート押出成形による比較運転を行った。評価は、(１）成形ダイ３から押出された直後のシート製品の温度のバラツキの計測、(２)シート３０の切断面におけるＰＡ原料７の分布の観察、により行った。ＰＡ原料７の分布の観察は、ヨウ素液によりＰＡ原料を着色して行った。
(１)温度のバラツキの計測結果を以下に示す。
図１の装置：２０７±１℃（本発明）
図５の装置：２０９±４℃（従来例）
すなわち、ミキシングデバイス４を装備した場合の温度のバラツキが小さいことは押出された製品がより均一な材料であることを示しており、ミキシングデバイス４を装備しない場合はバラツキが大きく、製品がより不均一な材料であることを示している。
(２)シート３０の断面におけるＰＡ原料７の分布の観察結果は、ミキシングデバイス４を装備した場合を図３、ミキシングデバイス４を装備しない場合を図７に示す。
両図から明らかなように、ミキシングデバイス４を装備した場合はシート３０の全幅においてＰＡ原料７が均一に分布し、ミキシングデバイス４を装備しない場合はシート３０の全幅においてＰＡ原料７が不均一に（幅の両端部分に偏って）分布している。 Next, examples performed by the present applicant will be described.
In an extrusion molding apparatus equipped with the mixing device 4 shown in FIG. 1 and an extrusion molding apparatus not equipped with the mixing device 4 shown in FIG. 5 by using a mixed raw material obtained by adding the pellet-like PA raw material 7 to the HDPE raw material 6 at a ratio of 20% by weight. A comparative operation by sheet extrusion was performed. The evaluation was performed by (1) measuring the variation in temperature of the sheet product immediately after being extruded from the forming die 3 and (2) observing the distribution of the PA raw material 7 on the cut surface of the sheet 30. The observation of the distribution of the PA raw material 7 was performed by coloring the PA raw material with an iodine solution.
(1) The measurement result of temperature variation is shown below.
1 apparatus: 207 ± 1 ° C. (invention)
Apparatus of FIG. 5: 209 ± 4 ° C. (conventional example)
That is, when the mixing device 4 is equipped, a small temperature variation indicates that the extruded product is a more uniform material, and when the mixing device 4 is not equipped, the variation is large and the product is more inefficient. It shows that the material is uniform.
(2) The observation results of the distribution of the PA raw material 7 in the cross section of the sheet 30 are shown in FIG. 3 when the mixing device 4 is equipped and in FIG. 7 when the mixing device 4 is not equipped.
As is clear from both figures, when the mixing device 4 is provided, the PA raw material 7 is uniformly distributed over the entire width of the sheet 30, and when the mixing device 4 is not provided, the PA raw material 7 is non-uniform over the entire width of the sheet 30. Distributed (biased at both ends of the width).

本発明による押出成形方法を実施するための押出成形装置を示す断面図である。It is sectional drawing which shows the extrusion molding apparatus for enforcing the extrusion molding method by this invention. 図１のダイプレート終端の溶融混合原料の断面図である。FIG. 2 is a cross-sectional view of the molten mixed raw material at the end of the die plate of FIG. 本発明の押出成形方法により押出成形されたシートあるいはフィルムの押出方向に直交して切断された断面図である。It is sectional drawing cut | disconnected orthogonally to the extrusion direction of the sheet | seat or film extruded by the extrusion method of this invention. 混合原料が理想的に押出成形されたシートあるいはフィルムの断面のイメージ図である。It is an image figure of the section of the sheet or film in which the mixed raw material was ideally extruded. 従来の押出成形方法を実施するためのシートあるいはフィルム押出成形装置を示す断面図である。It is sectional drawing which shows the sheet | seat or film extrusion molding apparatus for enforcing the conventional extrusion method. 図５のダイプレート終端の溶融混合原料の断面図である。FIG. 6 is a cross-sectional view of the molten mixed material at the end of the die plate of FIG. 従来の押出成形方法により押出成形されたシートあるいはフィルムの押出方向に直交して切断された断面図である。It is sectional drawing cut | disconnected orthogonally to the extrusion direction of the sheet | seat or film extruded by the conventional extrusion method. スクリュ式混練押出機における混練度が高い場合の押出成形されたシートあるいはフィルムの断面のイメージ図である。It is an image figure of the cross section of the sheet | seat or film extruded when the kneading degree in a screw-type kneading extruder is high.

符号の説明Explanation of symbols

１ スクリュ式混練押出機
２ ダイプレート
２ａ 内孔
３ Ｔダイ
３ａ 流路
３ｂ スリット
４ ミキシングデバイス
６ ＨＤＰＥ原料
７ ＰＡ原料
１１ シリンダ
１１ａ 内孔
１２ ホッパ
１３ スクリュ
２０ 押出成形装置
３０ シート DESCRIPTION OF SYMBOLS 1 Screw type kneading extruder 2 Die plate 2a Inner hole 3 T die 3a Flow path 3b Slit 4 Mixing device 6 HDPE raw material 7 PA raw material 11 Cylinder 11a Inner hole 12 Hopper 13 Screw 20 Extrusion device 30 Sheet

Claims (2)

スクリュ式混練押出機(1)、ダイプレート(2)および成形ダイ(3)からなり、前記ダイプレート(2)にミキシングデバイス(4)を有する押出成形装置を用い、ＨＤＰＥ原料とＰＡ原料とを混合した混合原料を前記スクリュ式混練押出機(1)に供給し、前記スクリュ式混練押出機(1)で前記ＨＤＰＥ原料のみの溶融混練を行い、その後、前記スクリュ式混練押出機(1)よりも温度が高い状態の前記ダイプレート(2)内で前記ＰＡ原料が溶融され、溶融状態の前記混合原料が前記ミキシングデバイスを経て前記成形ダイ(3)の先端より押出されることを特徴とする押出成形方法。   A screw-type kneading extruder (1), a die plate (2) and a molding die (3), and using an extrusion molding apparatus having a mixing device (4) on the die plate (2), HDPE raw material and PA raw material The mixed mixed raw material is supplied to the screw-type kneading extruder (1), and only the HDPE raw material is melt-kneaded in the screw-type kneading extruder (1), and then from the screw-type kneading extruder (1). The PA raw material is melted in the die plate (2) in a high temperature state, and the mixed raw material in the molten state is extruded from the tip of the forming die (3) through the mixing device. Extrusion method. 前記ＰＡ原料(7)は、前記ダイプレート(2)の後段において溶融されることを特徴とする請求項１記載の押出成形方法。   The extrusion molding method according to claim 1, wherein the PA raw material (7) is melted at a subsequent stage of the die plate (2).
JP2003330084A 2003-09-22 2003-09-22 Extrusion molding method Pending JP2005096123A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010125729A (en) * 2008-11-28 2010-06-10 Hatachi Kako Kk Extrusion screw of monolayer blow molding machine
WO2012073969A1 (en) * 2010-11-30 2012-06-07 三菱瓦斯化学株式会社 Molded article having excellent fuel barrier properties

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010125729A (en) * 2008-11-28 2010-06-10 Hatachi Kako Kk Extrusion screw of monolayer blow molding machine
WO2012073969A1 (en) * 2010-11-30 2012-06-07 三菱瓦斯化学株式会社 Molded article having excellent fuel barrier properties
AU2011337681B2 (en) * 2010-11-30 2014-11-13 Mitsubishi Gas Chemical Company, Inc. Molded article having excellent fuel barrier properties
RU2565685C2 (en) * 2010-11-30 2015-10-20 Мицубиси Гэс Кемикал Компани, Инк. Extruded article with fine barrier properties for fuel
JP5835226B2 (en) * 2010-11-30 2015-12-24 三菱瓦斯化学株式会社 Manufacturing method of molded product with excellent fuel barrier properties

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