JP2009149109A - Multilayered resin film, resin coated metal sheet, production process of multilayered resin film and production process of resin coated metal sheet - Google Patents

Multilayered resin film, resin coated metal sheet, production process of multilayered resin film and production process of resin coated metal sheet Download PDF

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JP2009149109A
JP2009149109A JP2009092400A JP2009092400A JP2009149109A JP 2009149109 A JP2009149109 A JP 2009149109A JP 2009092400 A JP2009092400 A JP 2009092400A JP 2009092400 A JP2009092400 A JP 2009092400A JP 2009149109 A JP2009149109 A JP 2009149109A
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resin
manifold
film
coloring component
thickness
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JP5186426B2 (en
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Yasuhiro Matsubara
康洋 松原
Tomomasa Maida
知正 毎田
Takushi Nakamura
琢司 中村
Hiroshi Inasawa
弘志 稲沢
Harunori Kojo
治則 古城
Kazuhiro Sato
一弘 佐藤
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Toyo Kohan Co Ltd
Toyo Seikan Group Holdings Ltd
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Toyo Kohan Co Ltd
Toyo Seikan Kaisha Ltd
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<P>PROBLEM TO BE SOLVED: To provide a multilayered resin film with small surface irregularity, a resin coated metal sheet made by laminating the multilayered resin film onto a metal sheet, a production process of the multilayered resin film which produces the multilayered resin film by laminating a plurality of molten resins different in melt viscocity with high-speed without making irregularity on the film surface, and a production process of the resin coated metal sheet which laminates the multilayered resin film onto the metal sheet in the multilayered film comprising a plurality of resin layers mutually different in melt viscosity. <P>SOLUTION: A non-oriented multilayered resin film comprises at least a polyester resin containing a coloring component and a polyester resin without coloring component. In addition, melting tension Tm under extrusion temperature of the polyester resin without coloring component fulfills 1.0g ≤Tm, and thickness of the film comprising the polyester resin without coloring component is one third or more of the total thickness. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、溶融張力および溶融粘度が互いに相違する複数の樹脂層からなる表面の凹凸が小さい多層樹脂フィルム、その多層樹脂フィルムを被覆してなる樹脂被覆金属板、多層樹脂フィルムの製造方法、および樹脂被覆金属板の製造方法に関する。特に、樹脂フィルムの製膜速度が100m/分以上と高速生産が可能な製造方法に関する。   The present invention is a multilayer resin film having a small surface irregularity composed of a plurality of resin layers having different melt tension and melt viscosity, a resin-coated metal plate coated with the multilayer resin film, a method for producing the multilayer resin film, and The present invention relates to a method for producing a resin-coated metal plate. In particular, the present invention relates to a manufacturing method capable of high-speed production with a resin film forming speed of 100 m / min or more.

飲料缶などの分野においては、樹脂フィルム被覆金属板を絞り加工や絞りしごき加工を施してなる缶が多用されている。これは、樹脂フィルムが加工時における金属板に対する優れた接着性と、内容物に対する優れた耐透過性を兼備していることによる。これらの樹脂フィルム被覆金属板を成形加工してなる缶においては、近年、缶に充填する内容物の多様化、および缶コストの削減を目的としたさらなる缶体の軽量化のための加工度の上昇に伴って、優れた耐透過性および優れた加工接着性を単層の樹脂フィルムで両立させることが困難になってきている。そのため、加工接着性と耐透過性をそれぞれの特性に優れた単層の樹脂フィルムを用いてそれぞれ別個に担わせ、それらの個々の単層フィルムを多層化したフィルムを金属板に被覆することにより、従来よりさらに優れた加工接着性と耐透過性を有する、樹脂フィルム被覆金属板に用いる樹脂フィルムとして適用することが試みられている。   In the field of beverage cans and the like, a can obtained by drawing or squeezing and squeezing a resin film-coated metal plate is frequently used. This is because the resin film has excellent adhesion to the metal plate during processing and excellent permeation resistance to the contents. In recent years, the cans formed by molding these resin film-coated metal plates have a processing degree for diversifying the contents to be filled in the cans and further reducing the weight of the cans for the purpose of reducing can costs. Along with the rise, it has become difficult to achieve both excellent permeation resistance and excellent work adhesion with a single-layer resin film. For this reason, by using a single-layer resin film having excellent properties and processing adhesion and permeation resistance separately, and by coating a metal plate with a film obtained by multilayering those individual single-layer films. Attempts have been made to apply it as a resin film used for a resin film-coated metal plate, which has even better work adhesion and permeation resistance than before.

しかし、上記のように物性の異なる樹脂フィルムを多層化して用いる場合、融点が異なり同一温度で加熱溶融させた場合の溶融粘度がそれぞれ異なる樹脂を加熱溶融し共押出してフィルムに製膜しなくてはならないが、融点が異なる樹脂を加熱溶融させる場合、同一温度で加熱溶融させると融解温度の高い樹脂の溶融粘度が高く、融解温度の低い樹脂の溶融粘度が低くなる場合が多い。そして、マルチマニフォルドダイを用いて同一温度でこのような樹脂を加熱溶融させた樹脂を多層化して積層する場合、隣接する樹脂の溶融粘度が異なると、個々のマニフォルドを通った個々の加熱溶融樹脂を多層樹脂として合流させる際に、樹脂層同士の界面において加熱溶融樹脂の流れに乱れが生じ、フィルム表面に厚みムラ(凹凸)が生じてしまうことがある。フィルム表面に生じる厚みムラはフローマークと呼ばれ、目視的に不良であるばかりでなく、缶体に成形するための絞り加工や絞りしごき加工、缶上部の開口部のネックイン(小径化)加工を実施する際に均一な加工が不可能となり、破胴などの原因となる。また、生産速度を向上させるために高速で溶融樹脂を押し出すと幅方向における寸法の差、すなわち耳の発生が大きくなったり、ダイリップから押し出された樹脂が均一に落下せず脈動しながら落下するようになり、均一な厚さのフィルムが得られなくなる。また、フィルムに着色成分である顔料が入ると、これらは発生しやすくなる。このような耳やフィルムの厚みムラ(凹凸、フローマーク)の発生を抑制するため、下記の公報に開示された方法が試みられている。   However, when resin films having different physical properties are used in multiple layers as described above, resins having different melting points and different melt viscosities when heated and melted at the same temperature are heated and melted and coextruded to form a film. However, when resins having different melting points are heated and melted, if they are heated and melted at the same temperature, the melt viscosity of a resin having a high melting temperature is high, and the melt viscosity of a resin having a low melting temperature is often low. And when multi-manifold dies are used to laminate and laminate a resin in which such resins are heated and melted at the same temperature, if the melt viscosity of adjacent resins is different, individual heated and melted resins that have passed through individual manifolds When the materials are joined together as a multilayer resin, the flow of the heated molten resin may be disturbed at the interface between the resin layers, resulting in uneven thickness (unevenness) on the film surface. The uneven thickness on the film surface is called a flow mark and is not only visually defective, but also draw processing and drawing ironing to form a can body, neck-in (small diameter) processing of the upper opening of the can When carrying out the process, uniform processing becomes impossible, which may cause broken bodies. Also, if the molten resin is extruded at a high speed in order to improve the production speed, the difference in dimensions in the width direction, that is, the generation of ears will increase, or the resin extruded from the die lip will fall without pulsating uniformly. Thus, a film having a uniform thickness cannot be obtained. Moreover, when the pigment which is a coloring component enters into a film, these will generate | occur | produce easily. In order to suppress the occurrence of such unevenness of the ears and film (unevenness, flow mark), the method disclosed in the following publication has been tried.

特許文献1においては、互いの融点や加熱溶融時の粘度の相違が小さい樹脂を選択して用いることにより、フローマークの発生を防止する方法が開示されているが、樹脂フィルムに要求される物性によっては、互いの融点や加熱溶融時の粘度が大きく相違する樹脂を選択せざるを得ない場合が多く、この公報に開示された方法は、極く限られた用途にしか適用できない。   Patent Document 1 discloses a method for preventing the occurrence of a flow mark by selecting and using a resin having a small difference in melting point and viscosity at the time of heating and melting. However, physical properties required for a resin film are disclosed. Depending on the case, it is often necessary to select resins having mutually different melting points or viscosities when heated and melted, and the method disclosed in this publication can be applied only to extremely limited applications.

特許文献2は、加熱溶融させた複数の樹脂層をTダイの前で合流させるフィードブロック法を用い、フィードブロックと、フィードブロックに接続して多層樹脂フィルムを成形するTダイを組み合わせた多層押出成型方法において、フィードブロックに設けた加熱ヒータを温度制御することにより、多層に合流する積層境界面におけるずれ(フローマーク)などの不良現象を低減させる方法を開示している。図2にその多層押出成形装置の一例の概略を示す。多層押出成形装置は複数のマニフォルド14a〜14gを有するフィードブロック10と、マニフォルド14a〜14gからの樹脂の合流部16の下方に、フィードブロック10に接続して設けられたTダイ12とで構成されている。それぞれのマニフォルド14a〜14gからの樹脂通路の合流部の周辺に、例えばマニフォルド14bの出側の樹脂通路に加熱ヒータ20b、22b、温度計28bなど(説明の簡略のため、マニフォルド14bにのみ言及)を設け、各マニフォルドから供給される各溶融樹脂材料の温度/粘度を制御して温度/粘度を均一化することにより、多層樹脂に合流する積層境界面における不良現象を低減させる。   Patent Document 2 uses a feed block method in which a plurality of heat-melted resin layers are joined in front of a T die, and a multilayer extrusion that combines a feed block and a T die that is connected to the feed block to form a multilayer resin film. In the molding method, a method is disclosed in which the temperature of a heater provided in a feed block is controlled to reduce a defective phenomenon such as a shift (flow mark) at a laminated boundary surface joining multiple layers. FIG. 2 shows an outline of an example of the multilayer extrusion molding apparatus. The multilayer extrusion molding apparatus is composed of a feed block 10 having a plurality of manifolds 14a to 14g, and a T die 12 provided below the junction 16 of the resin from the manifolds 14a to 14g and connected to the feed block 10. ing. Around the junction of the resin passages from the manifolds 14a to 14g, for example, the heaters 20b and 22b, the thermometer 28b, etc. in the resin passage on the outlet side of the manifold 14b (for the sake of simplicity, only the manifold 14b is mentioned) And controlling the temperature / viscosity of each molten resin material supplied from each manifold to equalize the temperature / viscosity, thereby reducing the defective phenomenon at the laminated interface joining the multilayer resin.

しかし、フィードブロック法においては、多層に合流した後に樹脂が流入するTダイの内部が単層構造であり、合流して多層化した樹脂が合流部16からダイリップ32の出口開口部34までに至る距離が大きくなり、その距離を溶融樹脂が移動する間、Tダイは全体として加熱されるのみであるために、各樹脂層が同一粘度となる合流直後の各樹脂層のそれぞれ異なる加熱温度を温度差を有したままで保つことが不可能であり、出口開口部34においては各樹脂層の加熱温度が変化することによって、各樹脂層の溶融粘度を同一に保てなくなるので、フローマークの発生を防止することが困難になる。このように、この公報による方法も、同一の溶融粘度が得られる融点の差がそれ程大きく相違しない樹脂を用いるような、限られた用途にしか適用できない。また、これらの公報に開示された方法においても、溶融樹脂の張力が小さい場合は製膜速度を増大することができない。   However, in the feed block method, the inside of the T die into which the resin flows after joining the multilayers has a single layer structure, and the joined and multilayered resin reaches from the joining part 16 to the outlet opening 34 of the die lip 32. Since the T die is only heated as a whole while the distance increases and the molten resin moves through the distance, the heating temperature of each resin layer immediately after merging is increased. Since it is impossible to keep the difference and the heating temperature of each resin layer is changed at the outlet opening 34, the melt viscosity of each resin layer cannot be kept the same. It becomes difficult to prevent. As described above, the method according to this publication can be applied only to a limited use such as using a resin that does not differ so much in melting point that the same melt viscosity is obtained. Also, in the methods disclosed in these publications, the film forming speed cannot be increased when the tension of the molten resin is small.

特開平08−290532号公報Japanese Patent Application Laid-Open No. 08-290532 特開平11−309770号公報Japanese Patent Laid-Open No. 11-309770

本発明は、溶融粘度が互いに相違する複数の樹脂層からなる多層フィルムにおいて、表面の凹凸が小さい多層樹脂フィルム、多層樹脂フィルムを金属板に積層してなる樹脂被覆金属板、および溶融粘度が互いに相違する複数の溶融樹脂を、高速でかつフィルム表面に凹凸を形成させずに積層して多層樹脂フィルムとする多層樹脂フィルムの製造方法、ならびに多層樹脂フィルムを金属板に積層する樹脂被覆金属板の製造方法を提供することを目的とする。特に、樹脂フィルムの製膜速度が100m/分以上と高速生産が可能な製造方法に関する。   The present invention relates to a multilayer film composed of a plurality of resin layers having different melt viscosities, a multilayer resin film having small surface irregularities, a resin-coated metal plate obtained by laminating a multilayer resin film on a metal plate, and a melt viscosity of each other A method for producing a multilayer resin film by laminating a plurality of different molten resins at high speed without forming irregularities on the film surface, and a resin-coated metal plate for laminating a multilayer resin film on a metal plate An object is to provide a manufacturing method. In particular, the present invention relates to a manufacturing method capable of high-speed production with a resin film forming speed of 100 m / min or more.

本発明によれば、少なくとも着色成分を含有するポリエステル樹脂及び着色成分を含有しないポリエステル樹脂から構成される多層樹脂フィルムにおいて、前記着色成分を含有しないポリエステル樹脂が、押出温度における溶融張力Tmが1.0g≦Tmであり、且つ該着色成分を含有しないポリエステル樹脂から成るフィルムの厚さが全厚さの3分の1以上であることを特徴とする無延伸の多層樹脂フィルムが提供される
本発明の多層樹脂フィルムにおいては、長さ方向の全幅方向で測定した最大厚さと最小厚さの差で表わされる厚みムラが、5.0μm以下である
また本発明によれば、上記多層樹脂フィルムを金属板に積層してなる樹脂被覆金属板が提供される
According to the present invention, in a multilayer resin film composed of a polyester resin containing at least a coloring component and a polyester resin not containing a coloring component, the polyester resin not containing the coloring component has a melt tension Tm of 1. There is provided an unstretched multilayer resin film characterized in that 0 g ≦ Tm and the thickness of the film made of a polyester resin not containing the coloring component is one third or more of the total thickness .
In the multilayer resin film of the present invention, the thickness unevenness represented by a difference between the maximum thickness and the minimum thickness was measured in the length direction of the full width direction is less than or equal to 5.0 .mu.m.
Moreover , according to this invention, the resin-coated metal plate formed by laminating | stacking the said multilayer resin film on a metal plate is provided .

本発明によればまた、押出温度における溶融張力Tmが1.0g≦Tmである着色成分を含有しないポリエステル樹脂及び着色成分を含有するポリエステル樹脂を少なくとも含む、2種類以上のポリエステル樹脂を、マルチマニフォルドダイを用いて、それぞれのマニフォルドに連続して設けられた押出機、それぞれのマニフォルド、およびそれぞれのマニフォルドに隣接するダイの部分のそれぞれの温度を制御し、溶融粘度の高い樹脂が通る押出機、マニフォルド、およびマニフォルドに隣接するダイの部分の温度を、溶融粘度の低い樹脂が通る押出機、マニフォルド、およびマニフォルドに隣接するダイの部分の温度より高温に保持して、着色成分を含有しないポリエステル樹脂から成るフィルムの厚さが全厚さの3分の1以上となるようにして、それぞれの溶融樹脂を積層して多層フィルムとすることを特徴とする、多層樹脂フィルムの製造方法が提供される
本発明の多層樹脂フィルムの製造方法においては、隣接する樹脂層の溶融粘度の差が、20〜500秒 −1 の剪断速度において3000ポアズ以下となるように、温度制御することが好適である。
According to the present invention, two or more kinds of polyester resins containing at least a polyester resin containing no coloring component and a polyester resin containing a coloring component having a melt tension Tm at an extrusion temperature of 1.0 g ≦ Tm Using a die, an extruder provided continuously in each manifold, each manifold, and an extruder through which a resin having a high melt viscosity passes, controlling the temperature of each manifold and the portion of the die adjacent to each manifold, Polyester resin that does not contain coloring components by maintaining the temperature of the manifold and the portion of the die adjacent to the manifold higher than the temperature of the extruder through which the low melt viscosity resin passes, the manifold, and the portion of the die adjacent to the manifold The thickness of the film will be more than one third of the total thickness Thus, there is provided a method for producing a multilayer resin film, wherein each molten resin is laminated to form a multilayer film.
In the method for producing a multilayer resin film of the present invention, it is preferable to control the temperature so that the difference in melt viscosity between adjacent resin layers is 3000 poise or less at a shear rate of 20 to 500 sec- 1 .

本発明よれば更に、押出温度における溶融張力Tmが1.0g≦Tmである着色成分を含有しないポリエステル樹脂及び着色成分を含有するポリエステル樹脂を少なくとも含む、2種類以上のポリエステル樹脂を、マルチマニフォルドダイを用いて、それぞれのマニフォルドに連続して設けられた押出機、それぞれのマニフォルド、およびそれぞれのマニフォルドに隣接するダイの部分のそれぞれの温度を制御し、溶融粘度の高い樹脂が通る押出機、マニフォルド、およびマニフォルドに隣接するダイの部分の温度を、溶融粘度の低い樹脂が通る押出機、マニフォルド、およびマニフォルドに隣接するダイの部分の温度より高温に保持して、着色成分を含有しないポリエステル樹脂から成るフィルムの厚さが全厚さの3分の1以上となるようにして、それぞれの溶融樹脂を積層して多層化した後、金属板上に押出すことを特徴とする、樹脂被覆金属板の製造方法が提供される
本発明の樹脂被覆金属板の製造方法煮においては、隣接する樹脂層の溶融粘度の差が、20〜500秒 −1 の剪断速度において3000ポアズ以下となるように、温度制御することが好適である。
According to the present invention, two or more kinds of polyester resins including at least a polyester resin not containing a coloring component having a melt tension Tm at an extrusion temperature of 1.0 g ≦ Tm and a polyester resin containing a coloring component are added to a multi-manifold die. Are used to control the temperature of each of the extruders continuously provided in each manifold, each manifold, and the portion of the die adjacent to each manifold, and the extruder through which the resin having a high melt viscosity passes. And the temperature of the die portion adjacent to the manifold is higher than the temperature of the extruder, manifold, and die portion adjacent to the manifold through which the low melt viscosity resin passes, and from the polyester resin containing no coloring component The thickness of the film to be more than one third of the total thickness Thus, a method for producing a resin-coated metal sheet is provided , wherein each molten resin is laminated and multilayered and then extruded onto the metal sheet.
In the method for producing a resin-coated metal sheet of the present invention, it is preferable to control the temperature so that the difference in melt viscosity between adjacent resin layers is 3000 poise or less at a shear rate of 20 to 500 sec- 1. is there.

本発明においては、着色成分を含有した樹脂を少なくとも1種類含み、同一の加熱溶融温度における、20〜500秒−1の剪断速度における溶融粘度の差が3000〜20000ポアズである2種類以上の樹脂を、マルチマニフォルドダイを用いて、それぞれのマニフォルドに連続して設けられた押出機、それぞれのマニフォルド、およびそれぞれのマニフォルドに隣接するダイの部分のそれぞれの温度を制御し、溶融粘度の高い樹脂が通る押出機、マニフォルド、およびマニフォルドに隣接するダイの部分の温度を、溶融粘度の低い樹脂が通る押出機、マニフォルド、およびマニフォルドに隣接するダイの部分の温度より高温に保持して、隣接する樹脂層の溶融粘度の差を、20〜500秒−1の剪断速度において3000ポアズ以下とした後、溶融張力が1g以上である着色成分を含有しない樹脂の厚さが全厚さの3分の1以上となるようにして、それぞれの溶融樹脂を積層して多層フィルムとするものであり、高速度で製膜しても脈動や耳発生が増大することがなく、得られた樹脂フィルムの厚みムラは極めて小さい。また、このようにして得られる多層フィルムは表面における厚みムラが5μm以下であるので、目視的な平滑性に優れているのみならず、樹脂フィルム中に通常の多層フィルムにおけるような溶融粘度に基づく応力が生じることがないので、多層樹脂フィルムを金属板に積層被覆して多層樹脂フィルム被覆金属板とした場合に、樹脂フィルムに疵が付いても樹脂フィルムが金属板から捲れ上がって剥離することがない。 In the present invention, two or more kinds of resins containing at least one kind of resin containing a coloring component and having a difference in melt viscosity of 3000 to 20000 poise at a shear rate of 20 to 500 sec- 1 at the same heating and melting temperature. Using a multi-manifold die, the temperature of the extruder provided continuously in each manifold, each manifold, and the portion of the die adjacent to each manifold is controlled, and a resin with a high melt viscosity is obtained. The temperature of the extruder, manifold, and die part adjacent to the manifold passing through is kept higher than the temperature of the extruder, manifold, and die part adjacent to the manifold through which the low melt viscosity resin passes. the difference in melt viscosities of the layers, and 3000 poises at a shear rate of 20 to 500 sec -1 And then, as the thickness of the resin melting tension does not contain coloring component is at least 1g becomes one third or more of the total thickness, in which a multilayer film by laminating each molten resin There is no increase in pulsation or ear generation even when the film is formed at high speed, and the thickness unevenness of the obtained resin film is extremely small. Moreover, since the multilayer film obtained in this way has a thickness unevenness of 5 μm or less on the surface, it is not only excellent in visual smoothness but also based on the melt viscosity as in a normal multilayer film in a resin film. Since no stress is generated, when a multilayer resin film is laminated and coated on a metal plate to form a multilayer resin film-coated metal plate, the resin film will roll up and peel off from the metal plate even if the resin film has wrinkles. There is no.

本発明の多層フィルムの製造方法の一例を示す概略図。Schematic which shows an example of the manufacturing method of the multilayer film of this invention. 従来の多層フィルムの製造方法の一例を示す概略図。Schematic which shows an example of the manufacturing method of the conventional multilayer film.

以下、図面を参照しながら本発明を説明する。図1は、溶融粘度が互いに相違する複数の樹脂層からなる本発明の多層フィルムの製造方法の一例を示す概略図である。説明を簡略にするため、2層樹脂フィルムの製膜に用いる場合を例示する。2個のマニフォルド2aおよび2bを有するマルチマニフォルドダイ1には、溶融粘度が高い方の樹脂を加熱溶融して押し出す押出機6aと溶融粘度が低い方の樹脂を加熱溶融して押し出す押出機6bが、それぞれ樹脂通路を介して2aおよび2bと接続して設けられている。マニフォルド2aおよび2bは、マルチマニフォルドダイ1の下方で合体してリップランド5となり、マルチマニフォルドダイ1の最下部のダイリップに設けられた吐出口7に連なっている。   The present invention will be described below with reference to the drawings. FIG. 1 is a schematic view showing an example of a method for producing a multilayer film of the present invention comprising a plurality of resin layers having different melt viscosities. In order to simplify the explanation, a case of using for forming a two-layer resin film is illustrated. The multi-manifold die 1 having two manifolds 2a and 2b includes an extruder 6a that heats and melts a resin having a higher melt viscosity and an extruder 6b that heats and melts a resin having a lower melt viscosity. Are respectively connected to 2a and 2b via resin passages. The manifolds 2a and 2b are combined below the multi-manifold die 1 to form a lip land 5, and are connected to a discharge port 7 provided in the lowermost die lip of the multi-manifold die 1.

マルチマニフォルドダイ1には、ダイ本体の溶融粘度が高い方の樹脂が通る側を加熱するためのヒータ11aと溶融粘度が低い方の樹脂が通る側を加熱するためのヒータ11bと、マニフォルド2aおよび2bを加熱するためにそれぞれのマニフォルドに隣接して設けられたヒータ3aおよび3b、ならびにヒータ4aと4bが設けられ、さらに、押出機6aおよび押出機6bとマルチマニフォルド2aおよび2bをそれぞれ接続する樹脂通路を加熱するためのヒータ10aおよび10bが設けられている。これらのそれぞれのヒータを設けた部位付近には、図示しない熱電対などの温度測定手段を設けてそれぞれの部位の温度を測定しながら加熱温度を一定に制御し、マニフォルド2aおよび2b内のそれぞれの加熱溶融樹脂の粘度の差が一定範囲以内となるように個別にそれぞれのヒータの温度を制御する。   The multi-manifold die 1 includes a heater 11a for heating the side through which the higher melt viscosity of the die body passes, a heater 11b for heating the side through which the lower melt viscosity passes, a manifold 2a, Heaters 3a and 3b provided adjacent to the respective manifolds for heating 2b, and heaters 4a and 4b are provided, and the extruder 6a and the extruder 6b are connected to the multi-manifolds 2a and 2b, respectively. Heaters 10a and 10b for heating the passage are provided. A temperature measuring means such as a thermocouple (not shown) is provided in the vicinity of the portion where each of these heaters is provided, and the heating temperature is controlled to be constant while measuring the temperature of each portion, and each of the manifolds 2a and 2b is controlled. The temperature of each heater is individually controlled so that the difference in viscosity of the heated molten resin is within a certain range.

押出機6aおよび押出機6bで加熱溶融された、同一の加熱溶融温度における溶融粘度の差が20〜500秒−1の剪断速度において3000〜20000ポアズである2種類の樹脂は、それぞれマルチマニフォルドダイ1内に設けられたマニフォルド2aおよび2bを通り、マルチマニフォルドダイ1の下方で合体したリップランド5の入口で積層され、ダイ1の最下部のダイリップに設けられた吐出口7から、吐出口7の下方に設けられた内部を水などの冷媒が循環するように構成された冷却ロール9上に吐出され、冷却固化した多層樹脂フィルム8となり、連続的にコイル状に巻き取るコイラーなどの巻取手段12に巻き取られる。   The two types of resins melted and melted by the extruder 6a and the extruder 6b and having a difference in melt viscosity at the same heating and melting temperature of 3000 to 20000 poise at a shear rate of 20 to 500 sec-1 are respectively multi-manifold dies. 1 through the manifolds 2a and 2b provided in the die 1, stacked at the inlet of the lip land 5 combined below the multi-manifold die 1, and from the outlet 7 provided in the lowermost die lip of the die 1 to the outlet 7 Winding of a coiler or the like which is discharged onto a cooling roll 9 configured to circulate a coolant such as water in the interior provided below and becomes a cooled and solidified multilayer resin film 8 and continuously wound in a coil shape It is wound up on the means 12.

このように構成された多層樹脂フィルムの製造装置を用いて、本発明の多層樹脂フィルムは以下のようにして製膜することができる。
適用可能な上記樹脂フィルムとしては、特に限定されるものではないが、例えば下記のポリエステル樹脂が適用できる。ポリエステル樹脂が誘導される酸成分としては、テレフタル酸、イソフタル酸、オルソフタール酸、P−β−オキシエトキシ安息香酸、ナフタレン−2,6−ジカルボン酸、ジフェノキシエタン−4,4’−ジカルボン酸、5−ナトリウムスルホイソフタル酸等の2塩基性芳香族ジカルボン酸、ヘキサヒドロテレフタル酸、シクロヘキサンジ酢酸等の脂環族ジカルボン酸、アジピン酸、セバシン酸、ダイマー酸等の脂肪族ジカルボン酸、トリメット酸、ピロメリット酸、ヘミメリット酸、1,1,2,2−エタンテトラカルボン酸、1,1,2−エタントリカルボン酸、1,3,5−ペンタントリカルボン酸、1,2,3,4−シクロペンタンテトラカルボン酸、ビフェニルー3,4,3’,4’−テトラカルボン酸等の多塩基酸等が挙げられる。勿論、これらは、単独でも或いは2種以上の組み合わせでも使用される。ポリエステルが誘導されるアルコール成分としては、エチレングリコール、プロピレングリコ−ル、1,4−ブタンジオール、ネオペンチルグリコール、1,6−へキシレングリコール、ジエチレングリコール、トリエチレングリコール、シクロヘキサンジメタノール等のジオール類や、ペンタエリスリトール、グリセロール、トリメチロールプロパン、1,2,6−へキサントリオール、ソルビトール、1,1,4,4−テトラキス(ヒドロキシメチル)シクロヘキサン等の多価アルコール等が挙げられる。勿論、これらは、単独でも或いは2種以上の組み合わせでも使用できる。
Using the multilayer resin film manufacturing apparatus configured as described above, the multilayer resin film of the present invention can be formed as follows.
Although it does not specifically limit as said applicable resin film, For example, the following polyester resin is applicable. Examples of the acid component from which the polyester resin is derived include terephthalic acid, isophthalic acid, orthophthalic acid, P-β-oxyethoxybenzoic acid, naphthalene-2,6-dicarboxylic acid, diphenoxyethane-4,4′-dicarboxylic acid, Dibasic aromatic dicarboxylic acids such as 5-sodiumsulfoisophthalic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid and cyclohexanediacetic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid and dimer acid, trimet acid, Pyromellitic acid, hemimellitic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2-ethanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, 1,2,3,4-cyclo And polybasic acids such as pentanetetracarboxylic acid and biphenyl-3,4,3 ′, 4′-tetracarboxylic acid. Of course, these may be used alone or in combination of two or more. Examples of the alcohol component from which the polyester is derived include diols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, and cyclohexanedimethanol. And polyhydric alcohols such as pentaerythritol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakis (hydroxymethyl) cyclohexane, and the like. Of course, these can be used alone or in combination of two or more.

本発明の多層樹脂フィルムに用いられる着色成分としては、従来樹脂フィルムの着色に用いられていた着色剤全てを用いることができ、例えば、次のものを例示できる。
黒色顔料:カーボンブラック、マグネタイト、アセチレンブラック、ランブラック、アニリンブラック。
黄色顔料:黄鉛、亜鉛黄、カドミウムイエロー、黄色酸化鉄、ミネラルファストイエロー、ニッケルチタンイエロー、ネーブルスイエロー、ナフトールイエローS、ハンザイエローG、ハンザイエロー10G、ベンジジンイエローG、ベンジジンイエローGR、キノリンイエローレーキ、パーマンネントイエローNCG、タートラジンレーキ。
橙色顔料:赤口黄鉛、モリブテンオレンジ、パーマネントオレンジGTR、ピラゾロンオレンジ、バルカンオレンジ、インダスレンブリリアントオレンジRK、ベンジジンオレンジG、インダスレンブリリアントオレンジGK。
赤色顔料:ベンガラ、カドミウムレッド、鉛丹、硫化水銀カドミウム、パーマネントレッド4R、リソールレッド、ピラゾロンレッド、ウオッチングレッドカルシウム塩、レーキレッドD、ブリリアントカーミン6B、エオシンレーキ、ローダミンレーキB、アリザリンレーキ、ブリリアントカーミン3B。
紫色顔料:マンガン紫、ファストバイオレットB、メチルバイオレットレーキ。
青色顔料:群青、紺青、コバルトブルー、アルカリブルーレーキ、ビクトリアブルーレーキ、フタロシアニンブルー、無金属フタロシアニンブルー、フタロシアニンブルー部分塩素化物、ファーストスカイブルー、インダスレンブルーBC。
緑色顔料:クロムグリーン、酸化クロム、ピグメントグリーンB、マラカイトグリーンレーキ、ファナルイエローグリーンG。
白色顔料:ルチル型又はアナターゼ方の二酸化チタン、亜鉛華、グロスホワイト、パーライト、硫酸沈降性パーライト、炭酸カルシウム、石膏、沈降性シリカ、エアロジル、タルク、焼成或いは未焼成クレイ、炭酸バリウム、アルミナホワイト、合成或いは天然マイカ、合成ケイ酸カルシウム、炭酸マグネシウム。
As the coloring component used in the multilayer resin film of the present invention, all the coloring agents conventionally used for coloring a resin film can be used. For example, the following can be exemplified.
Black pigment: carbon black, magnetite, acetylene black, run black, aniline black.
Yellow pigments: yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow Rake, Permanent Yellow NCG, Tartrazine Rake.
Orange pigments: reddish yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, indanthrene brilliant orange GK.
Red pigment: Bengala, cadmium red, red lead, mercury cadmium sulfide, permanent red 4R, risor red, pyrazolone red, watching red calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, brilliant Carmine 3B.
Purple pigment: Manganese purple, fast violet B, methyl violet lake.
Blue pigments: ultramarine blue, bituminous blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, indanthrene blue BC.
Green pigments: chrome green, chrome oxide, pigment green B, malachite green lake, fanal yellow green G.
White pigments: rutile or anatase titanium dioxide, zinc white, gloss white, perlite, sulfate precipitated perlite, calcium carbonate, gypsum, precipitated silica, aerosil, talc, calcined or uncalcined clay, barium carbonate, alumina white, Synthetic or natural mica, synthetic calcium silicate, magnesium carbonate.

着色剤の粒径は、一般に0.05乃至2μm、特に0.1乃至0.5μmの範囲にあることが好ましい。これにより、優れた加工性と隠蔽力の両方を兼ね備えることが可能となる。本発明の目的に特に好適な着色剤は、二酸化チタンであり、このものは白色で大きい隠蔽力を有している。
着色剤の樹脂への配合量は、着色成分含有樹脂の溶融粘度及び溶融張力を上述した範囲にし得る限り特に制限はなく、用途に応じて適宜決定することができる。
The particle size of the colorant is generally in the range of 0.05 to 2 μm, particularly 0.1 to 0.5 μm. This makes it possible to combine both excellent processability and hiding power. A particularly suitable colorant for the purposes of the present invention is titanium dioxide, which is white and has great hiding power.
The blending amount of the colorant to the resin is not particularly limited as long as the melt viscosity and melt tension of the color component-containing resin can be within the above-described ranges, and can be appropriately determined according to the application.

同一の加熱溶融温度における溶融粘度が上記のように20〜500秒−1の剪断速度において3000〜20000ポアズの範囲でそれぞれ異なり、かつそのうちの1種の着色成分を含有した樹脂(図1の場合は2種であり、説明を容易にするため、以下、図1に示す押出機6bで加熱溶融する方の樹脂が着色成分を含む場合を想定して説明する)のそれぞれのペレットを押出機6aおよび6bで加熱溶融し、それぞれの押出機の下方に設けられたマルチマニフォルドダイ1内のそれぞれの樹脂通路を介して接続されたマニフォルド2aおよび2bに導かれ、合体部に向かって進んでいく。このとき、それぞれの樹脂はヒータ10aおよび10b、ヒータ11aおよび11b、ヒータ3aおよび3b、ヒータ4aおよび4bにより、それぞれの樹脂の溶融粘度の差が、20〜500秒−1の剪断速度において3000ポアズ以下となるように、それぞれのヒータの加熱温度をそれぞれのヒータ付近に設けられた熱電対などの温度測定手段で測定しながら制御する。 Resins having different melt viscosities at the same heating and melting temperature in the range of 3000 to 20000 poises at a shear rate of 20 to 500 seconds- 1 as described above, and containing one coloring component (in the case of FIG. 1) Are two types, and for ease of explanation, the pellets of the extruder 6a will be described below assuming that the resin to be heated and melted by the extruder 6b shown in FIG. 1 contains a coloring component). And 6b are led to the manifolds 2a and 2b connected via the respective resin passages in the multi-manifold die 1 provided below the respective extruders, and proceed toward the combined portion. At this time, the respective resins have a difference in melt viscosity of 3000 poise at a shear rate of 20 to 500 seconds −1 by the heaters 10a and 10b, the heaters 11a and 11b, the heaters 3a and 3b, and the heaters 4a and 4b. As described below, the heating temperature of each heater is controlled while being measured by temperature measuring means such as a thermocouple provided in the vicinity of each heater.

次いで、以上のようにしてそれぞれの溶融粘度の差が20〜500秒−1の剪断速度において3000ポアズ以下とされた溶融樹脂はマニフォルド2aおよび2bの合体部で合体したリップランド5の入口で積層され、吐出口7から冷却ロール9上に吐出されて固化し、多層(2層)フィルム8となるが、特に高速度で溶融樹脂を押し出した場合、押出温度における着色成分を含有した樹脂の溶融張力が0.5g未満であるか、または着色成分を含有しない樹脂の溶融張力が1g未満であると押し出されるフィルム状の溶融樹脂が脈動して長手方向の厚さが不均一になったり幅方向で耳が発生するようになる。着色成分を含有した樹脂の溶融張力Tmが0.5g≦Tm<1.0gの樹脂を用い、押し出された多層フィルムの全厚さに対してこの溶融張力0.5g≦Tm<1.0gの樹脂の層が2分の1以上、あるいはTm≧1.0gの樹脂を用い、押し出された多層フィルムの全厚さに対してこの溶融張力0.5g≦Tm<1.0gの樹脂の層が3分の1以上となるように、または、着色成分を含有しない樹脂の溶融張力が1g以上の樹脂を用い、押し出された多層フィルムの全厚さに対してこの溶融張力が1g以上の樹脂の厚さが3分の1以上となるように押出量を制御することにより、脈動や耳の発生を防止することができる。そのため、より高速で製膜することができる。 Next, the molten resin having a difference in melt viscosity of 3000 poise or less at a shear rate of 20 to 500 seconds −1 as described above is laminated at the entrance of the lip land 5 merged at the merged portion of the manifolds 2a and 2b. Then, it is discharged from the discharge port 7 onto the cooling roll 9 and solidified to form a multilayer (two-layer) film 8. Especially when the molten resin is extruded at a high speed, the resin containing the coloring component at the extrusion temperature is melted. When the tension is less than 0.5 g, or the melt tension of the resin containing no coloring component is less than 1 g, the extruded film-like molten resin pulsates and the longitudinal thickness becomes nonuniform or the width direction Ears are generated. Using a resin having a color component containing a melt tension Tm of 0.5 g ≦ Tm <1.0 g, the melt tension of 0.5 g ≦ Tm <1.0 g is applied to the total thickness of the extruded multilayer film. A resin layer having a resin layer having a melt tension of 0.5 g ≦ Tm <1.0 g is used with respect to the total thickness of the extruded multilayer film. Use a resin with a melt tension of 1 g or more so that the resin does not contain a coloring component so that the melt tension is 1 g or more with respect to the total thickness of the extruded multilayer film. By controlling the amount of extrusion so that the thickness becomes one third or more, the occurrence of pulsation and ears can be prevented. Therefore, the film can be formed at a higher speed.

以上のようにして、溶融粘度の差を調整し、樹脂の少なくともいずれか1種に着色成分を含有した樹脂を用いて吐出量を調整した後、吐出口7から冷却ロール9上に吐出されて固化した多層(2層)フィルム8は、巻取手段12に巻き取られる。このようにして本発明の多層樹脂フィルムが製造される。   As described above, after adjusting the difference in melt viscosity and adjusting the discharge amount using a resin containing a coloring component in at least one of the resins, the resin is discharged from the discharge port 7 onto the cooling roll 9. The solidified multilayer (two-layer) film 8 is wound around the winding means 12. In this way, the multilayer resin film of the present invention is produced.

上記のようにして得られる本発明の多層樹脂フィルムは、多層樹脂フィルム表面における凹凸の差が5μm以下であることが好ましい。凹凸の差が5μmを超えると目視的に不良であるばかりでなく、多層樹脂フィルムを金属板に積層被覆して多層樹脂フィルム被覆金属板とした後、この多層樹脂フィルム被覆金属板を缶体に成形するために絞り加工や絞りしごき加工を実施したり、缶上部の開口部のネックイン加工を実施する際に樹脂フィルムが金属板から剥離したり、加工度が局所的に異なるために、絞り加工や絞りしごき加工において破胴したり、ネックイン加工においてクラッシュしたりして缶体に成形加工できない。   The multilayer resin film of the present invention obtained as described above preferably has a difference in unevenness on the surface of the multilayer resin film of 5 μm or less. When the unevenness difference exceeds 5 μm, it is not only visually inferior, but also after the multilayer resin film is laminated and coated on a metal plate to form a multilayer resin film-coated metal plate, the multilayer resin film-coated metal plate is applied to a can body. Drawing or ironing to form, or the resin film peels off from the metal plate when performing neck-in processing of the opening at the top of the can. Can not be formed into a can body due to breaking in processing and drawing ironing and crashing in neck-in processing.

また、本発明の多層樹脂フィルムは、上記の多層樹脂フィルムの製造方法を用いてダイリップの吐出部から加熱溶融した多層樹脂を、直接金属板にフィルム状に吐出して積層被覆して多層樹脂フィルム被覆金属板とすることができる。また、上記の多層樹脂フィルムの製造方法を用いて作成した多層樹脂フィルムを公知の積層方法を用いて、金属板に直接、または接着剤を介して積層して多層樹脂フィルム被覆金属板とすることもできる。なお、加熱溶融した多層樹脂を、直接金属板にフィルム状に吐出して積層被覆する場合、積層被覆後の多層樹脂フィルムの表面における凹凸の差は、上記と同様の理由で5μm以下であることが好ましい。
なお、以上の説明においては2種類の樹脂を用いる2層の樹脂フィルムを製膜する場合を説明したが、マニフォルド3個以上を設けたマルチマニフォルドダイとそれぞれのマニフォルドに接続して押出機を3個以上設けることにより、3層以上の樹脂フィルムを製膜可能であることはいうまでもない。
Further, the multilayer resin film of the present invention is a multilayer resin film in which the multilayer resin heated and melted from the discharge part of the die lip using the above-described method for producing a multilayer resin film is directly discharged onto a metal plate in a film form and coated. It can be a coated metal plate. In addition, a multilayer resin film prepared using the above-described multilayer resin film production method is laminated on a metal plate directly or via an adhesive to form a multilayer resin film-coated metal plate using a known lamination method. You can also. In addition, when the multilayer resin melted by heating is directly discharged onto a metal plate in the form of a film, the difference in unevenness on the surface of the multilayer resin film after the layer coating is 5 μm or less for the same reason as described above. Is preferred.
In the above description, the case where a two-layer resin film using two kinds of resins is formed has been described. However, a multi-manifold die provided with three or more manifolds and an extruder 3 connected to each manifold. Needless to say, it is possible to form a resin film having three or more layers by providing more than one.

以下、実施例を示し、本発明を詳細に説明する。
(比較例1)
耐透過性に優れたポリエステル樹脂A(エチレンテレフタレート/エチレンイソフタレート共重合体(エチレンイソフタレート10モル%)、融点:220℃、固有粘度:0.85、260℃、剪断速度:100秒−1における溶融粘度:7500ポアズ、溶融張力:0.7g)(以下、簡略に樹脂Aという。溶融張力は、キャピログラフ3A(商品名:東洋精機(株)製)を用い、樹脂温度:260℃、押出速度:10mm/分、巻取速度:10m/分、ノズル径:1mm、ノズル長さ:10mmの条件で測定した)と、加工接着性に優れたポリエステル樹脂B(エチレンテレフタレート/エチレンイソフタレート共重合体(エチレンイソフタレート15モル%)、融点:215℃、固有粘度:0.9、融点:215℃、温度260℃でかつ剪断速度:100秒−1における溶融粘度:9000ポアズ、溶融張力:0.7g)(以下、簡略に樹脂Bという)に着色成分としてTiOを27wt%添加した樹脂(260℃、剪断速度:100秒−1における溶融粘度:4000ポアズ、溶融張力:0.4g)を、それぞれ押出機を用いて樹脂Aを265℃、樹脂B(TiOを27wt%添加)を260℃加熱して溶融させた。次いで、2台の押出機に2個のマニフォルドが樹脂通路を介して連接し、それらのマニフォルドに隣接した個別に温度制御するヒータを設けたマルチマニフォルドダイのそれぞれのマニフォルドに、2層フィルムに製膜した後の樹脂Aの厚さと樹脂Bの厚さの比が1:3であり2層樹脂フィルムの厚さが16μmとなるように吐出量を調整して溶融樹脂Aおよび溶融樹脂Bを導いた。マルチマニフォルドダイの溶融樹脂Aが通る側と溶融樹脂Aが通る樹脂通路およびマニフォルド、およびマルチマニフォルドダイの溶融樹脂Bが通る側と溶融樹脂Bが通る樹脂通路およびマニフォルドはそれぞれに隣接するヒータでいずれも260℃に予め加熱しておき、溶融樹脂Aおよび溶融樹脂Bをそれぞれのマニフォルドを通過させた。この時、Tダイ直前の樹脂温度と剪断速度100秒−1における樹脂粘度は、樹脂A:265℃、約6500ポアズ、樹脂B+TiO:260℃、4000ポアズである。このようにして溶融樹脂Aと溶融樹脂Bを加熱した後、溶融樹脂Aと溶融樹脂Bをマニフォルドの合体部で合体させて積層し、マニフォルドの合体点からリップランドを経て70m/分の速度で吐出口から2層樹脂として吐出したところ、吐出樹脂は、耳揺れと脈動が発生し、長手方向の膜厚精度が7μm以上となった。吐出した後、吐出口の下方に設けた内部に水を循環させた冷却ロールに落下させて冷却固化し、幅約1mの2層樹脂フィルムとしてコイラーに巻き取った。
EXAMPLES Hereinafter, an Example is shown and this invention is demonstrated in detail.
(Comparative Example 1)
Polyester resin A (ethylene terephthalate / ethylene isophthalate copolymer (10 mol% ethylene isophthalate) excellent in permeation resistance, melting point: 220 ° C., intrinsic viscosity: 0.85, 260 ° C., shear rate: 100 sec −1 Melt viscosity: 7500 poise, melt tension: 0.7 g (hereinafter simply referred to as Resin A. Melt tension is Capillograph 3A (trade name: manufactured by Toyo Seiki Co., Ltd.), resin temperature: 260 ° C., extrusion Speed: 10 mm / min, winding speed: 10 m / min, nozzle diameter: 1 mm, nozzle length: measured at 10 mm) and polyester resin B (ethylene terephthalate / ethylene isophthalate copolymer) excellent in work adhesion Coalescence (ethylene isophthalate 15 mol%), melting point: 215 ° C, intrinsic viscosity: 0.9, melting point: 215 ° C, temperature 260 ° C Melt viscosity at 100 sec -1: shear rate 9000 poises, melt tension: 0.7 g) (hereinafter, briefly resin TiO 2 as coloring component in) that the resin B was added 27 wt% (260 ° C., shear rate: 100 The melt viscosity at second −1 : 4000 poise and melt tension: 0.4 g) were melted by heating Resin A at 265 ° C. and Resin B (27 wt% of TiO 2 added) at 260 ° C. using an extruder, respectively. . Next, two manifolds are connected to the two extruders via resin passages, and two-layer film is produced on each manifold of the multi-manifold die provided with heaters for individually controlling the temperature adjacent to the manifolds. The molten resin A and the molten resin B are led by adjusting the discharge amount so that the ratio of the thickness of the resin A and the thickness of the resin B after the film formation is 1: 3 and the thickness of the two-layer resin film is 16 μm. It was. The side of the multi-manifold die through which the molten resin A passes and the resin passage and manifold through which the molten resin A passes, and the side of the multi-manifold die through which the molten resin B passes and the resin passage through which the molten resin B passes and the manifold are respectively adjacent to the heater. Was previously heated to 260 ° C., and the molten resin A and the molten resin B were passed through the respective manifolds. At this time, the resin temperature immediately before the T-die and the resin viscosity at a shear rate of 100 seconds −1 are resin A: 265 ° C., about 6500 poise, and resin B + TiO 2 : 260 ° C., 4000 poise. After the molten resin A and the molten resin B are heated in this way, the molten resin A and the molten resin B are united and laminated at the united portion of the manifold, and at a speed of 70 m / min through the lip land from the united point of the manifold. When the two-layer resin was discharged from the discharge port, the discharge resin generated ear shaking and pulsation, and the film thickness accuracy in the longitudinal direction became 7 μm or more. After discharging, it was dropped on a cooling roll in which water was circulated inside the discharge port and solidified by cooling, and wound around a coiler as a two-layer resin film having a width of about 1 m.

(実施例1)
上記樹脂Aと、ポリエステル樹脂C(エチレンテレフタレート/エチレンイソフタレート共重合体(エチレンイソフタレート15モル%)をトリメリット酸(0.3モル%)で変性したもの、融点:215℃、固有粘度:0.8、温度260℃でかつ剪断速度:100秒−1における溶融粘度:8000ポアズ、溶融張力:1.2g)(以下、簡略に樹脂Cという)に、着色成分としてTiOを27wt%添加した樹脂(260℃、剪断速度:100秒−1における溶融粘度:4500ポアズ、溶融張力:0.65g)を、それぞれ押出機を用いて樹脂Aを265℃、樹脂C(TiOを27wt%添加)を260℃加熱して溶融させた。次いで、2台の押出機に2個のマニフォルドが樹脂通路を介して連接し、それらのマニフォルドに隣接した個別に温度制御するヒータを設けたマルチマニフォルドダイのそれぞれのマニフォルドに、2層フィルムに製膜した後の樹脂Aの厚さと樹脂C(TiOを27wt%含む)の厚さの比が1:3であり2層樹脂フィルムの厚さが16μmとなるように吐出量を調整して溶融樹脂Aおよび溶融樹脂Cを導いた。マルチマニフォルドダイの溶融樹脂Aが通る側と溶融樹脂Aが通る樹脂通路およびマニフォルドはそれに隣接するヒータで260℃に、マルチマニフォルドダイの溶融樹脂Aが通る側と溶融樹脂Cが通る樹脂通路およびマニフォルドはそれぞれに隣接するヒータで250℃に予め加熱しておき、溶融樹脂Aおよび溶融樹脂Cをそれぞれのマニフォルドを通過させた。この時、Tダイ直前の樹脂温度と剪断速度100秒−1における樹脂粘度は、樹脂A:265℃、約6500ポアズ、樹脂C+TiO:250℃、約5000ポアズである。このようにして溶融樹脂Aと溶融樹脂Cを加熱した後、溶融樹脂Aと溶融樹脂Cをマニフォルドの合体部で合体させて積層し、マニフォルドの合体点からリップランドを経て100m/分の速度で吐出口から2層樹脂として吐出したところ、吐出樹脂は脈動せず、フィルムの幅方向に耳は生じなかった。吐出した後、吐出口の下方に設けた内部に水を循環させた冷却ロールに落下させて冷却固化し、幅約1mの2層樹脂フィルムとしてコイラーに巻き取った。
Example 1
Resin A and polyester resin C (ethylene terephthalate / ethylene isophthalate copolymer (15 mol% ethylene isophthalate) modified with trimellitic acid (0.3 mol%), melting point: 215 ° C., intrinsic viscosity: 0.8 wt. Temperature, 260 ° C. and shear rate: 100 sec- 1 melt viscosity: 8000 poise, melt tension: 1.2 g) (hereinafter simply referred to as “resin C”) 27 wt% of TiO 2 added as a coloring component The resin (260 ° C., shear rate: 100 seconds −1 melt viscosity: 4500 poise, melt tension: 0.65 g) was added to resin A at 265 ° C. and resin C (TiO 2 at 27 wt%, respectively) using an extruder. ) Was heated to 260 ° C. and melted. Next, two manifolds are connected to the two extruders via resin passages, and two-layer film is produced on each manifold of the multi-manifold die provided with heaters for individually controlling the temperature adjacent to the manifolds. After the film is formed, the ratio of the thickness of the resin A to the thickness of the resin C (containing 27 wt% of TiO 2 ) is 1: 3, and the discharge amount is adjusted so that the thickness of the two-layer resin film is 16 μm. Resin A and molten resin C were led. The side of the multi-manifold die through which the molten resin A passes and the resin passage and manifold through which the molten resin A pass are heated to 260 ° C. by the heater adjacent to the side, and the side of the multi-manifold die through which the molten resin A passes and the resin passage through which the molten resin C passes. Were preheated to 250 ° C. with heaters adjacent to each, and the molten resin A and the molten resin C were passed through the respective manifolds. At this time, the resin temperature immediately before the T-die and the resin viscosity at a shear rate of 100 seconds −1 are resin A: 265 ° C., about 6500 poise, and resin C + TiO 2 : 250 ° C., about 5000 poise. In this way, after the molten resin A and the molten resin C are heated, the molten resin A and the molten resin C are combined and laminated at the united portion of the manifold, and at a speed of 100 m / min through the lip land from the united point of the manifold. When the two-layer resin was discharged from the discharge port, the discharge resin did not pulsate and no ears were generated in the width direction of the film. After discharging, it was dropped on a cooling roll in which water was circulated inside the discharge port and solidified by cooling, and wound around a coiler as a two-layer resin film having a width of about 1 m.

(実施例2)
上記樹脂Bに、着色成分としてTiOを27wt%添加した樹脂(260℃、剪断速度:100秒−1における溶融粘度:4000ポアズ、溶融張力:0.4g)と樹脂Cを、それぞれ押出機を用いて樹脂B(TiOを27wt%添加)を260℃、樹脂Cを270℃加熱して溶融させた。次いで、2台の押出機に2個のマニフォルドが樹脂通路を介して連接し、それらのマニフォルドに隣接した個別に温度制御するヒータを設けたマルチマニフォルドダイのそれぞれのマニフォルドに、2層フィルムに製膜した後の樹脂Cの厚さと樹脂B(TiOを27wt%含む)の厚さの比が1:2であり2層樹脂フィルムの厚さが16μmとなるように吐出量を調整して溶融樹脂Cおよび溶融樹脂Bを導いた。マルチマニフォルドダイの溶融樹脂Cが通る側と溶融樹脂Bが通る樹脂通路およびマニフォルドはそれに隣接するヒータで260℃に、マルチマニフォルドダイの溶融樹脂Cが通る側と溶融樹脂Bが通る樹脂通路およびマニフォルドはそれぞれに隣接するヒータで260℃に予め加熱しておき、溶融樹脂Cおよび溶融樹脂Bをそれぞれのマニフォルドを通過させた。この時、Tダイ直前の樹脂温度と剪断速度100秒−1における樹脂粘度は、樹脂C:268℃、約6300ポアズ、樹脂B+TiO:260℃、約4000ポアズである。このようにして溶融樹脂Cと溶融樹脂Bを加熱した後、溶融樹脂Cと溶融樹脂Bをマニフォルドの合体部で合体させて積層し、マニフォルドの合体点からリップランドを経て100m/分の速度で吐出口から2層樹脂として吐出したところ、吐出樹脂は脈動せず、フィルムの幅方向に耳は生じなかった。吐出した後、吐出口の下方に設けた内部に水を循環させた冷却ロールに落下させて冷却固化し、幅約1mの2層樹脂フィルムとしてコイラーに巻き取った。
(Example 2)
Resin B with 27% by weight of TiO 2 added as a coloring component (260 ° C., shear rate: 100 ps- 1 melt viscosity: 4000 poise, melt tension: 0.4 g) and resin C, respectively, Resin B (27 wt% of TiO 2 added) was heated at 260 ° C. and Resin C was heated at 270 ° C. to be melted. Next, two manifolds are connected to the two extruders via resin passages, and two-layer film is produced on each manifold of the multi-manifold die provided with heaters for individually controlling the temperature adjacent to the manifolds. After the film is formed, the ratio of the thickness of the resin C to the thickness of the resin B (containing 27 wt% of TiO 2 ) is 1: 2, and the discharge amount is adjusted so that the thickness of the two-layer resin film is 16 μm. Resin C and molten resin B were led. The resin passage and manifold through which the molten resin C of the multi-manifold die passes and the resin passage and manifold through which the molten resin B pass are heated to 260 ° C. by the heater adjacent thereto, and the resin passage and manifold through which the molten resin C passes through the side of the multi-manifold die. Were preheated to 260 ° C. with heaters adjacent to each, and the molten resin C and the molten resin B were passed through the respective manifolds. At this time, the resin temperature immediately before the T-die and the resin viscosity at a shear rate of 100 seconds −1 are resin C: 268 ° C., about 6300 poise, and resin B + TiO 2 : 260 ° C., about 4000 poise. After the molten resin C and the molten resin B are heated in this way, the molten resin C and the molten resin B are united and laminated at the united portion of the manifold, and at a speed of 100 m / min through the lip land from the united point of the manifold. When the two-layer resin was discharged from the discharge port, the discharge resin did not pulsate, and no ears were generated in the width direction of the film. After discharging, it was dropped on a cooling roll in which water was circulated inside the discharge port and solidified by cooling, and wound around a coiler as a two-layer resin film having a width of about 1 m.

[特性評価]
上記のようにして作成した実施例1〜2、比較例1の樹脂フィルムの特性を、下記のように評価した。
<厚みムラ>
実施例1〜2、比較例1の樹脂フィルムを、製膜開始5分後の樹脂フィルムの長手方向の15mの部分で1m毎(16箇所)に全幅方向(約1m)の厚さを連続測定し、長さ方向16箇所の全幅方向で測定した全ての測定値の最大厚さと最小厚さの差を厚みムラとして求めた。
評価結果を表1に示す。
[Characteristic evaluation]
The characteristics of the resin films of Examples 1-2 and Comparative Example 1 prepared as described above were evaluated as follows.
<Thickness unevenness>
For the resin films of Examples 1 and 2 and Comparative Example 1, the thickness in the full width direction (about 1 m) was continuously measured every 1 m (16 places) at the 15 m portion in the longitudinal direction of the resin film 5 minutes after the start of film formation. And the difference of the maximum thickness of all the measured values measured in the full width direction of 16 length directions and the minimum thickness was calculated | required as thickness nonuniformity.
The evaluation results are shown in Table 1.

Figure 2009149109
Figure 2009149109

表1に示すように、少なくとも1種類の着色成分を含んだフィルムの着色成分を含有した樹脂の溶融張力:Tmが0.5g≦Tm<1.0gでかつ厚さが全厚さの2分の1以上、あるいはTm≧1.0gでかつ厚さが全厚さの3分の1以上であるか、または着色成分を含まないフィルムの溶融張力が1g以上で、かつ、厚さが全厚さの3分の1以上である多層樹脂フィルムを製膜した場合は、高速度で製膜しても脈動や耳発生が増大することがなく、得られた樹脂フィルムの厚みムラは極めて小さい。   As shown in Table 1, the melt tension of the resin containing the coloring component of the film including at least one coloring component: Tm is 0.5 g ≦ Tm <1.0 g and the thickness is 2 minutes. 1 or more, or Tm ≧ 1.0 g and the thickness is 1/3 or more of the total thickness, or the melt tension of the film containing no coloring component is 1 g or more and the thickness is the total thickness. When a multilayer resin film having a thickness of 1/3 or more is formed, even if the film is formed at a high speed, pulsation and ear generation do not increase, and the thickness unevenness of the obtained resin film is extremely small.

本発明の多層樹脂フィルムを金属板に積層してなる樹脂被覆金属板は、絞り缶や絞りしごき缶への成形に適しており、絞り加工や絞りしごき加工を実施したり、缶上部の開口部のネックイン加工を実施しても、樹脂フィルムが金属板から剥離することがなく、また局所的に加工度が異なる部位がないので、絞り加工や絞りしごき加工において破胴したり、ネックイン加工においてクラッシュしたりすることがなく、安定して缶体に成形加工することができる。   The resin-coated metal plate obtained by laminating the multilayer resin film of the present invention on a metal plate is suitable for forming into a drawn can and a drawn and ironed can. Even if the neck-in processing is performed, the resin film does not peel from the metal plate, and there are no parts with locally different processing degrees. Can be stably formed into a can without crashing.

Claims (7)

少なくとも着色成分を含有するポリエステル樹脂及び着色成分を含有しないポリエステル樹脂から構成される多層樹脂フィルムにおいて、前記着色成分を含有しないポリエステル樹脂が、押出温度における溶融張力Tmが1.0g≦Tmであり、且つ該着色成分を含有しないポリエステル樹脂から成るフィルムの厚さが全厚さの3分の1以上であることを特徴とする無延伸の多層樹脂フィルム。 In a multilayer resin film composed of a polyester resin containing at least a coloring component and a polyester resin not containing a coloring component, the polyester resin not containing the coloring component has a melt tension Tm at an extrusion temperature of 1.0 g ≦ Tm, An unstretched multilayer resin film, wherein the thickness of the film made of a polyester resin not containing the coloring component is at least one third of the total thickness . 長さ方向の全幅方向で測定した最大厚さと最小厚さの差で表わされる厚みムラが、5.0μm以下であることを特徴とする、請求項1記載の多層樹脂フィルム。 The multilayer resin film according to claim 1 , wherein the thickness unevenness represented by the difference between the maximum thickness and the minimum thickness measured in the full width direction in the length direction is 5.0 µm or less. 請求項1又は2記載の多層樹脂フィルムを金属板に積層してなる樹脂被覆金属板。   A resin-coated metal plate obtained by laminating the multilayer resin film according to claim 1 or 2 on a metal plate. 押出温度における溶融張力Tmが1.0g≦Tmである着色成分を含有しないポリエステル樹脂及び着色成分を含有するポリエステル樹脂を少なくとも含む、2種類以上のポリエステル樹脂を、マルチマニフォルドダイを用いて、それぞれのマニフォルドに連続して設けられた押出機、それぞれのマニフォルド、およびそれぞれのマニフォルドに隣接するダイの部分のそれぞれの温度を制御し、溶融粘度の高い樹脂が通る押出機、マニフォルド、およびマニフォルドに隣接するダイの部分の温度を、溶融粘度の低い樹脂が通る押出機、マニフォルド、およびマニフォルドに隣接するダイの部分の温度より高温に保持して、着色成分を含有しないポリエステル樹脂から成るフィルムの厚さが全厚さの3分の1以上となるようにして、それぞれの溶融樹脂を積層して多層フィルムとすることを特徴とする、多層樹脂フィルムの製造方法。 Two or more kinds of polyester resins including at least a polyester resin not containing a coloring component and a polyester resin containing a coloring component having a melt tension Tm of 1.0 g ≦ Tm at an extrusion temperature are obtained using a multi-manifold die. Adjacent to the extruder, manifold, and manifold through which the high melt melt resin passes, controlling the temperature of each extruder continuously provided in the manifold, each manifold, and the portion of the die adjacent to each manifold The temperature of the die part is kept higher than the temperature of the extruder, manifold, and die part adjacent to the manifold through which the low-viscosity resin passes, so that the thickness of the film made of polyester resin containing no coloring component is increased. Each thickness should be at least one third of the total thickness. A method for producing a multilayer resin film, comprising laminating a molten resin to form a multilayer film. 隣接する樹脂層の溶融粘度の差が、20〜500秒Difference in melt viscosity between adjacent resin layers is 20 to 500 seconds −1-1 の剪断速度において3000ポアズ以下となるように、温度制御することを特徴とする請求項4記載の多層樹脂フィルムの製造方法。The method for producing a multilayer resin film according to claim 4, wherein the temperature is controlled so that the shear rate is 3000 poise or less. 押出温度における溶融張力Tmが1.0g≦Tmである着色成分を含有しないポリエステル樹脂及び着色成分を含有するポリエステル樹脂を少なくとも含む、2種類以上のポリエステル樹脂を、マルチマニフォルドダイを用いて、それぞれのマニフォルドに連続して設けられた押出機、それぞれのマニフォルド、およびそれぞれのマニフォルドに隣接するダイの部分のそれぞれの温度を制御し、溶融粘度の高い樹脂が通る押出機、マニフォルド、およびマニフォルドに隣接するダイの部分の温度を、溶融粘度の低い樹脂が通る押出機、マニフォルド、およびマニフォルドに隣接するダイの部分の温度より高温に保持して、着色成分を含有しないポリエステル樹脂から成るフィルムの厚さが全厚さの3分の1以上となるようにして、それぞれの溶融樹脂を積層して多層化した後、金属板上に押出すことを特徴とする、樹脂被覆金属板の製造方法。 Two or more kinds of polyester resins including at least a polyester resin not containing a coloring component and a polyester resin containing a coloring component having a melt tension Tm of 1.0 g ≦ Tm at an extrusion temperature are obtained using a multi-manifold die. Adjacent to the extruder, manifold, and manifold through which the high melt melt resin passes, controlling the temperature of each extruder continuously provided in the manifold, each manifold, and the portion of the die adjacent to each manifold The temperature of the die part is kept higher than the temperature of the extruder, manifold, and die part adjacent to the manifold through which the low-viscosity resin passes, so that the thickness of the film made of polyester resin containing no coloring component is increased. Each thickness should be at least one third of the total thickness. A method for producing a resin-coated metal plate, comprising: laminating a molten resin to form a multilayer, and then extruding the molten resin onto a metal plate. 隣接する樹脂層の溶融粘度の差が、20〜500秒Difference in melt viscosity between adjacent resin layers is 20 to 500 seconds −1-1 の剪断速度において3000ポアズ以下となるように、温度制御することを特徴とする請求項6記載の樹脂被覆金属板の製造方法。The method for producing a resin-coated metal sheet according to claim 6, wherein the temperature is controlled so that the shear rate is 3000 poise or less.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54124067A (en) * 1978-03-20 1979-09-26 Mitsubishi Heavy Ind Ltd Extrusion die
JPS63120629A (en) * 1986-11-11 1988-05-25 Toray Ind Inc Composite extrusion die
JPH1086308A (en) * 1996-07-22 1998-04-07 Kishimoto Akira Laminate and container using it
JP2000127227A (en) * 1998-10-29 2000-05-09 Teijin Ltd Film extrusion device and manufacture of film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54124067A (en) * 1978-03-20 1979-09-26 Mitsubishi Heavy Ind Ltd Extrusion die
JPS63120629A (en) * 1986-11-11 1988-05-25 Toray Ind Inc Composite extrusion die
JPH1086308A (en) * 1996-07-22 1998-04-07 Kishimoto Akira Laminate and container using it
JP2000127227A (en) * 1998-10-29 2000-05-09 Teijin Ltd Film extrusion device and manufacture of film

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