JP4226407B2 - Metal plate laminated with fluororesin thin film and method for manufacturing the same - Google Patents
Metal plate laminated with fluororesin thin film and method for manufacturing the same Download PDFInfo
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Description
本発明はフッ素樹脂フィルムが積層された金属板に関し、該フッ素樹脂フィルムが薄肉であり、且つ、その上に該フッ素樹脂フィルムと剥離可能なフィルムが積層された金属板及びその製造方法に関する。 The present invention relates to a metal plate on which a fluororesin film is laminated, and relates to a metal plate on which the fluororesin film is thin and on which a film that can be peeled off from the fluororesin film is laminated, and a method for producing the metal plate.
金属板の表面に、防汚性、耐候性、離型性等の性能を付与するために、又、エレクトレット用の樹脂皮膜を形成するために、該金属板表面上にフッ素樹脂フィルムをラミネートすることが知られている（例えば特許文献１〜３）。該ラミネートはフッ素樹脂フィルムを、所定の接着剤層を介して加熱しながら又は加熱無しに圧着して金属板上に貼り合わせることにより行われる。 In order to impart antifouling properties, weather resistance, releasability, etc. to the surface of the metal plate, and to form a resin film for electrets, a fluororesin film is laminated on the surface of the metal plate. It is known (for example, Patent Documents 1 to 3). The laminating is performed by bonding a fluororesin film onto a metal plate by pressing through a predetermined adhesive layer with or without heating.
フッ素樹脂は高価であるので、フッ素樹脂フィルムは前記各性能を付与するために必要最低限の厚みを有することが好ましい。しかし、フッ素樹脂フィルムは腰が無いために、例えば１０μｍ以下の薄いフィルムをラミネートしようとすると、しわ入りや破断が起こる場合がある。特許文献１には、フッ素樹脂フィルムの厚さは１０〜２００μｍの範囲で選択されることが好ましいとあるが（特許文献１、段落００１３）、使用されているフッ素樹脂フィルムの厚みは３０μｍである（特許文献１、段落００１７）。また、特許文献２及び３においても４０μｍ以上のフッ素樹脂フィルムが使用されている（特許文献２段落００３９、特許文献３段落００５０）。 Since the fluororesin is expensive, it is preferable that the fluororesin film has a minimum thickness necessary for imparting each performance. However, since the fluororesin film has no elasticity, for example, when a thin film having a thickness of 10 μm or less is to be laminated, wrinkling or breaking may occur. According to Patent Document 1, the thickness of the fluororesin film is preferably selected in the range of 10 to 200 μm (Patent Document 1, paragraph 0013), but the thickness of the fluororesin film used is 30 μm. (Patent Document 1, paragraph 0017). Also in Patent Documents 2 and 3, a fluororesin film of 40 μm or more is used (Patent Document 2, paragraph 0039, Patent Document 3, paragraph 0050).
そこで、本発明は、１０μｍ以下の厚みのフッ素樹脂フィルムが積層されてなる金属板を提供することを目的とする。また、本発明は、１０μｍ以下の厚みであっても皺入り等の問題が無く金属上に積層することができる方法を提供することを目的とする。 Then, an object of this invention is to provide the metal plate by which the fluororesin film of thickness of 10 micrometers or less is laminated | stacked. Another object of the present invention is to provide a method that can be laminated on a metal without a problem of wrinkles even if the thickness is 10 μm or less.
すなわち、本発明は、金属板の少なくとも片面上にフッ素樹脂フィルムが積層されてなる金属板において、該フッ素樹脂フィルムの厚みが２〜１０μmであり且つ該フッ素樹脂がテトラフロロエチレン−ヘキサフロロプロピレン共重合体、テトラフロロエチレン−パーフロロアルキルビニルエーテル共重合体、テトラフロロエチレン−エチレン共重合体、ポリフッ化ビニリデン、ポリクロロトリフルオロエチレン、トリフロロエチレン−エチレン共重合体、ポリテトラフロロジオキソールコポリマー及びポリフッ化ビニルからなる群より選ばれる少なくとも１種であり、該フッ素樹脂フィルム上に、ポリエチレン、ポリプロピレン、及び、ポリエステルからなる群より選ばれる少なくとも１種の樹脂からなるフィルムが剥離可能に積層されてなることを特徴とするフッ素樹脂フィルム積層金属板である。
また、本発明は、（１）厚みが２〜１０μmのフッ素樹脂フィルム上に、該フッ素樹脂フィルムと剥離可能なフィルムが積層されてなる積層フィルムを形成する工程、
（２）該積層フィルムのフッ素樹脂フィルム側と、金属板の少なくとも片面とを熱圧着する工程、
を含むことを特徴とするフッ素樹脂フィルム積層金属板の製造方法である。
好ましくは、フッ素樹脂が、テトラフロロエチレン−ヘキサフロロプロピレン共重合体、テトラフロロエチレン−パーフロロアルキルビニルエーテル共重合体、テトラフロロエチレン−エチレン共重合体、ポリフッ化ビニリデン、ポリクロロトリフルオロエチレン、トリフロロエチレン−エチレン共重合体、ポリテトラフロロジオキソールコポリマー及びポリフッ化ビニルからなる群より選ばれる少なくとも１種である。
好ましくは、フッ素樹脂フィルムと剥離可能なフィルムが、ポリエチレン、ポリプロピレン、及び、ポリエステルからなる群より選ばれる少なくとも１種の樹脂からなる。
好ましくは、金属板が、アルミニウム又はアルミニウム合金からなる。
上記方法における工程（１）は、該フッ素樹脂フィルムと該剥離可能なフィルムとを、ドライラミネート、押出しラミネートまたは共押出しすることにより行われてよい。
また、工程（２）における熱圧着は、[フッ素樹脂の融解開始温度（℃）−５０℃]以上の温度であって該フッ素樹脂の熱分解温度未満の温度で行われること、及び、フッ素樹脂積層フィルムと金属板とを１対のロールの間に挿入して挟圧することにより連続的に行われることが好ましい。
上記工程に加え、（３）[フッ素樹脂の融解開始温度（℃）−５０℃]以上の温度であって該フッ素樹脂の熱分解温度未満の温度で再加熱する工程、を含むことが好ましい。
That is, the present invention relates to a metal plate in which a fluororesin film is laminated on at least one surface of the metal plate, the fluororesin film has a thickness of 2 to 10 μm, and the fluororesin is a copolymer of tetrafluoroethylene-hexafluoropropylene. Polymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, trifluoroethylene-ethylene copolymer, polytetrafluorodioxole copolymer And a film made of at least one resin selected from the group consisting of polyethylene, polypropylene, and polyester is releasably laminated on the fluororesin film. Tena It is a fluorine resin film laminated metal sheet according to claim.
The present invention also includes (1) a step of forming a laminated film in which a film that can be peeled off from the fluororesin film is laminated on a fluororesin film having a thickness of 2 to 10 μm,
(2) a step of thermocompression bonding the fluororesin film side of the laminated film and at least one surface of the metal plate;
It is a manufacturing method of the fluororesin film laminated metal plate characterized by including.
Preferably, the fluororesin is a tetrafluoroethylene-hexafluoropropylene copolymer, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, a tetrafluoroethylene-ethylene copolymer, a polyvinylidene fluoride, a polychlorotrifluoroethylene, It is at least one selected from the group consisting of a fluoroethylene-ethylene copolymer, a polytetrafluorodioxol copolymer, and polyvinyl fluoride.
Preferably, the film peelable from the fluororesin film is made of at least one resin selected from the group consisting of polyethylene, polypropylene, and polyester.
Preferably, the metal plate is made of aluminum or an aluminum alloy.
Step (1) in the above method may be performed by dry-laminating, extrusion-laminating or co-extrusion of the fluororesin film and the peelable film.
In addition, the thermocompression bonding in the step (2) is performed at a temperature equal to or higher than [melting start temperature of fluororesin (° C.) − 50 ° C.] and lower than the thermal decomposition temperature of the fluororesin, and fluororesin It is preferable that the lamination film and the metal plate are continuously formed by inserting and sandwiching between a pair of rolls.
In addition to the above steps, it is preferable to include a step of (3) reheating at a temperature equal to or higher than [melting start temperature of fluororesin (° C.) − 50 ° C.] and lower than the thermal decomposition temperature of the fluororesin.
上記本発明によれば、フッ素樹脂フィルムと剥離可能なフィルムがフッ素樹脂フィルムの支持体として作用するので、厚み１０μm以下の薄肉フッ素樹脂フィルムであっても皺入り等が無く金属板上に積層することができる。 According to the present invention, since the fluororesin film and the peelable film act as a support for the fluororesin film, even a thin fluororesin film having a thickness of 10 μm or less is laminated on a metal plate without wrinkles or the like. be able to.
本発明で使用される、金属製の板としては、例えば各種めっき鋼、ステンレス、アルミニウム、銅、チタン、及びそれらの合金からなる板が使用できる。好ましくは、アルミニウム合金が使用される。該板の厚みは特に制限は無いが、ロールにより連続処理する場合には、好ましくは、0.2〜0.4mm、より好ましくは0.25〜0.35mmである。該金属板の表面は、クロメート処理、ジルコニウム処理等の化成処理を施してあってもよい。 As a metal board used by this invention, the board which consists of various plating steel, stainless steel, aluminum, copper, titanium, and those alloys can be used, for example. Preferably, an aluminum alloy is used. The thickness of the plate is not particularly limited, but is preferably 0.2 to 0.4 mm, more preferably 0.25 to 0.35 mm when continuously processed by a roll. The surface of the metal plate may be subjected to chemical conversion treatment such as chromate treatment or zirconium treatment.
フッ素樹脂としては、例えばテトラフロロエチレン（PTFE）、テトラフロロエチレン−パーフロロアルキルビニルエーテル共重合体（PFA）、テトラフロロエチレン−エチレン共重合体（ETFE）、テトラフロロエチレン−ヘキサフロロプロピレン共重合体（FEP）、クロロトリフルオロエチレン（CTFE）、フッ化ビニリデン（VｄF）、トリフルオロエチレン−エチレン共重合体、ポリテトラフロロジオキソールコポリマー、ポリフッ化ビニル等が挙げられる。好ましくは、耐薬品性、耐候性、防汚性、熱的及び電気的特性の点から、FEP又はPFAが使用される。 Examples of the fluororesin include tetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), and tetrafluoroethylene-hexafluoropropylene copolymer. (FEP), chlorotrifluoroethylene (CTFE), vinylidene fluoride (VdF), trifluoroethylene-ethylene copolymer, polytetrafluorodioxol copolymer, polyvinyl fluoride, and the like. Preferably, FEP or PFA is used in terms of chemical resistance, weather resistance, antifouling property, thermal and electrical properties.
該フッ素樹脂フィルムの厚みは、２〜10μm、より好ましくは３〜７μmである。 The thickness of the fluororesin film is 2 to 10 μm, more preferably 3 to 7 μm.
本発明の金属板は、フッ素樹脂フィルムの上に該フッ素樹脂と剥離可能なフィルムが積層されていることを特徴とする。ここで「剥離可能」とは、手で端部を一部剥離してフッ素樹脂フィルムから引き離すことによって容易に剥離することができることを意味する。該フッ素樹脂と剥離可能な樹脂としては、公知の各種フィルムを用いることができる。例えば、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリカーボネート、ポリエステル、ポリアミド、ポリイミド、ポリアセタール、ポリスルフォン、セルロースアセテート等を上げることができる。好ましくは、ポリエチレン、ポリプロピレン、ポリエステルが使用され、特に、２軸延伸ポリエチレンテレフタレートフィルムが、熱的特性、機械的特性、価格などの点から好ましい。 The metal plate of the present invention is characterized in that a film that can be peeled off from the fluororesin is laminated on the fluororesin film. Here, “releasable” means that it can be easily peeled off by partially peeling the end part by hand and pulling it away from the fluororesin film. As the resin that can be peeled off from the fluororesin, various known films can be used. For example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, polyester, polyamide, polyimide, polyacetal, polysulfone, cellulose acetate, and the like can be raised. Preferably, polyethylene, polypropylene, and polyester are used, and in particular, a biaxially stretched polyethylene terephthalate film is preferable from the viewpoint of thermal properties, mechanical properties, cost, and the like.
本発明では、該フッ素樹脂フィルムと該剥離可能なフィルムとが積層されたフィルム（以下、「フッ素系積層フィルム」という）を用意し、該フッ素系積層フィルムを金属板へ積層する。該剥離可能な樹脂フィルムが支持体として作用することによって、フッ素樹脂フィルムが薄くとも、フッ素樹脂フィルムにしわが入る等の問題無く金属板上に積層できる。該フッ素系積層フィルムは、例えば本願出願人による特開平2002-067241号に記載されるようにドライラミネートすることによって作ることができる。また、薄肉のフッ素樹脂を、ポリオレフィン樹脂などと共押出しする、または、転写用フィルムに押出しラミネートによって貼り合せて調製してもよい。 In the present invention, a film in which the fluororesin film and the peelable film are laminated (hereinafter referred to as “fluorinated laminated film”) is prepared, and the fluorine laminated film is laminated on a metal plate. When the peelable resin film acts as a support, even if the fluororesin film is thin, it can be laminated on the metal plate without problems such as wrinkling of the fluororesin film. The fluorine-based laminated film can be produced, for example, by dry lamination as described in Japanese Patent Application Laid-Open No. 2002-067241 by the present applicant. Alternatively, a thin fluororesin may be coextruded with a polyolefin resin or the like, or may be prepared by bonding to a transfer film by extrusion lamination.
該フッ素系積層フィルムにおけるフッ素樹脂と剥離可能な樹脂フィルムの厚さは、５〜300μm、好ましくは25〜100μmである。前記下限値より薄いと、得られるフッ素系積層フィルムの腰が十分でなく本発明の目的が十分に達成できない。一方、前記上限値より厚いと、製造コストや廃棄物が多くなる等の問題がある。 The thickness of the resin film peelable from the fluororesin in the fluorine-based laminated film is 5 to 300 μm, preferably 25 to 100 μm. If it is thinner than the lower limit, the resulting fluorine-based laminated film is not sufficiently elastic and the object of the present invention cannot be achieved sufficiently. On the other hand, when it is thicker than the upper limit, there are problems such as an increase in manufacturing cost and waste.
該剥離可能な樹脂フィルムは、金属板に積層した直後に剥離してもよいが、金属板を使用する直前までそのままにして、フッ素樹脂フィルムの保護フィルムの役割を果たすようにすることが好ましい。 The peelable resin film may be peeled off immediately after being laminated on the metal plate, but it is preferable to leave it as it is until just before using the metal plate to serve as a protective film for the fluororesin film.
該フッ素系積層フィルムを、該フッ素樹脂の[融解開始温度（℃）−５０℃]以上であって該フッ素樹脂の熱分解温度（℃）未満の温度、好ましくは、[融解開始温度（℃）−２０℃]以上且つ[熱分解開始温度（℃）−２０℃]以下の温度で、金属板上に熱圧着する。前記下限値未満の温度であると、熱圧着時に気泡を抱き込み易く均一な接着が得られない。一方、前記上限値を超えると、フッ素樹脂が劣化して接着表面の平滑性が悪くなる。本発明において、融解開始温度及び熱分解開始温度は、DSCにより、１０℃／分で昇温、降温、再昇温実施して測定した。分解温度はTGAにて、10℃／分で昇温して求めた。 The fluorine-based laminated film is at a temperature not lower than the [melting start temperature (° C.) − 50 ° C.] of the fluororesin and lower than the thermal decomposition temperature (° C.) of the fluororesin, preferably [melting start temperature (° C.)]. Thermocompression bonding is performed on the metal plate at a temperature of −20 ° C. or more and [thermal decomposition start temperature (° C.) − 20 ° C.] or less. When the temperature is lower than the lower limit, bubbles are easily entrapped during thermocompression bonding, and uniform adhesion cannot be obtained. On the other hand, when the upper limit is exceeded, the fluororesin is deteriorated and the smoothness of the adhesive surface is deteriorated. In the present invention, the melting start temperature and the thermal decomposition start temperature were measured by DSC, raising, lowering, and raising the temperature at 10 ° C./min. The decomposition temperature was determined by raising the temperature at 10 ° C./min with TGA.
熱圧着の方法は、予め金属板を上記温度範囲に加熱し、該金属板とフッ素系積層フィルムのフッ素樹脂フィルム面を対向させて挟圧する。金属板とフッ素系積層フィルムを１対の加熱されたロールの間に挿入して連続的に挟圧することにより、圧着速度を速くすることが好ましい。加熱ロール上で上記温度に加熱して圧着してもよい。 In the method of thermocompression bonding, the metal plate is heated in advance to the above temperature range, and the metal plate and the fluororesin film surface of the fluorinated laminated film are opposed to each other and pressed. It is preferable to increase the pressure-bonding speed by inserting the metal plate and the fluorine-based laminated film between a pair of heated rolls and continuously pinching them. You may press-fit by heating to the said temperature on a heating roll.
より好ましくは、一旦熱圧着した後に、得られた積層板を熱圧着の温度に再加熱する。これにより、より強固な接着が得られる。再加熱は、熱風ヒーター、赤外ヒーター等のヒーターを備えた加熱炉中を、積層板を通すことによって行うことができる。 More preferably, after thermocompression bonding, the obtained laminate is reheated to the thermocompression bonding temperature. Thereby, stronger adhesion can be obtained. Reheating can be performed by passing the laminate through a heating furnace equipped with a heater such as a hot air heater or an infrared heater.
以下、実施例によって、本発明をより詳細に説明する。
使用フィルム
１）厚み 50μmのポリエチレンテレフタレートフィルム（PET）上に5μmのテトラフロロエチレン−ヘキサフロロプロピレン共重合体（FEP、融解開始温度225℃、分解開始温度400℃）フィルムが積層されたフィルム（フッ素積層フィルム）：三菱樹脂（株）製。
２）テトラフロロエチレン−エチレン共重合体フィルム：三菱樹脂製、厚み５μmのもの。
Hereinafter, the present invention will be described in more detail by way of examples.
Films used 1) Film (fluorine) in which a 5 μm tetrafluoroethylene-hexafluoropropylene copolymer (FEP, melting start temperature 225 ° C., decomposition start temperature 400 ° C.) film is laminated on a 50 μm thick polyethylene terephthalate film (PET) (Laminated film): Made by Mitsubishi Plastics.
2) Tetrafluoroethylene-ethylene copolymer film: Mitsubishi resin, 5 μm thick.
評価方法
（１） フッ素樹脂フィルムの皺の有無：金属板に積層した後のフッ素樹脂フィルムに、皺が顕著に認められたものをC、皺が若干認められたものをB、認められなかったものをAとした。
（２）生産性：引き取り速度１０ｍ／分で熱圧着できたものをA、５ｍ／分以下でなければ圧着できなかったものをBとした。
Evaluation method (1) Presence / absence of wrinkles in fluororesin film: C in the fluororesin film after being laminated on the metal plate, B in which wrinkles were recognized remarkably, B in which some wrinkles were observed were not recognized The thing was A.
(2) Productivity: A that could be thermocompression bonded at a take-up speed of 10 m / min was A, and B that could not be crimped unless it was 5 m / min or less.
表１に示す金属板と、積層フッ素フィルムとを、３７０℃に加熱した金属ロールとゴムロールの間に挿入し、該板が熱圧着時に３００℃程度になるように、１ｍ／分の速度で引き取りながら熱圧着した。 The metal plate shown in Table 1 and the laminated fluorine film are inserted between a metal roll and a rubber roll heated to 370 ° C., and taken up at a speed of 1 m / min so that the plate becomes about 300 ° C. during thermocompression bonding. It was thermocompression bonded.
予め370℃に加熱した表１に示す板を、積層フッ素フィルムと、１対のシリコンゴムロール（各ロール直径１５cm）の間に連続的に挿入し、１0ｍ／分の速度で引き取りながら熱圧着した。その後、得られた積層金属板を310℃の熱風式加熱炉中で連続的に再加熱した。 The plate shown in Table 1 previously heated to 370 ° C. was continuously inserted between the laminated fluorine film and a pair of silicon rubber rolls (each roll diameter 15 cm), and thermocompression bonded while being pulled at a speed of 10 m / min. Thereafter, the obtained laminated metal plate was continuously reheated in a 310 ° C. hot air heating furnace.
比較例１及び２
積層フィルムに代えて、厚みの5μmのETFE単層フィルムを用いたことを除き、実施例１と２と同様に夫々熱圧着を試みた。比較例２ではフィルムが破断して熱圧着できなかった。
Comparative Examples 1 and 2
Thermocompression bonding was attempted in the same manner as in Examples 1 and 2 except that a 5 μm thick ETFE monolayer film was used instead of the laminated film. In Comparative Example 2, the film was broken and thermocompression bonding was not possible.
本発明の金属板は、薄いフッ素樹脂フィルムが積層されているので、フッ素樹脂の防汚性等の性能と、経済性との双方が要求される用途に好適である。 Since the thin fluororesin film is laminated | stacked, the metal plate of this invention is suitable for the use where both performance, such as antifouling property of fluororesin, and economical efficiency are requested | required.
Claims (10)
（２）該積層フィルムのフッ素樹脂フィルム側と、金属板の少なくとも片面とを熱圧着する工程、
を含むことを特徴とするフッ素樹脂フィルム積層金属板の製造方法。 (1) A step of forming a laminated film in which a film that can be peeled off from the fluororesin film is laminated on a fluororesin film having a thickness of 2 to 10 μm,
(2) a step of thermocompression bonding the fluororesin film side of the laminated film and at least one surface of the metal plate;
The manufacturing method of the fluororesin film laminated metal plate characterized by including.
をさらに含むことを特徴とする請求項３〜６のいずれか１項記載の方法。 (3) A step of reheating at a temperature equal to or higher than [melting start temperature of fluororesin (° C.) − 50 ° C.] and lower than the thermal decomposition temperature of the fluororesin,
The method according to claim 3 , further comprising:
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