JPWO2010092942A1 - フッ化ビニリデン系樹脂フィルム - Google Patents
フッ化ビニリデン系樹脂フィルム Download PDFInfo
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Abstract
Description
なお、ここで規定する酸化チタン表面のアルミナ及びシリカの付着量は、蛍光X線(XRF:X-ray fluorescence)法により測定した値であり、以下の発明においても同様である。
本発明においては、表面にアルミナ及びシリカが特定量付着している酸化チタンを、無機顔料として配合しているため、無機顔料の配合量を多くしても、良好な分散性が得られる。また、フッ化ビニリデン樹脂にメタクリル酸エステル樹脂を配合しているため、基材との接着性も良好である。
この樹脂フィルムでは、フッ化ビニリデン樹脂:70〜95質量%及びメタクリル酸エステル樹脂:5〜30質量%からなる樹脂成分100質量部に対して、前記酸化チタンを10〜25質量部、ポリエチレングリコールの脂肪酸エステル及び/又はその誘導体を合計で0.1〜5質量部配合することができる。
本発明においては、表面にアルミナ及びシリカが特定量付着している酸化チタンを、無機顔料として配合しているため、無機顔料の配合量を多くしても、良好な分散性が得られる。また、表面層はフッ化ビニリデン樹脂の配合比が高く、裏面層ではメタクリル酸エステル樹脂の配合比が高いため、耐候性及び耐熱性に加えて、基材との接着性にも優れている。
この樹脂フィルムでは、表面層及び裏面層のうち少なくとも一方が、フッ化ビニリデン樹脂及びメタクリル酸エステル樹脂からなる樹脂成分100質量部に対して、前記酸化チタンを10〜25質量部、ポリエチレングリコールの脂肪酸エステル及び/又はその誘導体を合計で0.1〜5質量部含有していてもよい。
また、前記酸化チタンにおけるアルミナ及びシリカの総付着量は、6〜10質量%であることが好ましい。
更に、前記酸化チタンにおけるアルミナ及びシリカの付着量は、それぞれ2.5質量%以上であることが好ましい。
先ず、本発明の第1の実施形態に係るフッ化ビニリデン系樹脂フィルム(以下、単に樹脂フィルムともいう。)について説明する。本実施形態の樹脂フィルムは、少なくとも、フッ化ビニリデン樹脂及びメタクリル酸エステル樹脂からなる樹脂成分と、酸化チタンと、ポリエチレングリコールの脂肪酸エステル及び/又はその誘導体とを含有している。
フッ化ビニリデン樹脂は、耐候性及び耐熱性に優れており、本実施形態の樹脂フィルムの主成分である。本実施形態の樹脂フィルムに配合されるフッ化ビニリデン樹脂は、フッ化ビニリデン単量体単位を有するビニル化合物であれば、その構造などは特に限定されるものではなく、フッ化ビニリデンの単独重合体でもよく、フッ化ビニリデンと他のビニル化合物単量体の共重合体であってもよい。
メタクリル酸エステル樹脂は、フッ化ビニリデン樹脂と共に樹脂成分を構成するものであり、基材などとの接着性を改善する効果がある。フッ化ビニリデン樹脂は他の素材との接着性に劣るが、このメタクリル酸エステル樹脂を配合することにより、高価な接着剤を使用しなくても、基材などに接着することが可能となる。
本実施形態の樹脂フィルムにおける樹脂成分は、前述したフッ化ビニリデン樹脂及びメタクリル酸エステル樹脂からなり、その配合比は、質量比で、フッ化ビニリデン樹脂:メタクリル酸エステル樹脂=70:30〜95:5であることが望ましい。なお、メタクリル酸エステル樹脂の配合量が少なく、樹脂成分全質量あたりのフッ化ビニリデン樹脂量が95質量%を超えると、成形加工時に樹脂が熱分解し、黄色や褐色などに樹脂が変色し、目的とする色調のフィルムが得られないことがある。
本実施形態の樹脂フィルムには、紫外線を吸収又は反射する目的で、無機顔料が配合されており、これにより白色に着色されている。具体的には、無機顔料として、アルミナ及びシリカにより表面処理された酸化チタンが配合されている。フッ化ビニリデン樹脂は耐候性に優れているため、樹脂フィルム自体の耐候性は十分に確保することできるが、例えば保護フィルムとして使用する場合は、下層に位置する保護対象物に、紫外線が照射されないようにする必要がある。そこで、本実施形態の樹脂フィルムでは、酸化チタンにより光を吸収又は反射することで、紫外線の透過を防止している。
フッ素系樹脂は、表面張力が最も小さい樹脂の一つであり、各物質に対する濡れ性が著しく低い。このため、フィルムを着色するために多量の顔料を配合すると、分散不良が発生しやすく、フィルムなどを加工成形する際に、ピンホールなどの不良が発生する原因となる。そこで、本実施形態の樹脂フィルムでは、顔料(酸化チタン)の分散性を向上させる目的で、フッ素系樹脂との相溶性に優れるポリエチレングリコールの脂肪酸エステル及び/又はその誘導体を配合している。
次に、本発明の第2の実施形態に係るフッ化ビニリデン系樹脂フィルムについて説明する。本実施形態の樹脂フィルムは、組成が異なる2以上の層を備える多層フィルムであって、少なくとも表面層及び裏面層は、フッ化ビニリデン樹脂と、メタクリル酸エステル樹脂と、アルミナ及びシリカによって表面処理された酸化チタンと、ポリエチレングリコールの脂肪酸エステル及び/又はその誘導体と、を含有している。
本実施形態の樹脂フィルムにおける樹脂成分は、前述したフッ化ビニリデン樹脂及びメタクリル酸エステル樹脂からなり、その配合比は、表面層では、質量比で、フッ化ビニリデン樹脂:メタクリル酸エステル樹脂=70:30〜95:5であり、裏面層では、質量比で、フッ化ビニリデン樹脂:メタクリル酸エステル樹脂=5:95〜45:55である。即ち、本実施形態の樹脂フィルムでは、表面層と裏面層とで、フッ化ビニリデン樹脂とメタクリル酸エステル樹脂との配合比が異なっている。
本実施形態の樹脂フィルムは、少なくとも表面層及び裏面層に、紫外線を吸収又は反射する目的で、無機顔料が配合されており、これにより白色に着色されている。具体的には、無機顔料として、アルミナ及びシリカにより表面処理された酸化チタンが配合されている。そして、本実施形態の樹脂フィルムに配合されている酸化チタンは、アルミナ及びシリカにより表面処理されており、これらの総付着量は、酸化チタン全質量あたり5〜11質量%である。なお、ここでいう「酸化チタン全質量」とは、表面に付着しているアルミナ及びシリカを含めた質量である。
以下、本発明の実施例及び比較例を挙げて、本発明の効果について説明する。先ず、本発明の第1の実施形態の実施例として、下記表1に示す組成の樹脂組成物から、実施例1〜8の樹脂フィルムを作製し、その顔料分散性及び熱安定性について評価した。
各樹脂フィルムの裏面から光を当て、きょう雑物測定図表(JIS P8145)を使用し、フィルム面積0.3m2に存在する0.05mm2以上の面積の顔料凝集体の個数を、目視にて測定した。その結果、顔料凝集体の個数が10未満のものを「優良」、顔料凝集体の個数が10以上30未満のものを「良」、顔料凝集体の個数が30以上のものを「不良」として、各フィルムにおける顔料分散性の優劣を評価した。
上記表1及び表2に示すコンパウンドを、熱プレス機を使用し、230℃で5MPaの圧力にてプレス成形して、厚さが約0.3mmの測定用シートを作製した。次に、この測定用シートをオーブンに入れ、条件A:265℃で30分間、条件B:265℃で60分間、加熱した。そして、加熱前後のシートの色の変化を、測色計(クラボウ社製 COLOR−7X)により測定した。その結果に基づいて、下記数式1から色差(ΔE*ab)を算出した。なお、下記数式1におけるL*は明度、a*及びb*は色度である。
次に、本発明の第2の実施形態の実施例として、下記表4及び表5に示す組成の樹脂組成物から、表面層及び裏面層からなる二層構造の樹脂フィルム(実施例11〜18)を作製し、その顔料分散性、熱安定性、耐候性及び接着性について評価した。
実施例及び比較例の各樹脂フィルムについて、促進耐候試験機(ダイプラウインテス社製 アイスーパーUVテスター W−1型)を用いて、耐候性試験を行った。試験条件は、ブラックパネル温度:63℃、照射/結露サイクル:6時間/2時間とした。そして、試験前の各フィルムの表面光沢度と、200時間試験後の表面光沢度を、60°光沢度計(堀場製作所社製 IG−320)で測定し、その比(試験後の光沢度/試験前の光沢度)で表される光沢保持率(%)を算出した。この光沢保持率の値が高いほど、耐候性に優れていることとなる。
基材としてポリ塩化ビニル(Poly Vinyl Chloride:PVC)製マーキングフィルムを使用し、この基材に、実施例及び比較例の各樹脂フィルムを加熱ラミネートして、その接着性について評価した。具体的には、実施例及び比較例の各樹脂フィルム表面にアクリル系接着剤を塗布した後、ロールラミネーターにより、加熱温度を150℃にして、基材と樹脂フィルムとを接着した。接着性は、基材と樹脂フィルムとが手で剥離できるか否かで評価した。その結果、手で剥離することができず、接着性が良好なものを○、基材と樹脂フィルムとが手で剥離できたものを×とした。
Claims (7)
- フッ化ビニリデン樹脂と、
メタクリル酸エステル樹脂と、
アルミナ及びシリカによって表面処理された酸化チタンと、
ポリエチレングリコールの脂肪酸エステル及び/又はその誘導体とを含有し、
前記酸化チタンにおけるアルミナ及びシリカの総付着量が5〜11質量%であるフッ化ビニリデン系樹脂フィルム。 - フッ化ビニリデン樹脂:70〜95質量%及びメタクリル酸エステル樹脂:5〜30質量%からなる樹脂成分100質量部に対して、前記酸化チタンを10〜25質量部、ポリエチレングリコールの脂肪酸エステル及び/又はその誘導体を合計で0.1〜5質量部含有することを特徴とする請求項1に記載のフッ化ビニリデン系樹脂フィルム。
- 組成が異なる2以上の層を備える多層フィルムであって、
少なくとも表面層及び裏面層は、フッ化ビニリデン樹脂と、メタクリル酸エステル樹脂と、アルミナ及びシリカによって表面処理された酸化チタンと、ポリエチレングリコールの脂肪酸エステル及び/又はその誘導体とを含有し、
表面層におけるフッ化ビニリデン樹脂とメタクリル酸エステル樹脂との配合比が、質量比で、70:30〜95:5であり、
裏面層におけるフッ化ビニリデン樹脂とメタクリル酸エステル樹脂との配合比が、質量比で、5:95〜45:55であり、
かつ、前記酸化チタンにおけるアルミナ及びシリカの総付着量が5〜11質量%であるフッ化ビニリデン系樹脂フィルム。 - 表面層及び/又は裏面層は、フッ化ビニリデン樹脂及びメタクリル酸エステル樹脂からなる樹脂成分100質量部に対して、前記酸化チタンを10〜25質量部、ポリエチレングリコールの脂肪酸エステル及び/又はその誘導体を合計で0.1〜5質量部含有することを特徴とする請求項3に記載のフッ化ビニリデン系樹脂フィルム。
- 前記酸化チタンの含有量が12〜20質量部であることを特徴とする請求項2又は4に記載のフッ化ビニリデン系樹脂フィルム。
- 前記酸化チタンにおけるアルミナ及びシリカの総付着量が6〜10質量%であることを特徴とする請求項1乃至5のいずれか1項に記載のフッ化ビニリデン系樹脂フィルム。
- 前記酸化チタンにおけるアルミナ及びシリカの付着量が、それぞれ2.5質量%以上であることを特徴とする請求項1乃至6のいずれか1項に記載のフッ化ビニリデン系樹脂フィルム。
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CN102317371A (zh) | 2012-01-11 |
EP2397519A1 (en) | 2011-12-21 |
CN102317371B (zh) | 2014-08-13 |
US8895140B2 (en) | 2014-11-25 |
EP2397519B1 (en) | 2015-11-25 |
KR101659280B1 (ko) | 2016-09-26 |
US20110293945A1 (en) | 2011-12-01 |
EP2397519A4 (en) | 2015-03-04 |
KR20110128836A (ko) | 2011-11-30 |
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