JP7200525B2 - 保護フィルムおよびシート - Google Patents
保護フィルムおよびシート Download PDFInfo
- Publication number
- JP7200525B2 JP7200525B2 JP2018140252A JP2018140252A JP7200525B2 JP 7200525 B2 JP7200525 B2 JP 7200525B2 JP 2018140252 A JP2018140252 A JP 2018140252A JP 2018140252 A JP2018140252 A JP 2018140252A JP 7200525 B2 JP7200525 B2 JP 7200525B2
- Authority
- JP
- Japan
- Prior art keywords
- protective film
- polyolefin resin
- mass
- resin layer
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2419/00—Buildings or parts thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2451/00—Decorative or ornamental articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2571/00—Protective equipment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2590/00—Signboards, advertising panels, road signs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Landscapes
- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
このヒンダードアミン系光安定剤には高分子タイプと低分子タイプがあり、高分子タイプは一般的にポリオレフィンなどの樹脂中で動きにくいためブルームやブリードしにくく、保護フィルムの耐候性が長期間保持される。一方、低分子タイプは高分子タイプより光安定剤としての性能が高いことが知られるが、ブルームやブリードの懸念がある。
NOアルキル型低分子光安定剤はブリードに問題なければ有望な材料であるが、当該光安定剤の透明ポリオレフィンへの適用において、どのような材料がブリード耐性に優れ高耐候性を付与するか知見がなかった。
本発明の第一実施形態として、透明ポリオレフィン樹脂層11に表面保護層12を設けた保護フィルム10の構成について、図1を用いて説明する。ただし、以下に説明する各図において相互に対応する部分には同一符号を付し、重複部分においては後述での説明を適宜省略する。また、本実施形態は、本発明の技術的思想を具体化するための構成を例示するものであって、各部の材質、形状、構造、配置、寸法などを下記のものに特定するものでない。本発明の技術的思想は、特許請求の範囲に記載された請求項が規定する技術的範囲内において、種々の変更を加えることができる。
本実施形態に係る保護フィルム10は、透明ポリオレフィン樹脂層11と、透明ポリオレフィン樹脂層11の一方の面側、即ち透明ポリオレフィン樹脂層11の上層に形成された表面保護層12と、を備えている。
本実施形態に係る透明ポリオレフィン樹脂層11を構成するオレフィン樹脂としては、例えば、ポリプロピレン、ポリエチレン、ポリブテンなどの他に、αオレフィン(例えば、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-ノネン、1-デセン、1-ウンデセン、1-ドデセン、トリデセン、1-テトラデセン、1-ペンタデセン、1-ヘキサデセン、1-ヘプタデセン、1-オクタデセン、1-ノナデセン、1-エイコセン、3-メチル-1-ブテン、3-メチル-1-ペンテン、3-エチル-1-ペンテン、4-メチル-1-ペンテン、4-メチル-1-ヘキセン、4,4-ジメチル-1-ペンテン、4-エチル-1-ヘキセン、3-エチル-1-ヘキセン、9-メチル-1-デセン、11-メチル-1-ドデセン、12-エチル-1-テトラデセンなどを)を単独重合あるいは2種類以上共重合させたものや、エチレン・酢酸ビニル共重合体、エチレン・ビニルアルコール共重合体、エチレン・メチルメタクリレート共重合体、エチレン・エチルメタクリレート共重合体、エチレン・ブチルメタクリレート共重合体、エチレン・メチルアクリレート共重合体、エチレン・エチルアクリレート共重合体、エチレン・ブチルアクリレート共重合体などのように、エチレンまたはαオレフィンとそれ以外のモノマーとを共重合させたものが挙げられる。また、保護フィルム10の表面強度の向上を図る場合には、例えば、高結晶性のポリプロピレンを用いることが好ましい。
その他光安定剤の例としては、例えば、2-(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)-2’-n-ブチルマロン酸ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)セバケート、テトラキス(2,2,6,6-テトラメチル-4-ピペリジル)-1,2,3,4-ブタンテトラカルボキシレートなどのヒンダードアミン系光安定剤が挙げられる。
透明ポリオレフィン樹脂層11には意匠性を付与するために表面凹凸を設けてもよい。凹凸を設ける方法としては、例えば、透明ポリオレフィン樹脂フィルムを押出成形した後に熱エンボス加工を施す方法、押出形成時に凹凸を設けた冷却ロールを用い押出し成形と同時にエンボス加工を施す方法がある。
表面保護層12は、保護フィルム10に、耐候性、耐傷性、耐汚染性、意匠性などの機能を付与するために設けられ、材料としては特に限定されるものではないが、ウレタン系、アクリル系、アクリルシリコン系、フッ素系、エポキシ系などの樹脂材料より適宜選択して用いられる。
本実施形態に係る表面保護層12は、必要に応じて、例えば、紫外線吸収剤、熱安定剤、光安定剤、ブロッキング防止剤、触媒捕捉剤、着色剤、光散乱剤および艶調整剤などの各種添加剤を配合してもよい。紫外線吸収剤および光安定剤としては、例えば前述の透明ポリオレフィン樹脂層11に適用されるものを用いることができる。
表面保護層12の形成方法は特に限定されるものではなく、前述の材料を塗液化したものを、例えば、グラビアコート、マイクログラビアコート、コンマコート、ナイフコート、ダイコートなど通常の方法で塗布した後、熱硬化、紫外線硬化など材料に適合した方法で硬化させることで表面保護層12を形成してもよい。
また、表面保護層12は、透明ポリオレフィン樹脂層11を後述の基材30と接合した後に設けてもよい。
本発明の第二実施形態として、第一実施形態に係る保護フィルム10と、基材30を接合し、化粧シート40とした構成について、図2を用いて説明する。
化粧シート40は、表面保護層12と透明ポリオレフィン樹脂層11を備える保護フィルム10、即ち第一実施形態に係る保護フィルム10を、接着層20を介して基材30に接合することで構成される。なお、図2では、保護フィルム10に備わる透明ポリオレフィン樹脂層11と、後述する基材30に備わる絵柄層32とが接着層20を介して接合した化粧シート40が示されている。
基材30は、原反31と、原反31の一方の面側に設けられた絵柄層32と、を備えている。
原反31としては、例えば、薄葉紙、チタン紙、樹脂含浸紙などの紙、ポリエチレン、ポリプロピレン、ポリブチレン、ポリスチレン、ポリカーボネート、ポリエステル、ポリアミド、エチレン-酢酸ビニル共重合体、ポリビニルアルコール、アクリルなどの合成樹脂、あるいはこれら合成樹脂の発泡体、エチレン-プロピレン共重合ゴム、エチレン-プロピレン-ジエン共重合ゴム、スチレン-ブタジエン共重合ゴム、スチレン-イソプレン-スチレンブロック共重合ゴム、スチレン-ブタジエン-スチレンブロック共重合ゴム、ポリウレタンなどのゴム、有機もしくは無機系の不織布、合成紙、アルミニウム、鉄、金、銀などの金属箔などから任意に選定可能である。
原反31は、原反31に隣接する層との密着性を補うため、原反31の片面あるいは両面に、例えばプライマ層(図示せず)を設けてもよいし、コロナ処理、プラズマ処理、オゾン処理、電子線処理、紫外線処理、重クロム酸処理などの表面処理を施してもよい。
絵柄層32は、例えば、原反31に対してインキを用いて施された絵柄印刷である。絵柄層32の形成に用いられるインキはバインダを含んでいてもよく、そのバインダとしては、例えば、硝化綿、セルロース、塩化ビニル-酢酸ビニル共重合体、ポリビニルブチラール、ポリウレタン、アクリル、ポリエステル系などの単独もしくは各変性物の中から適宜選定して用いることができる。また、それらは水性、溶剤系、エマルジョンタイプのいずれでもよく、また1液タイプでも硬化剤を使用した2液タイプでもよい。
絵柄層32の形成に用いられるインキを硬化させる方法としては、紫外線や電子線などの照射によりインキを硬化させる方法が挙げられる。中でも最も一般的な方法は、ウレタン系のインキを用いるもので、イソシアネートによって硬化させる方法である。
絵柄層32の形成に用いられるインキは、これらのバインダ以外に、例えば、通常のインキに含まれている顔料、染料などの着色剤、体質顔料、溶剤、光安定剤など各種添加剤などが添加されている。汎用性の高い顔料としては、例えば、縮合アゾ、不溶性アゾ、キナクリドン、イソインドリン、アンスラキノン、イミダゾロン、コバルト、フタロシアニン、カーボン、酸化チタン、酸化鉄、雲母などのパール顔料などが挙げられる。
基材30に保護フィルム10を接合する方法は特に限定されるものではなく、必要に応じて、例えば接着層20を介した熱ラミネート、押出ラミネート、ドライラミネート、サンドラミネートなどの各種ラミネート手法を用いることができる。
接着層20は特に限定されるものではなく、例えば、ウレタン系、アクリル系、アクリルシリコン系、フッ素系、エポキシ系などの樹脂材料から適宜選択しインキ化した材料を、例えば、グラビアコート、マイクログラビアコート、コンマコート、ナイフコート、ダイコートなど通常の塗布方法を用いて形成される。
<実施例1>
透明なホモポリプロピレン樹脂(プライムPP;(株)プライムポリマー製)100質量部に紫外線吸収剤(チヌビン1600;BASFジャパン(株)製)を0.3質量部および光安定剤として、下記式(A)に示す光安定剤(光安定剤A)(アデカスタブLA-81;(株)ADEKA製)0.5質量部を添加した樹脂組成物を厚さ80μmで溶融押し出しすることで実施例1の保護フィルムを得た。
次に、隠蔽性のあるポリエチレン原反(厚さ70μm)に、2液型ウレタンインキ(V180;東洋インキ(株)製)を用い木目柄をグラビア印刷し絵柄層(厚さ3μm)を設けることで得られた基材に、ドライラミネート用接着剤(タケラックA540;三井化学(株)製)(厚み2μm)を介して上記保護フィルムをドライラミネートした。さらに表面保護層としてアクリルポリオール(メチルメタクリレートと2ヒドロキシメタクリレートの共重合体)と硬化剤(ヘキサメチレンジイソシアネートのヌレート体)からなる2液硬化ポリウレタン樹脂層を、上記保護フィルム上に塗布形成(層厚8μm)し、実施例1の化粧シートを得た。
実施例1において、光安定剤として光安定剤Aを0.75質量部添加した以外は実施例1と同様の方法で実施例2の化粧シートを得た。
<実施例3>
実施例1において、光安定剤として光安定剤Aを1.0質量部添加した以外は実施例1と同様の方法で実施例3の化粧シートを得た。
実施例1において、光安定剤として下記式(B)に示す光安定剤(光安定剤B)(チヌビン123;BASFジャパン(株)製)を0.5質量部添加した以外は実施例1と同様の方法で比較例1の化粧シートを得た。
<比較例2>
実施例1において、光安定剤として光安定剤Bを0.75質量部添加した以外は実施例1と同様の方法で比較例2の化粧シートを得た。
実施例1において、光安定剤として光安定剤Bを1.0質量部添加した以外は実施例1と同様の方法で比較例3の化粧シートを得た。
<比較例4>
実施例1において、光安定剤として下記式(C)に示す光安定剤(光安定剤C)(チヌビンNOR371;BASFジャパン(株)製)0.5質量部を添加した以外は実施例1と同様の方法で比較例4の化粧シートを得た。
実施例1において、光安定剤として光安定剤Cを0.75質量部添加した以外は実施例1と同様の方法で比較例5の化粧シートを得た。
<比較例6>
実施例1において、光安定剤として光安定剤Cを1.0質量部添加した以外は実施例1と同様の方法で比較例6の化粧シートを得た。
上記実施例および比較例で得られた化粧シートについて、以下の方法で耐候性を評価した。評価結果を下記表1に示す。
化粧シートの耐候促進試験後の外観を以下の基準により目視評価した。耐候促進試験はアイスーパーUVテスター(SUV-W161;岩崎電気(株))を用い、ブラックパネル温度63℃、照度65mW/cm2にて、(UV照射20時間+結露4時間)を1サイクルとし、20サイクル(480時間)、25サイクル(600時間)、30サイクル(720時間)とそれぞれ実施した後の化粧シートの外観を目視評価した。
(目視評価基準)
〇:化粧シートに外観変化なし
△:化粧シートに白化が認められる
×:化粧シートにワレが認められる
なお、耐候性の評価が「○」および「△」であれば使用上問題がないため、合格とした。
11 透明ポリオレフィン樹脂層
12 表面保護層
20 接着層
30 基材
31 原反
32 絵柄層
40 化粧シート
Claims (9)
- 透明ポリオレフィン樹脂層と、前記透明ポリオレフィン樹脂層の上層に形成された表面保護層とを少なくとも含む保護フィルムであって、
前記透明ポリオレフィン樹脂層が下記一般式(I)で表されるヒンダードアミン系光安定剤を、前記透明ポリオレフィン樹脂層に含まれる透明オレフィン樹脂100質量部に対し0.05質量部以上5質量部以下の範囲内で含有し、
前記表面保護層は、2液硬化ポリウレタン樹脂で形成されており、
前記ポリウレタン樹脂は、メチルメタクリレートと2ヒドロキシエチルメタクリレートとの共重合体であることを特徴とする保護フィルム。
- 前記透明ポリオレフィン樹脂層が、ヒドロキシフェニルトリアジン系の紫外線吸収剤及びベンゾトリアゾール系の紫外線吸収剤の少なくとも一方をさらに含有していることを特徴とする請求項1に記載の保護フィルム。
- 前記紫外線吸収剤の含有量が前記ヒンダードアミン系光安定剤の含有量よりも少ないことを特徴とする請求項2または請求項3に記載の保護フィルム。
- 前記紫外線吸収剤の含有量が前記ヒンダードアミン系光安定剤の含有量よりも少なく、
前記透明ポリオレフィン樹脂層が前記ヒンダードアミン系光安定剤を、前記透明ポリオレフィン樹脂層に含まれる透明オレフィン樹脂100質量部に対し0.5質量部以上1質量部以下の範囲内で含有していることを特徴とする請求項2から請求項4のいずれか1項に記載の保護フィルム。 - 前記透明ポリオレフィン樹脂層が前記ヒンダードアミン系光安定剤を、前記透明ポリオレフィン樹脂層に含まれる透明オレフィン樹脂100質量部に対し0.75質量部以上1質量部以下の範囲内で含有していることを特徴とする請求項2から請求項5のいずれか1項に記載の保護フィルム。
- 請求項1から請求項7のいずれか1項に記載の保護フィルムと、基材とを少なくとも含むことを特徴とするシート。
- 請求項1から請求項7のいずれか1項に記載の保護フィルムと、基材とが接着層で接合された構成であり、
前記基材は、原反と、前記接着層側に位置する絵柄層とを備えることを特徴とするシート。
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EP3024650A1 (en) * | 2013-07-22 | 2016-06-01 | E. I. du Pont de Nemours and Company | Multilayer polymeric sheets and light weight laminates produced therefrom |
IL281313B2 (en) | 2014-11-20 | 2024-03-01 | Cytec Ind Inc | Stabilizers and methods of using them to protect organic polymeric materials against ultraviolet light and thermal decomposition |
JP2017197639A (ja) | 2016-04-27 | 2017-11-02 | 住江織物株式会社 | 表面保護フィルム及びその製造方法並びに該表面保護フィルムを最表面に積層した床材 |
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JP2005120255A (ja) | 2003-10-17 | 2005-05-12 | Toppan Printing Co Ltd | オーバーラミネート用フィルム |
WO2005082852A1 (ja) | 2004-03-02 | 2005-09-09 | Adeka Corporation | カーボネート骨格を有する低塩基性ヒンダードアミン化合物、合成樹脂組成物及び塗料組成物 |
JP2006103074A (ja) | 2004-10-04 | 2006-04-20 | Toppan Printing Co Ltd | オーバーラミネート用フィルム |
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CN112469568B (zh) | 2023-11-14 |
WO2020022384A1 (ja) | 2020-01-30 |
US20210138774A1 (en) | 2021-05-13 |
CN112469568A (zh) | 2021-03-09 |
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JP2020015250A (ja) | 2020-01-30 |
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