JP4068701B2 - Exterior decorative sheet - Google Patents

Description

（式中、Ｘは水素又は塩素であり、Ｙは水酸基又はカルボキシル基である）
また、アクリルポリオール樹脂は、ポリ（メタ）アクリル酸エステル系重合体やポリアクリロニトリル樹脂と、ビニルアルコールやヒドロキシアルキルビニルエーテル等の水酸基を有するモノマーとの共重合体である。上記のポリ（メタ）アクリル酸エステル系重合体としては、ポリ（メタ）アクリル酸メチル、ポリ（メタ）アクリル酸エチル、ポリ（メタ）アクリル酸ブチル、（メタ）アクリル酸メチル−（メタ）アクリル酸ブチル共重合体、（メタ）アクリル酸エチル−（メタ）アクリル酸ブチル共重合体、（メタ）アクリル酸エステル−スチレン共重合体等を挙げることができる。尚、上記の（メタ）アクリルは、アクリルまたはメタアクリルのことである。
【００２０】
絵柄層３の樹脂成分におけるポリ三フッ化エチレンとアクリルポリオール樹脂との重量比は１：１〜９：１の範囲内であることが好ましい。ポリ三フッ化エチレンの割合が上記範囲を超えると、絵柄層３を形成するためのインキの溶剤溶解性、溶融温度が高くなり印刷適性、接着性が低下するとともに、また、基材フィルム２や透明保護層４に対する密着性が低下するので好ましくない。一方、アクリルポリオール樹脂の割合が上記範囲を超えると、絵柄層３が硬くなりすぎ、また、外装化粧シート１の加工適性や耐候性が低下するので好ましくない。
【００２１】
尚、絵柄層３の樹脂成分は、上記のポリ三フッ化エチレンとアクリルポリオール樹脂の他に、上記のようなアクリル酸エステル系重合体、塩化ビニル酢酸ビニル共重合体等の副成分の樹脂、紫外線吸収剤、あるいは、光安定剤等を含有していてもよい。
【００２２】
絵柄層３に使用する顔料としては、下記のような耐候性顔料を挙げることができる。
【００２３】
（黄色顔料）
イソインドリノン、スレンイエローＧ、および、パーマネントイエローＨＲ等の有機顔料、黄色酸化鉄、ニッケルチタンイエロー等の無機顔料
（赤色顔料）
キナクリドンレッド、パーマネントレッドＦＧＲ、および、パーマネントレッドＦ４ＲＨ等の有機顔料、ベンガラ、硫化水銀（朱）、カドミウムレッド等の無機顔料
（青色顔料）
フタロシアニンブルー、インダスレンブルーＲＳ等の有機顔料、群青、紺青等の無機顔料
（黒色顔料）
カーボンブラック等
（白色顔料）
二酸化チタン、三酸化二アンチモン等
絵柄層３は、上記のポリ三フッ化エチレンとアクリルポリオール樹脂との混合物を主成分とする樹脂成分と、顔料と、必要に応じて硬化剤（架橋剤）を含有したインキを使用して、グラビア印刷、シルクスクリーン印刷、オフセット印刷等により形成することができる。絵柄としては、木目柄、石目柄、布目柄、幾何学模様、全面ベタ等である。硬化剤としては、熱変色防止、耐候性の観点から脂肪族または脂環式イソシアネートが好ましく、具体的には、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、水素添化トリレンジイソシアネート等を挙げることができる。このような硬化剤は、ポリ三フッ化エチレンとアクリルポリオール樹脂との混合物１００重量部に対して１０〜２０重量部の範囲で含有させることが好ましく、硬化剤の添加により絵柄層３の接着力を向上させることができる。このような絵柄層３の厚みは、２〜６μｍの範囲で設定することが好ましい。
【００２４】
尚、絵柄層３２は、２−（２′−ヒドロキシ−３′，５′−ジ−ｔｅｒｔ−ブチルフェニル）−５−クロロベンゾトリアゾール等のベンゾトリアゾール系、２，４−ジ−ｔ−ブチルフェニル−３，５−ジ−ｔ−ブチル−４−ヒドロキシベンゾエート等のベンゾエート系、ベンゾフェノン系、サリシレート系等の公知の紫外線吸収剤を０．１〜５重量％の範囲で含有していてもよく、また、ビス−（２，２，６，６−テトラメチル−４−ピペリジニル）セバケート、ビス−（Ｎ−メチル−２，２，６，６−テトラメチル−４−ピペリジニル）セバケート等のヒンダードアミン系ラジカル捕捉剤等の公知の光安定剤を０．１〜５重量％の範囲で含有していてもよい。
【００２５】
外装化粧シート１を構成する透明保護層４は、ポリ三フッ化エチレンとアクリルポリオール樹脂との混合物を主成分とするものである。ポリ三フッ化エチレンおよびアクリルポリオール樹脂は、上述の絵柄層３に使用するポリ三フッ化エチレンおよびアクリルポリオール樹脂と同様である。また、透明保護層４におけるポリ三フッ化エチレンとアクリルポリオール樹脂との重量比は１：１〜９：１の範囲内であることが好ましい。ポリ三フッ化エチレンの割合が上記範囲を超えると、透明保護層４を形成するためのインキの溶剤溶解性、溶融温度が高くなり印刷適性が低下し、また、基材フィルム２や絵柄層３との密着性が低下するので好ましくない。一方、アクリルポリオール樹脂の割合が上記範囲を超えると、透明保護層４が硬くなりすぎ、外装化粧シート１の加工適性や耐候性が低下するので好ましくない。
【００２６】
また、透明保護層４は、上記のポリ三フッ化エチレンとアクリルポリオール樹脂の他に、必要に応じて上記のようなアクリル酸エステル系重合体、塩化ビニル酢酸ビニル共重合体等の副成分の樹脂、紫外線吸収剤、光安定剤、あるいは、シリカ、球状アルミナ等の微粒子からなる艶消剤、上記の耐候性顔料、銀イオン担持ゼオライト微粒子等の抗菌剤、ワックス等の滑剤等を透明性を損わない範囲で含有していてもよい。
【００２７】
透明保護層４の形成は、上記のポリ三フッ化エチレンとアクリルポリオール樹脂との混合物と、必要に応じて硬化剤を含有したインキを使用して、グラビアロールコータ、カーテンフローコータ等により行うことができる。硬化剤は、上述の絵柄層３に使用する硬化剤と同様であり、インキ中の硬化剤の含有量は、ポリ三フッ化エチレンとアクリルポリオール樹脂との混合物１００重量部に対して１０〜２０重量部の範囲が好ましい。このように形成される透明保護層４の厚みは２〜１０μｍの範囲で設定することが好ましい。
【００２８】
本発明の外装化粧シートの貼り合わせ対象となる金属板としては、例えば、鉄またはステンレス鋼等の鉄合金、アルミニウム、ジュラルミン等のアルミニウム合金、銅等からなる金属板で適当な厚みのものを選ぶことができる。
【００２９】
尚、本発明の外装化粧シートは、２液硬化型ウレタン樹脂等の接着剤を用いて、金属板等の基体に接着積層し、サイジング板等の外壁材、屋根材、柵、塀、扉、窓枠、扉枠、車輌や船舶の外装材等として用いることができる。
【００３０】
【実施例】
次に、実施例を示して本発明を更に詳細に説明する。
（試料１の作製）
基材フィルムとして、ポリフッ化ビニル（ＰＶＦ）フィルム（デュポン（株）製テドラー（登録商標）（厚み３８μｍ））を準備し、このＰＶＦフィルム上に下記組成の絵柄層用インキＡを使用してグラビア印刷で石目柄の絵柄層（４０℃で４８時間のエージング後の厚み３μｍ）を形成した。
【００３１】
絵柄層用インキＡの組成
・ポリ三フッ化エチレン … ８０重量部
（分子中に水酸基を含有する分子量５×１０⁵ のもの）
・アクリルポリオール樹脂 … ２０重量部
・顔料（弁柄、カーボンブラックを主体とする） … ３０重量部
・ヘキサメチレンジイソシアネート … １０重量部
次いで、上記の絵柄層の上から下記組成の透明保護層用インキ１を使用してグラビア印刷で透明保護層（４０℃で４８時間のエージング後の厚み３μｍ）を形成した。これにより外装化粧シート（試料１）を得た。
【００３２】
透明保護層用インキ１の組成
・ポリ三フッ化エチレン … ６７重量部
（分子中に水酸基を含有する分子量５×１０⁵ のもの）
・アクリルポリオール樹脂 … ３３重量部
・ヘキサメチレンジイソシアネート … １５重量部
（試料２の作製）
絵柄層用インキとして、下記組成の絵柄層用インキＢを使用した他は、試料１と同様にして、外装化粧シート（試料２）を得た。
【００３３】
絵柄層用インキＢの組成
・ポリ三フッ化エチレン … ５０重量部
（分子中に水酸基を含有する分子量５×１０⁵ のもの）
・アクリルポリオール樹脂 … ５０重量部
・顔料（弁柄、カーボンブラックを主体とする） … ３０重量部
・ヘキサメチレンジイソシアネート … １０重量部
（試料３の作製）
絵柄層用インキとして、下記組成の絵柄層用インキＣを使用した他は、試料１と同様にして、外装化粧シート（試料３）を得た。
【００３４】
絵柄層用インキＣの組成
・ポリ三フッ化エチレン … ９０重量部
（分子中に水酸基を含有する分子量５×１０⁵ のもの）
・アクリルポリオール樹脂 … １０重量部
・顔料（弁柄、カーボンブラックを主体とする） … ３０重量部
・ヘキサメチレンジイソシアネート … １０重量部
（試料４の作製）
透明保護層用インキとして下記組成の透明保護層用インキ２を使用した他は、試料１と同様にして外装化粧シート（試料４）を得た。
【００３５】
透明保護層用インキ２の組成
・ポリ三フッ化エチレン … ５０重量部
（分子中に水酸基を含有する分子量５×１０⁵ のもの）
・アクリルポリオール樹脂 … ５０重量部
・ヘキサメチレンジイソシアネート … １５重量部
（試料５の作製）
透明保護層用インキとして下記組成の透明保護層用インキ３を使用した他は、試料１と同様にして外装化粧シート（試料５）を得た。
【００３６】
透明保護層用インキ３の組成
・ポリ三フッ化エチレン … ９０重量部
（分子中に水酸基を含有する分子量５×１０⁵ のもの）
・アクリルポリオール樹脂 … １０重量部
・ヘキサメチレンジイソシアネート … １５重量部
（試料６の作製）
基材フィルムとして、ポリフッ化ビニリデン（ＰＶＤＦ）を主成分とし、これにポリメチルメタアクリレートを添加してなるフィルム（電気化学（株）製ＤＸフィルム（厚み４０μｍ））を使用した他は、試料１と同様にして外装化粧シート（試料６）を得た。
（試料７の作製）
基材フィルムとして、樹脂１００重量部に対して可塑剤を２３重量部含有するポリ塩化ビニル（ＰＶＣ）フィルム（三宝樹脂（株）製（厚み２００μｍ））を使用した他は、試料１と同様にして外装化粧シート（試料７）を得た。
（試料８の作製）
絵柄層用インキとして、下記組成の絵柄層用インキＤを使用した他は、試料１と同様にして、外装化粧シート（試料８）を得た。
【００３７】
絵柄層用インキＤの組成
・ポリ三フッ化エチレン … ３０重量部
（分子中に水酸基を含有する分子量５×１０⁵ のもの）
・アクリルポリオール樹脂 … ６０重量部
・顔料（弁柄、カーボンブラックを主体とする） … ３０重量部
・ヘキサメチレンジイソシアネート … ９重量部
（試料９の作製）
絵柄層用インキとして、下記組成の絵柄層用インキＥを使用した他は、試料１と同様にして、外装化粧シート（試料９）を得た。
【００３８】
絵柄層用インキＥの組成
・ポリ三フッ化エチレン … １２０重量部
（分子中に水酸基を含有する分子量５×１０⁵ のもの）
・アクリルポリオール樹脂 … １０重量部
・顔料（弁柄、カーボンブラックを主体とする） … ３０重量部
・ヘキサメチレンジイソシアネート … １３重量部
（試料１０の作製）
透明保護層用インキとして下記組成の透明保護層用インキ４を使用した他は、試料１と同様にして外装化粧シート（試料１０）を得た。
【００３９】
透明保護層用インキ４の組成
・ポリ三フッ化エチレン … ３０重量部
（分子中に水酸基を含有する分子量５×１０⁵ のもの）
・アクリルポリオール樹脂 … ６０重量部
・ヘキサメチレンジイソシアネート … １４重量部
（試料１１の作製）
透明保護層用インキとして下記組成の透明保護層用インキ５を使用した他は、試料１と同様にして外装化粧シート（試料１１）を得た。
【００４０】
透明保護層用インキ５の組成
・ポリ三フッ化エチレン … １２０重量部
（分子中に水酸基を含有する分子量５×１０⁵ のもの）
・アクリルポリオール樹脂 … １０重量部
・ヘキサメチレンジイソシアネート … ２０重量部
（試料１２の作製）
基材フィルムとして、樹脂１００重量部に対して可塑剤を２３重量部含有するポリ塩化ビニル（ＰＶＣ）フィルム（三宝樹脂（株）製（厚み２００μｍ））を準備し、このＰＶＣフィルム上に下記組成の絵柄層用インキＦを使用してグラビア印刷で石目柄の絵柄層（厚み３μｍ）を形成した。
【００４１】
絵柄層用インキＦの組成
・アクリル樹脂 … ８０重量部
・塩化ビニル−酢酸ビニル共重合体 … ２０重量部
・顔料（弁柄、カーボンブラックを主体とする） … ３０重量部
次いで、上記の絵柄層の上から下記組成の透明保護層用インキ６を使用してグラビア印刷で透明保護層（厚み３μｍ）を形成した。これにより外装化粧シート（試料１２）を得た。
【００４２】
透明保護層用インキ６の組成
・アクリルシリコーン … ８０重量部
・塩化ビニル−酢酸ビニル共重合体 … ２０重量部
（評価）
上記のように作製した各外装化粧シート（試料１〜１２）について、下記の条件で耐候性、耐溶剤性、耐汚染性を評価して結果を下記の表１に示した。
【００４３】
耐候性の評価条件
サンシャインカーボンアーク灯型ウエザオメータ（スガ試験機（株）製）中で１０，０００時間暴露させて、変色状態を目視で下記基準により評価した。尚、１２０分当たり１８分間を降雨時間とし、ブラックパネル温度を６３℃とした。
【００４４】
（評価基準）
○：変色、退色、クラック、層間剥離がまったくみられない
△：変色、退色が若干みられる
×：変色、退色が顕著で、クラック、層間剥離もみられる
耐溶剤性の評価条件
メチルエチルケトン中に３０日間浸漬した後の透明保護層および絵柄層の状態を下記基準で評価した。
【００４５】
（評価基準）
○：インキの溶解がまったくみられない
△：インキの溶解が若干みられる
×：インキが溶解して絵柄の乱れが顕著である
耐汚染性の評価条件
外装化粧シートの透明保護層上に油性赤マヂックインキ、クレヨン、インクで文字、線等を描き、その後、石油ベンジンを含ませた布でふきとった状態を目視により下記の基準で評価した。
【００４６】
（評価基準）
○：透明保護層上への色残りがまったくみられない
△：透明保護層上への色残りが若干みられる
×：透明保護層上への色残りが顕著である
次に、上記のように作製した各外装化粧シート（試料１〜１２）を、加熱温度１８０〜２００℃で厚み０．６ｍｍの鋼板上に貼り合わせて外装材とし、各外装材について、下記の条件で加工適性を評価して結果を下記の表１に示した。
【００４７】
加工適性の評価条件
ＪＩＳ Ｋ６７４４のエリクセン試験に準じて、曲げ加工および絞り加工における外装化粧シートの状態を目視により下記の基準で評価した。
【００４８】
（評価基準）
○：曲げ加工部および絞り加工部に変化がみられない
△：曲げ加工部に亀裂、白化が若干みられ、絞り加工部に剥離が若干みられる
×：曲げ加工部に亀裂、白化がみられ、絞り加工部の剥離が顕著である
【００４９】
【表１】

表１に示されるように、試料１〜６は、耐候性、耐溶剤性、耐汚染性および加工適性ともに良好であった。
【００５０】
また、絵柄層または透明保護層におけるポリ三フッ化エチレンとアクリルポリオール樹脂との重量比が１：１〜９：１の範囲からはずれる試料８〜１１は、試料１〜６に比べて耐候性、耐溶剤性、耐汚染性および加工適性のいずれかが劣るものであった。
【００５１】
一方、基材フィルムにＰＶＣを使用した試料７、および、従来の外装化粧シートである試料１２は、耐候性、耐溶剤性、耐汚染性および加工適性が不十分なものであった。
【００５２】
【発明の効果】
以上詳述したように、本発明によればポリフッ化ビニルおよびポリフッ化ビニリデンの少なくとも一方を主成分とする基材フィルム上に、ポリ三フッ化エチレンとアクリルポリオール樹脂との混合物を主成分とする樹脂成分と顔料とからなる絵柄層を設け、この絵柄層を覆うように、ポリ三フッ化エチレンとアクリルポリオール樹脂との混合物を主成分とする透明保護層を基材フィルム上に形成して外装化粧シートとするので、基材フィルムが金属板および他の層に対して良好な接着性を示し、絵柄層および透明保護層を構成するポリ三フッ化エチレンにより可撓性と耐候性が付与され、絵柄層および透明保護層を構成するアクリルポリオール樹脂により印刷適性、接着性および適度の硬さが付与されて、可撓性を有し加工適性に優れるとともに、高い耐候性を備える外装化粧シートが可能となる。
【図面の簡単な説明】
【図１】本発明の外装化粧シートの一実施形態を示す概略断面図である。
【符号の説明】
１…外装化粧シート
２…基材フィルム
３…絵柄層
４…透明保護層[0001]
[Technical field to which the invention belongs]
The present invention relates to an exterior decorative sheet, and more particularly to an exterior decorative sheet having excellent processability and weather resistance.
[0002]
[Prior art]
Conventionally, after a decorative sheet on which a pattern is printed is pasted on a metal plate such as a steel plate, it is processed into a desired shape to produce an exterior material. As an exterior decorative sheet used for this purpose, there is a sheet in which a desired picture is printed on a flexible base film such as polyvinyl chloride, and a transparent protective film such as an acrylic resin is laminated thereon.
[0003]
[Problems to be solved by the invention]
However, conventional exterior decorative sheets are cracked or whitened on the exterior decorative sheet of the processed part or peeled from the metal sheet at the stage of bending or drawing after bonding to the metal plate. In addition, discoloration and fading may occur over time, and the processability and weather resistance were insufficient.
[0004]
This invention is made | formed in view of the above situations, and it aims at providing the exterior decorative sheet which is flexible, is excellent in workability, and is equipped with high weather resistance.
[0005]
[Means for Solving the Problems]
In order to achieve such an object, the exterior decorative sheet of the present invention is a base film, a pattern layer formed on the base film, and the pattern layer in an exterior decorative sheet for laminating metal plates. A transparent protective layer formed on the base film so as to cover the base film, the base film is mainly composed of at least one of polyvinyl fluoride and polyvinylidene fluoride, and the pattern layer includes at least a resin component and a pigment. The resin component is mainly composed of a mixture of poly (trifluoroethylene) and acrylic polyol resin, and the weight ratio of poly (trifluoroethylene) and acrylic polyol resin in the pattern layer is 1: 1 to 9: 1. in the range, the transparent protective layer is composed mainly of a mixture of poly ethylene trifluoride and acrylic polyol resin, poly trifluoride in the transparent protective layer The weight ratio of styrene and acrylic polyol resin 1: 1-9: and that there configuration within 1.
[0008]
Moreover, the exterior decorative sheet of the present invention was configured such that the average molecular weight of polytrifluoroethylene was in the range of 3 × 10 ^{5 to} 6 × 10 ⁵ .
[0009]
In addition, the exterior decorative sheet of the present invention is configured such that at least one of the base film, the pattern layer, and the transparent protective layer contains an ultraviolet absorber.
[0010]
In addition, the exterior decorative sheet of the present invention is configured such that at least one of the base film, the pattern layer, and the transparent protective layer contains an antioxidant.
[0011]
Furthermore, the exterior decorative sheet of the present invention is configured such that the thickness of the base film is in the range of 10 to 100 μm, the thickness of the pattern layer is 2 to 6 μm, and the thickness of the transparent protective layer is in the range of 2 to 10 μm. .
[0012]
In the present invention, the base film mainly composed of at least one of polyvinyl fluoride and polyvinylidene fluoride has high adhesiveness to the steel plate and other layers, and is used to form the pattern layer and the transparent protective layer. Ethylene trifluoride imparts flexibility and weather resistance, and the acrylic polyol resin constituting the pattern layer and the transparent protective layer imparts printability, adhesion, and appropriate hardness.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Next, an optimal embodiment of the present invention will be described.
[0014]
FIG. 1 is a schematic cross-sectional view showing an embodiment of the exterior decorative sheet of the present invention. In FIG. 1, an exterior decorative sheet 1 includes a base film 2, a pattern layer 3 formed on the base film 2, and a transparent protective layer laminated on the base film 2 so as to cover the pattern layer 3. 4 is provided.
[0015]
The base film 2 constituting the exterior decorative sheet 1 has at least one of polyvinyl fluoride and polyvinylidene fluoride as a main component. Here, the main component is to occupy 50% by weight or more (hereinafter the same in the present invention), when polyvinyl fluoride occupies 50% by weight or more, when polyvinylidene fluoride occupies 50% by weight, and A mixture of polyvinyl fluoride and polyvinylidene fluoride may occupy 50% by weight or more. In addition, as a subcomponent added with respect to a main component, it is preferable to select a thing with good compatibility with a main component, high transparency, and some weather resistance (light) property. Representative examples of such subcomponents include acrylic resins such as polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl (meth) acrylate (however, (meth) acrylate is an acrylate) Or methacrylate). Thus, by using a film mainly composed of at least one of polyvinyl fluoride and polyvinylidene fluoride as the base film 2, the base film 2 can be applied to the metal plate, the pattern layer 3 and the transparent protective layer 4. It will have high adhesion. For example, when a film made of an ethylene-tetrafluoroethylene copolymer or a polytrifluoroethylene resin is used as the base film 2, the adhesiveness to the metal plate, the pattern layer 3, and the transparent protective layer 4 is insufficient. It becomes.
[0016]
Such a base film 2 has a thickness of 10 to 100 μm, preferably 25 to 40 μm. If the thickness is less than 10 μm, it is difficult to form a film, and the strength of the base film 2 is insufficient, and if it exceeds 100 μm, no further improvement in the properties of the exterior decorative sheet 1 can be expected. It will increase, which is not preferable.
[0017]
The base film 2 is a benzotriazole-based compound such as 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,4-di-t-butyl. It may contain a known UV absorber such as phenyl-3,5-di-t-butyl-4-hydroxybenzoate such as benzoate, benzophenone and salicylate in the range of 0.1 to 5% by weight. Hindered amines such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate A known light stabilizer such as a radical scavenger may be contained in the range of 0.1 to 5% by weight. Furthermore, the base film 2 may be a colored film containing a weatherable pigment as described later. The base film 2 can be subjected to corona discharge treatment as necessary. By this corona discharge treatment, the adhesive strength between the pattern layer 3 and the transparent protective layer 4 can be further improved.
[0018]
The resin component used for the pattern layer 3 constituting the exterior decorative sheet 1 is mainly composed of a mixture of poly (ethylene trifluoride) and acrylic polyol resin. Polytrifluoroethylene is a copolymer having a hydroxyl group or a carboxyl group in the molecule, represented by the following general formula, and is a block copolymer, a random copolymer, or a graft copolymer. The average molecular weight is preferably in the range of 3 × 10 ^{5 to} 6 × 10 ⁵ . When the average molecular weight is less than 3 × 10 ⁵ , the dryness to touch when printed without a curing agent is insufficient, and when the average molecular weight exceeds 6 × 10 ⁵ , the solvent solubility and the flow when converted to ink are used. This is not preferable because of insufficient properties.
[0019]
[Chemical 1]

(Wherein X is hydrogen or chlorine and Y is a hydroxyl group or a carboxyl group)
The acrylic polyol resin is a copolymer of a poly (meth) acrylic acid ester-based polymer or a polyacrylonitrile resin and a monomer having a hydroxyl group such as vinyl alcohol or hydroxyalkyl vinyl ether. Examples of the poly (meth) acrylate polymer include poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate butyl, and (meth) acrylate methyl- (meth) acryl. Examples thereof include butyl acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, and (meth) acrylate ester-styrene copolymer. In addition, said (meth) acryl is an acryl or a methacryl.
[0020]
The weight ratio of polytrifluoroethylene and acrylic polyol resin in the resin component of the pattern layer 3 is preferably in the range of 1: 1 to 9: 1. When the ratio of polytrifluoroethylene exceeds the above range, the solvent solubility and melting temperature of the ink for forming the pattern layer 3 are increased, and the printability and adhesiveness are lowered. Since the adhesiveness with respect to the transparent protective layer 4 falls, it is not preferable. On the other hand, when the ratio of the acrylic polyol resin exceeds the above range, the pattern layer 3 becomes too hard, and the processability and weather resistance of the exterior decorative sheet 1 are lowered, which is not preferable.
[0021]
The resin component of the pattern layer 3 includes, in addition to the above polytrifluoride ethylene and acrylic polyol resin, subcomponent resins such as the above acrylic ester polymers and vinyl chloride vinyl acetate copolymers, An ultraviolet absorber or a light stabilizer may be contained.
[0022]
Examples of the pigment used in the pattern layer 3 include the following weather-resistant pigments.
[0023]
(Yellow pigment)
Organic pigments such as isoindolinone, selenium yellow G, and permanent yellow HR, and inorganic pigments such as yellow iron oxide and nickel titanium yellow (red pigments)
Organic pigments such as quinacridone red, permanent red FGR, and permanent red F4RH, inorganic pigments (blue pigment) such as Bengala, mercury sulfide (red), and cadmium red
Organic pigments such as phthalocyanine blue and indanthrene blue RS, inorganic pigments such as ultramarine and bitumen (black pigments)
Carbon black, etc. (white pigment)
The pattern layer 3 such as titanium dioxide and diantimony trioxide is composed of a resin component mainly composed of a mixture of the above-described poly (trifluoroethylene) and acrylic polyol resin, a pigment, and a curing agent (crosslinking agent) as necessary. Using the contained ink, it can be formed by gravure printing, silk screen printing, offset printing or the like. Examples of the design include a wood grain pattern, a stone pattern, a cloth pattern, a geometric pattern, and a solid surface. As the curing agent, aliphatic or alicyclic isocyanates are preferable from the viewpoint of preventing thermal discoloration and weather resistance, and specific examples include hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and the like. Such a curing agent is preferably contained in an amount of 10 to 20 parts by weight with respect to 100 parts by weight of the mixture of poly (trifluoroethylene) and acrylic polyol resin. Can be improved. The thickness of the pattern layer 3 is preferably set in the range of 2 to 6 μm.
[0024]
The pattern layer 32 is made of benzotriazole such as 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,4-di-t-butylphenyl. It may contain a known ultraviolet absorber such as benzoate-based, benzophenone-based, salicylate-based, such as -3,5-di-t-butyl-4-hydroxybenzoate in the range of 0.1 to 5% by weight, In addition, hindered amine radicals such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate You may contain well-known light stabilizers, such as a trap, in the range of 0.1 to 5% by weight.
[0025]
The transparent protective layer 4 constituting the exterior decorative sheet 1 is mainly composed of a mixture of poly (trifluoroethylene) and acrylic polyol resin. The polytrifluoride ethylene and the acrylic polyol resin are the same as the polytrifluoride ethylene and the acrylic polyol resin used for the pattern layer 3 described above. Moreover, it is preferable that the weight ratio of polytrifluoride ethylene and acrylic polyol resin in the transparent protective layer 4 is in the range of 1: 1 to 9: 1. When the ratio of poly (trifluoroethylene) exceeds the above range, the solvent solubility and melting temperature of the ink for forming the transparent protective layer 4 are increased, and the printability is lowered. Also, the base film 2 and the pattern layer 3 are reduced. This is not preferable because the adhesion to the resin is lowered. On the other hand, when the ratio of the acrylic polyol resin exceeds the above range, the transparent protective layer 4 becomes too hard, and the processability and weather resistance of the exterior decorative sheet 1 are deteriorated.
[0026]
Further, the transparent protective layer 4 may contain, in addition to the above polytrifluoride ethylene and acrylic polyol resin, auxiliary components such as the above acrylate polymer and vinyl chloride vinyl acetate copolymer as necessary. Transparent resin, ultraviolet absorber, light stabilizer, matting agent composed of fine particles such as silica, spherical alumina, antibacterial agents such as the above weather-resistant pigments, silver ion-carrying zeolite fine particles, and lubricants such as wax. You may contain in the range which does not impair.
[0027]
The transparent protective layer 4 is formed using a gravure roll coater, a curtain flow coater, or the like, using a mixture of the above polytrifluoride ethylene and acrylic polyol resin and an ink containing a curing agent as necessary. Can do. The curing agent is the same as the curing agent used for the pattern layer 3 described above, and the content of the curing agent in the ink is 10 to 20 with respect to 100 parts by weight of the mixture of polytrifluoroethylene and acrylic polyol resin. A range of parts by weight is preferred. The thickness of the transparent protective layer 4 thus formed is preferably set in the range of 2 to 10 μm.
[0028]
As a metal plate to be bonded to the exterior decorative sheet of the present invention, for example, an iron alloy such as iron or stainless steel, an aluminum alloy such as aluminum or duralumin, a metal plate made of copper or the like having an appropriate thickness is selected. be able to.
[0029]
In addition, the exterior decorative sheet of the present invention is bonded and laminated to a base such as a metal plate using an adhesive such as a two-component curable urethane resin, an outer wall material such as a sizing plate, a roof material, a fence, a fence, a door, It can be used as a window frame, a door frame, an exterior material of a vehicle or a ship.
[0030]
【Example】
Next, an Example is shown and this invention is demonstrated further in detail.
(Preparation of sample 1)
A polyvinyl fluoride (PVF) film (Tedlar (registered trademark) (thickness: 38 μm) manufactured by DuPont Co., Ltd.) was prepared as a base film, and gravure using the pattern layer ink A having the following composition on the PVF film. A stone pattern pattern (thickness 3 μm after aging at 40 ° C. for 48 hours) was formed by printing.
[0031]
Composition of the ink A for the pattern layer: poly (ethylene trifluoride) 80 parts by weight (with a molecular weight of 5 × 10 ⁵ containing a hydroxyl group in the molecule)
-Acrylic polyol resin: 20 parts by weight-Pigment (mainly petrol, carbon black) ... 30 parts by weight-Hexamethylene diisocyanate ... 10 parts by weight Next, the transparent protective layer ink having the following composition from above the pattern layer 1 was used to form a transparent protective layer (thickness 3 μm after aging at 40 ° C. for 48 hours) by gravure printing. Thus, an exterior decorative sheet (Sample 1) was obtained.
[0032]
Composition of ink 1 for transparent protective layer Polyethylene trifluoride: 67 parts by weight (with a molecular weight of 5 × 10 ⁵ containing a hydroxyl group in the molecule)
Acrylic polyol resin: 33 parts by weight Hexamethylene diisocyanate: 15 parts by weight (Preparation of sample 2)
An exterior decorative sheet (Sample 2) was obtained in the same manner as Sample 1, except that Pattern Layer Ink B having the following composition was used as the pattern layer ink.
[0033]
Composition of pattern layer ink B: Polytrifluoroethylene: 50 parts by weight (with a molecular weight of 5 × 10 ⁵ containing a hydroxyl group in the molecule)
• Acrylic polyol resin: 50 parts by weight • Pigment (mainly petrol, carbon black): 30 parts by weight • Hexamethylene diisocyanate: 10 parts by weight (Preparation of sample 3)
An exterior decorative sheet (Sample 3) was obtained in the same manner as Sample 1, except that Pattern Layer Ink C having the following composition was used as the pattern layer ink.
[0034]
Composition of pattern layer ink C: poly (trifluorotrifluoroethylene) 90 parts by weight (with a molecular weight of 5 × 10 ⁵ containing a hydroxyl group in the molecule)
Acrylic polyol resin: 10 parts by weightPigment (mainly petrol, carbon black): 30 parts by weightHexamethylene diisocyanate: 10 parts by weight (Preparation of sample 4)
An exterior decorative sheet (Sample 4) was obtained in the same manner as Sample 1, except that the transparent protective layer ink 2 having the following composition was used as the transparent protective layer ink.
[0035]
Composition of ink 2 for transparent protective layer: Polytrifluoroethylene : 50 parts by weight (with a molecular weight of 5 × 10 ⁵ containing a hydroxyl group in the molecule)
Acrylic polyol resin: 50 parts by weight Hexamethylene diisocyanate: 15 parts by weight (Preparation of sample 5)
An exterior decorative sheet (Sample 5) was obtained in the same manner as Sample 1, except that the transparent protective layer ink 3 having the following composition was used as the transparent protective layer ink.
[0036]
Composition of ink 3 for transparent protective layer Polyethylene trifluoride: 90 parts by weight (with a molecular weight of 5 × 10 ⁵ containing a hydroxyl group in the molecule)
Acrylic polyol resin: 10 parts by weight Hexamethylene diisocyanate: 15 parts by weight (Preparation of sample 6)
Sample 1 except that a base film made of polyvinylidene fluoride (PVDF) as a main component and a polymethyl methacrylate added thereto (DX film (thickness 40 μm) manufactured by Electrochemical Co., Ltd.) was used. In the same manner as above, an exterior decorative sheet (Sample 6) was obtained.
(Preparation of sample 7)
The same as sample 1 except that a polyvinyl chloride (PVC) film (manufactured by Sanpo Resin Co., Ltd. (thickness: 200 μm)) containing 23 parts by weight of a plasticizer with respect to 100 parts by weight of the resin was used as the base film. Thus, an exterior decorative sheet (Sample 7) was obtained.
(Preparation of sample 8)
An exterior decorative sheet (Sample 8) was obtained in the same manner as Sample 1, except that the pattern layer ink D having the following composition was used as the pattern layer ink.
[0037]
Composition of the ink D for the pattern layer: Poly (trifluoroethylene) 30 parts by weight (with a molecular weight of 5 × 10 ⁵ containing a hydroxyl group in the molecule)
• Acrylic polyol resin: 60 parts by weight • Pigment (mainly petrol, carbon black): 30 parts by weight • Hexamethylene diisocyanate: 9 parts by weight (Preparation of sample 9)
An exterior decorative sheet (Sample 9) was obtained in the same manner as Sample 1, except that the pattern layer ink E having the following composition was used as the pattern layer ink.
[0038]
Composition of the ink E for the pattern layer , poly (trifluoroethylene): 120 parts by weight (with a molecular weight of 5 × 10 ⁵ containing a hydroxyl group in the molecule)
-Acrylic polyol resin: 10 parts by weight-Pigment (mainly petrol, carbon black): 30 parts by weight-Hexamethylene diisocyanate: 13 parts by weight (Preparation of sample 10)
An exterior decorative sheet (Sample 10) was obtained in the same manner as Sample 1, except that the transparent protective layer ink 4 having the following composition was used as the transparent protective layer ink.
[0039]
Composition of ink 4 for transparent protective layer Polyethylene trifluoride: 30 parts by weight (with a molecular weight of 5 × 10 ⁵ containing a hydroxyl group in the molecule)
Acrylic polyol resin: 60 parts by weight Hexamethylene diisocyanate: 14 parts by weight (Preparation of sample 11)
An exterior decorative sheet (Sample 11) was obtained in the same manner as Sample 1, except that the transparent protective layer ink 5 having the following composition was used as the transparent protective layer ink.
[0040]
Composition of ink 5 for transparent protective layer Polyethylene trifluoride: 120 parts by weight (with a molecular weight of 5 × 10 ⁵ containing a hydroxyl group in the molecule)
Acrylic polyol resin: 10 parts by weight Hexamethylene diisocyanate: 20 parts by weight (Preparation of sample 12)
As a base film, a polyvinyl chloride (PVC) film (manufactured by Sanpo Resin Co., Ltd. (thickness: 200 μm)) containing 23 parts by weight of a plasticizer with respect to 100 parts by weight of a resin is prepared. A pattern layer (thickness 3 μm) of a stone pattern was formed by gravure printing using the ink F for pattern layer.
[0041]
Composition of ink F for pattern layer · Acrylic resin · · 80 parts by weight · Vinyl chloride-vinyl acetate copolymer · · 20 parts by weight · Pigment (mainly petrol and carbon black) · 30 parts by weight Next, the above pattern layer From above, a transparent protective layer (thickness 3 μm) was formed by gravure printing using the transparent protective layer ink 6 having the following composition. This obtained the exterior decorative sheet (sample 12).
[0042]
Composition of ink 6 for transparent protective layer: Acrylic silicone: 80 parts by weight. Vinyl chloride-vinyl acetate copolymer: 20 parts by weight (evaluation)
About each exterior decorative sheet (samples 1-12) produced as mentioned above, the weather resistance, solvent resistance, and contamination resistance were evaluated on the following conditions, and the result was shown in following Table 1.
[0043]
Conditions for evaluating weather resistance Exposed for 10,000 hours in a sunshine carbon arc lamp type weatherometer (manufactured by Suga Test Instruments Co., Ltd.), the discoloration state was visually evaluated according to the following criteria. In addition, 18 minutes per 120 minutes was set as the rain time, and the black panel temperature was 63 degreeC.
[0044]
(Evaluation criteria)
○: No discoloration, fading, cracks, or delamination Δ: Discoloration or fading is observed slightly ×: Discoloration, fading is remarkable, cracks, delamination are also observed
Conditions for evaluating solvent resistance The conditions of the transparent protective layer and the pattern layer after being immersed in methyl ethyl ketone for 30 days were evaluated according to the following criteria.
[0045]
(Evaluation criteria)
○: Ink is not dissolved at all Δ: Ink is slightly dissolved ×: The ink is dissolved and the pattern is significantly disturbed
Evaluation conditions for stain resistance <br/> Draw letters, lines, etc. with oil-based red magic ink, crayon, ink on the transparent protective layer of the exterior decorative sheet, and then visually observe the state wiped with a cloth containing petroleum benzine Based on the following criteria.
[0046]
(Evaluation criteria)
○: No color residue on the transparent protective layer is observed Δ: Some color residue on the transparent protective layer is observed ×: Color residue on the transparent protective layer is remarkable Next, as described above The prepared exterior decorative sheets (samples 1 to 12) are laminated on a steel plate having a thickness of 0.6 mm at a heating temperature of 180 to 200 ° C. to make an exterior material, and the processability of each exterior material is evaluated under the following conditions. The results are shown in Table 1 below.
[0047]
Evaluation conditions for workability According to the Erichsen test of JIS K6744, the condition of the exterior decorative sheet in bending and drawing was visually evaluated according to the following criteria.
[0048]
(Evaluation criteria)
○: No change is observed in the bent portion and the drawn portion Δ: Some cracks and whitening are observed in the bent portion, and some peeling is observed in the drawn portion ×: Cracks and whitening are observed in the bent portion , The peeling of the drawn part is remarkable. [0049]
[Table 1]

As shown in Table 1, Samples 1 to 6 were good in weather resistance, solvent resistance, stain resistance and processability.
[0050]
Samples 8 to 11 in which the weight ratio of polytrifluoride ethylene and acrylic polyol resin in the pattern layer or the transparent protective layer deviates from the range of 1: 1 to 9: 1 are weather resistance compared to samples 1 to 6, Any of solvent resistance, contamination resistance and processability was inferior.
[0051]
On the other hand, Sample 7 using PVC as the base film and Sample 12 which is a conventional exterior decorative sheet had insufficient weather resistance, solvent resistance, contamination resistance and processability.
[0052]
【The invention's effect】
As described above in detail, according to the present invention, a base film mainly composed of at least one of polyvinyl fluoride and polyvinylidene fluoride is mainly composed of a mixture of poly (ethylene trifluoride) and an acrylic polyol resin. A pattern layer composed of a resin component and a pigment is provided, and a transparent protective layer mainly composed of a mixture of poly (trifluoroethylene) and acrylic polyol resin is formed on the base film so as to cover the pattern layer. Because it is a decorative sheet, the base film exhibits good adhesion to metal plates and other layers, and flexibility and weather resistance are imparted by polytrifluoride ethylene that constitutes the pattern layer and the transparent protective layer. The acrylic polyol resin constituting the pattern layer and the transparent protective layer imparts printability, adhesiveness and appropriate hardness, and has flexibility and excellent workability. In, it is possible to exterior decorative sheets with a high weather resistance.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an embodiment of an exterior decorative sheet of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Exterior decorative sheet 2 ... Base film 3 ... Picture layer 4 ... Transparent protective layer

Claims (5)

In the exterior decorative sheet for bonding metal plates,
A base film, a picture layer formed on the base film, and a transparent protective layer formed on the base film so as to cover the picture layer, the base film comprising polyvinyl fluoride and as a main component at least one of polyvinylidene fluoride, wherein the pattern layer comprises at least a resin component and a pigment, said resin component as a main component a mixture of poly ethylene trifluoride and acrylic polyol resin, poly in the pattern layer The weight ratio of ethylene trifluoride and acrylic polyol resin is in the range of 1: 1 to 9: 1, and the transparent protective layer is mainly composed of a mixture of polytrifluoroethylene and acrylic polyol resin , the weight ratio of poly ethylene trifluoride and acrylic polyol resin in the transparent protective layer 1: 1-9: exterior decorative sheet, characterized in that within the first range 2. The exterior decorative sheet according to claim 1, wherein the polytrifluoride ethylene has an average molecular weight in the range of 3 × 10 ^{5 to} 6 × 10 ⁵ . The exterior decorative sheet according to claim 1 or 2, wherein at least one of the base film, the pattern layer, and the transparent protective layer contains an ultraviolet absorber. The exterior decorative sheet according to any one of claims 1 to 3 , wherein at least one of the base film, the pattern layer, and the transparent protective layer contains an antioxidant. Any thickness of the base film is 10 to 100 [mu] m, the thickness of the pattern layer is 2-6 [mu] m, the thickness of the transparent protective layer of claims 1 to 4, characterized in that in the range of 2~10μm The exterior decorative sheet according to crab.

Images