JPWO2003045690A1 - Laminated resin sheet, embossed sheet and coated substrate - Google Patents

Abstract

Embossing sheet that can use the current embossing device for PVC without causing problems of sheet fusing, sticking to a heating roll or winding even when using the current embossing device for PVC, and this embossing The coated substrate using a sheet is made of a resin composition that is substantially amorphous or low crystalline or an embossable layer (A) that contains a large amount of the resin composition that is substantially amorphous or low crystalline. Layer) and a substantially crystalline resin composition or a base material layer (B layer) containing a large amount of the substantially crystalline resin composition, The A layer enables embossing.

Description

表１及び表２から明らかなように、Ａ層が非晶性、Ｂ層が結晶性である本発明品に相当する実施例１〜実施例４の積層樹脂シートは、エンボス付与時、加熱ロールへの貼り付きがなく、エンボス付与が可能であった。
これに対し、Ｂ層が非晶性の比較例１，２は加熱ロールに貼り付き、エンボス付与がうまくいかなかった。比較例４も高温になると貼り付きが発生した。
また、Ａ層が結晶性である比較例２，４，５はエンボス付与ができなかった。実施例３と比較例３のエンボス付与結果の差は、上地層（延伸ＰＥＴ）の高温弾性率、延伸倍率等の差による。
＜第２の発明＞
各実施例及び比較例に用いたシートの樹脂組成を表３に示す。なお、試験で使用した原料は以下のとおりである。
・実質非晶性のポリエステル系樹脂：ＥＡＳＴＥＲ６７６３ イーストマンケミカル（株）製（ガラス転移点；８１［℃］、結晶融解ピーク温度；観測されず）・実質結晶性のポリエステル系樹脂：ＮＯＶＡＤＵＲ５００８ 三菱エンジニアリングプラスチック（株）製（ガラス転位点；４６［℃］、結晶融解ピーク温度；２２１［℃］）

（実施例５〜７、比較例６〜１１）
製膜にはＴダイを備えた二軸混練押出機を用いて、総厚み１５０μｍになるように調整した。続いて前記４種類のエンボス付与方法にて、エンボス付与を行い、それぞれの評価を行った。但し、１−１及び１−２の方法の場合は、シートにて評価を行い、２−１及び２−２の方法の場合は、被覆基材にてそれぞれ評価を行った。なお、金属板（鋼板）との積層にはポリエステル系の熱硬化性接着剤を使用した。結果を表４に示す。

表４から明らかなように、本発明の範囲にある実施例５〜実施例７の積層シートは、全てのエンボス付与方法が適応可能であった。これに対し、本発明の範囲外の比較例６〜１１の積層シート及び単層シートでは、エンボス付与方法１−１、２−１及び２−２によるエンボス付与は可能であったが、１−２によるエンボス付与は種々の問題発生により実現できなかった。
そこで発生した不具合点について説明する。単層シートにおいて、実質結晶性のポリエステル系樹脂（比較例８）あるいは、実質結晶性のポリエステル系樹脂を主成分とした混合物（比較例９）では、比較的高温まで加熱ロールへの粘着はないが、エンボスを付与するため融点以上まで昇温すると、シートが溶断してしまった。
単層シートにおいて、実質非晶性のポリエステル系樹脂（比較例１０）あるいは実質非晶性のポリエステル系樹脂を主成分とした混合物（比較例１１）では、加熱ロールへ粘着してしまった。
比較例６の積層シート、即ち、Ａ層を構成するポリエステル系樹脂として実質結晶性のポリエステル系樹脂を主成分とする混合物を用いた場合、エンボスを付与するために、シートの温度を樹脂Ａの融点以上まで上げると、Ｂ層を構成するポリエステル系樹脂も同様に軟化してしまい、基材の役割を果たせず、シートが溶断してしまった。
比較例７の積層シート、即ち、Ｂ層を構成するポリエステル系樹脂が実質非晶性のポリエステル系樹脂を主成分とする混合物を用いた場合、実質非晶性のポリエステル系樹脂あるいは実質非晶性のポリエステル系樹脂を主成分とした混合物の単層シートの結果（比較例１０，１１）と同様に加熱ロールに粘着してしまった。
＜第３の発明＞
（実施例８〜１９、比較例１２〜２２）
［積層樹脂シートの作製］
Ａ層を構成するポリエステル系樹脂として表５に示す樹脂組成を用い、Ｂ層を構成するポリエステル系樹脂として表６に示す樹脂組成を用い、表１０に示す組合せで積層樹脂シートを作製した。総厚み１７０μｍでエンボス付与可能層１２の厚みが１４０μｍ、基材層１３の厚みが３０μｍとした。
なお、比較例の一部に関しては、表７に示す厚み１７０μｍの単層シートを用いており、また、比較例２２では被覆基材用に一般的に使用されている厚み１５０μｍのカレンダー法によるポリプロピレン系軟質樹脂シートを用いている。
シート製膜方法は、上記比較例の一部を除き、二軸混練押出機を２台使用したフィードブロック方式の共押出製膜であり、Ｔダイより流出した樹脂をキャスティングロールで引き取る一般的方法に依っている。表７に示す単層のシートは二軸混練押出機１台で同様に製膜したものである。
また、表５〜表７で使用した各原料は以下の通りである。
・実質結晶性のポリエステル系樹脂（１）：ＮＯＶＡＤＵＲ５００８三菱エンジニアリングプラスチック（株）製ポリブチレンテレフタレート系樹脂（ガラス転位点；４６［℃］、結晶融解ピーク温度；２２１［℃］）
・実質結晶性のポリエステル系樹脂（２）：ＮＯＶＡＤＵＲ５０２０Ｓ三菱エンジニアリングプラスチック（株）製ポリブチレンテレフタレート系樹脂（ガラス転位点；４５［℃］、結晶融解ピーク温度；２２３［℃］）
・実質非晶性のポリエステル系樹脂：ＥＡＳＴＥＲ６７６３イーストマンケミカル（株）製（ガラス転移点；８１［℃］、結晶融解ピーク温度；観測されず）

なお、表５〜表９における「ｐｈｒ」は、樹脂分を１００とした場合の添加剤の重量比率（重量部）を意味する。
［透明被覆層の付与］
表８に示すコーティング塗膜、若しくは表９に示すフィルムを積層樹脂シートのエンボス付与可能層側に設けた。積層樹脂シートとの組合せ及び透明被覆層の厚みは表１０に示した。コーティング塗膜はロールコーターによる塗布後、加熱乾燥を行うものである。実施例１１のみ積層シートにエンボス付与装置３０でエンボス模様を付与した後に透明被覆層を設けた。
フィルムを積層する場合はフィルムの接着面側にシアネート架橋型のポリエステル系接着剤を塗布、乾燥後、積層樹脂シートのＡ層側表面と重ね合わせ、５０℃に加熱された金属ロールとゴムロールの間を通過させることで加熱、加圧して積層一体化した。
また、表８及び表９で使用した各原料は以下の通りである。
・アクリルポリオール：一般的にアクリルワニスに使用されるものの中では比較的ガラス転位温度（Ｔｇ）の低いグレード。
・ユーダブルＵＶＧ−１００：ＨＡＬＳ
・紫外線吸収剤共重合型架橋性アクリル樹脂。日本触媒（株）製
・ルミフロンＬＦ−２００：フロロエチレン・ビニルエーテル共重合体 旭硝子（株）製
・シリコーングラフトアクリル：Ｘ２２−８００４ 水酸基含有のもの 信越シリコーン（株）製
・アクリルフィルム半硬質：市販のフィルムグレードアクリル樹脂の原料パウダーを単軸押出機を用い製膜。引張り破断伸び１１０％程度（２３℃、引張り速度２００ｍｍ／ｍｉｎ）。
・アクリルフィルム軟質：市販のフィルムグレードアクリルと柔軟性アクリル樹脂の原料パウダーを混合し、単軸押出機を用い製膜。引張り破断伸び２００％程度（２３℃、引張り速度２００ｍｍ／ｍｉｎ）。
・チヌビン４００：トリアジン系紫外線吸収剤、分子量＝６４７ チバスヘシャリティ ケミカルス（株）製
・ＰＵＶＡ−５０Ｍ：高分子量（ＭＭＡ共重合型）紫外線吸収剤、分子量＝約１００００ 大塚化学（株）製
・ＬＡ−３１：ベンゾトリアゾール系紫外線吸収剤、分子量＝６５９ 旭電化（株）製［エンボス模様の付与］
軟質塩化ビニル系シートでも一般的に使用されている連続法による図３に示すエンボス付与装置３０にて、エンボス模様の付与を行った。連続法によるエンボス付与の概略としては、まず金属加熱ロールを用いた接触型加熱によりシートの予備加熱を行い、続いて赤外ヒーターを用いた非接触型加熱により任意の温度までシートを加熱し、エンボスロールによりエンボス模様を転写させるものである。
［被覆基材の作製］
次にポリ塩化ビニル被覆金属板用として一般的に用いられているポリエステル系接着剤を、金属面に乾燥後の接着剤膜厚が２〜４μｍ程度になるように塗布して熱硬化型接着剤を形成する。次いで熱風加熱炉及び赤外線ヒーターにより塗布面の乾燥及び加熱を行い、亜鉛メッキ鋼板（厚み０．４５ｍｍ）の表面温度を２３５℃に設定し、直ちにロールラミネーターを用いて積層樹脂シート（ポリエステル系樹脂シート）を被覆、冷却することにより樹脂被覆鋼板を作製した。
［積層樹脂シート及び被覆基材の評価］
前記各項目を評価した。結果を表１１にまとめて示した。

表１１から明らかなように、本発明の範囲にある実施例８〜実施例１９では、ＰＶＣシートへのエンボス付与に用いられてきたエンボス付与装置によるエンボス付与において、粘着やシートの溶断を生ぜずに良好なエンボス模様の転写が得られるとともに、耐候性に優れ、加工性及び表面硬度のいずれも良好であった。
これに対し、本発明の範囲外の比較例１２〜２２の積層シート及び単層シートでは、エンボス付与適性、耐候性、加工性及び表面硬度のうち少なくとも一つが不合格（×）の評価となった。
比較例１２及び比較例１３は、紫外線吸収性を有する透明被覆層が無い場合であるが、耐候性促進試験の結果、いずれも問題が発生している。即ち、Ａ層への酸化チタン顔料の添加量が多い比較例１２では顕著な噴き出しが発生し、比較的顔料添加量の少ない比較例２では樹脂自体の黄変が目立っていた。
比較例１４は透明被覆層の厚みを本発明の範囲より厚く（２５μｍ）したものであるが、エンボス模様の転写性が劣っている。また、透明被覆層の厚みを本発明の範囲より厚くしたことにより、加工性も劣った。
比較例１５は「エンボス付与可能層１２＋基材層１３」の構成の積層樹脂シートを用いず、Ａ層に好ましい組成の単層シートを用いたものであるが、エンボス付与装置３０の加熱された金属ロールへの粘着を生じ、エンボスを付与することができなかった。これに対し、比較例１６はＢ層に好ましい組成の単層シートを用いたもので、加熱された金属ロールへの粘着は生じないものの、通常のＰＶＣシートへのエンボス付与条件ではエンボス模様の転写が全く得られなかった。
比較例１７は積層シートを用いているが、Ａ層となるべき層の組成が実質結晶性の組成のため、比較例１６と同様の結果となった。
比較例１８〜比較例２１は、積層樹脂シートのＡ層の表面に厚み５０μｍのアクリルフィルムを積層したものであり、アクリルフィルムが実質的にエンボス付与可能層として作用し、Ａ層の組成に拘わらずエンボス模様の転写は可能であった。しかし、紫外線吸収剤を添加しない比較例２０及び比較例２１では、耐候性は改善されておらず、しかも、耐候性評価後のサンプルではアクリルフィルムが部分的に剥離した。
一方、紫外線吸収剤が添加された比較例１８及び比較例１９では、ポリエステル系樹脂より成るＡ層及びＢ層の変色を効果的に抑制している。しかし、比較的硬質のアクリルフィルムを積層した比較例１８、比較例２０及び比較例２１の場合は、曲げ加工時に完全にアクリルフィルムが破断し、加工性が劣る。また、比較的軟質のアクリルフィルムを積層した比較例１９の場合は、加工性には問題が出なかったが、表面硬度は問題があった。そして、比較的硬質のアクリルフィルムを積層した比較例１８、比較例２０及び比較例２１の場合も、本発明である各実施例に比較して表面硬度が劣っていた。
また、比較例２２の被覆基材用のＰＰ系樹脂フィルムの単層シートを使用した場合は、表面硬度が軟質ＰＶＣに比較して劣っていた。
＜第４の発明＞
（実施例２０〜３３、比較例２３〜３４）
［積層樹脂シートの作製］
Ａ層を形成する樹脂として表１２に示す樹脂組成を用い、Ｂ層を形成する樹脂として表１３に示す樹脂組成を用い、表１５及び表１７に示す組合せで積層樹脂シートを作製した。総厚み１５０μｍでＡ層の厚みが１２０μｍ、Ｂ層の厚みが３０μｍとした。また、Ａ層を形成する樹脂は酸化チタン系のベージュ色顔料を１７重量部（樹脂分全量を１００重量部として）含んでいる。なお、表１４は表１２及び表１３の各樹脂組成におけるＡ層を形成する樹脂及びＢ層を形成する樹脂のＤＳＣ測定値を示す。

シート製膜方法は、二軸混練押出機を２台使用したフィードブロック方式の共押出し製膜であり、Ｔダイより流出した樹脂をキャスティングロールで引き取る一般的方法に依っている。キャスティングロールは鏡面のものを使用し、温水循環装置により６５℃にロール温度を保った。
なお、比較例３０のシートに関しては、キャスティングロールでの引き取り後に、赤外ヒーターを有する加熱炉内に導入し、非接触加熱で１６０℃×４０秒間の後加熱処理を行った。
また、表１２及び表１３で使用した各原料は以下の通りである。
・ノバデュラン５００８：ホモＰＢＴ 樹脂 三菱エンジニアリングプラスチック（株）製（ガラス転移点；４６［℃］、結晶融解ピーク温度；２２１［℃］）・ノバデュラン５０２０Ｓ：ホモＰＢＴ樹脂 三菱エンジニアリングプラスチック（株）製（ガラス転移点；４５［℃］、結晶融解ピーク温度；２２３［℃］）・デュラネックス５００ＪＰ：イソフタル酸共重合ＰＢＴ樹脂 ウィンテックポリマー（株）製（ガラス転移点；３２［℃］、結晶融解ピーク温度；２０４［℃］）
・ｃｏ−ＰＥＴ ＢＫ−２１８０：イソフタル酸共重合ＰＥＴ樹脂 三菱化学（株）製（ガラス転移点；７６［℃］、結晶融解ピーク温度；２４６［℃］）
・コルテラＣＰ５０９２００：ホモＰＴＴ樹脂 シェル（株）製（ガラス転移点；４９［℃］、結晶融解ピーク温度；２２５［℃］）
・イースター６７６３：ポリエチレンテレフタレートのエチレングリコール部分の約３１％を１，４−シクロヘキサンジメタノールで置換した非晶性ポリエステル系樹脂 イーストマンケミカル（株）製（ガラス転移点；８１［℃］、結晶融解ピーク温度；観測されず）
・ＰＣＴＧ５４４５：ポリエチレンテレフタレートのエチレングリコール部分の約７０％を１，４−シクロヘキサンジメタノールで置換した非晶性ポリエステル系樹脂 イーストマンケミカル（株）製（ガラス転移点；８８［℃］、結晶融解ピーク温度；観測されず）
［エンボス模様の付与］
軟質ＰＶＣシートでも一般的に使用されている図３に示すエンボス付与装置３０にて、連続法によるエンボス模様の付与を行った。連続法によるエンボス付与の概略としては、まず金属加熱ロールを用いた接触型加熱によりシートの予備加熱を行い、続いて赤外ヒーターを用いた非接触型加熱により任意の温度までシートを加熱し、エンボスロールによりエンボス模様を転写させるものである。加熱ドラムは１００℃に設定し、実施例２０〜２９及び比較例２３〜３０に関しては、ヒーターにより、エンボスロールと接する前のシートが１６５℃に加熱される。また、エンボスロールの温度は８０℃である。
実施例３０〜３３及び比較例３１〜３４に関しては、加熱ドラムは１００℃に設定し、ヒーター加熱によるシート温度を変更したものである。この場合もエンボスロールの温度は８０℃である。
［被覆基材の作製］
次にポリ塩化ビニル被覆金属板用として一般的に用いられているポリエステル系熱硬化型接着剤を、金属面に乾燥後の接着剤膜厚が２〜４μｍ程度になるように塗布して熱硬化型接着剤層を形成する。次いで熱風加熱炉及び赤外線ヒーターにより塗布面の乾燥及び加熱を行い、亜鉛メッキ鋼板（厚み０．４５ｍｍ）の表面温度を２３５℃に設定し、直ちにロールラミネーターを用いて積層樹脂シート（ポリエステル系樹脂シート）を被覆、水冷にて冷却することによりエンボス意匠性樹脂被覆鋼板を作製した。
［積層樹脂シート及び被覆基材の評価］
前記各項目を評価した。結果を表１６及び表１８にまとめて示した。表１６中、エンボス付与装置の加熱ドラムに粘着を生じたものに関しては、以降の評価を行っておらず、表１８中、ラミネート時のエンボス戻りが顕著なものに関しては高温耐熱性の評価を実施していない。
比較例２３はＡ層を形成する樹脂として完全非結晶性樹脂のみを用いた場合であるが、Ｂ層を形成する樹脂として本発明の要件に合致するものを用いていることにより、エンボス付与装置でのシートの粘着や溶融破断は生じていない。ただ、Ａ層を形成する樹脂の組成自体が耐沸騰水性を有するものではないため、沸騰水に浸漬することでエンボス柄は完全に消失していた。
比較例２４では、Ａ層を形成する樹脂が結晶性を有しているが、ΔＨｍの値が本発明の範囲より低い。この場合も比較例２３と同様に沸騰水に浸漬することでエンボス柄が完全に消失していた。
比較例２５は、Ａ層を形成する樹脂の「（ΔＨｍ（Ａ）−ΔＨｃ（Ａ））／ΔＨｍ（Ａ）」の値が本発明の範囲より高い場合で、エンボス柄転写性が悪くなっており、更に「（ΔＨｍ（Ａ）−ΔＨｃ（Ａ））／ΔＨｍ（Ａ）」が大きな値となる比較例２６ではエンボス柄転写が困難であった。Ａ層を形成する樹脂がエンボスロールに通される前から比較的高い結晶性を有していると、ヒーターによるシート加熱を行ってもシートの弾性率が低下せず、エンボスロールで押圧しても充分な歪み（エンボス柄転写）を付与できないことによる。
比較例２７は、Ａ層を形成する樹脂の組成が本発明の要件を満たすが、結晶性樹脂として結晶化速度の遅いイソフタル酸共重合のポリエチレンテレフタレート樹脂を用いていることにより、実質的に樹脂Ａが完全非結晶性の場合と同様の挙動を示し、比較例２３及び比較例２４と同様に耐沸騰水性が悪い。
比較例２８及び比較例２９は、Ｂ層を形成する樹脂の「（ΔＨｍ（Ｂ）−ΔＨｃ（Ｂ））／ΔＨｍ（Ｂ）」の値が本発明の範囲より低い場合で、エンボス付与装置の加熱ドラムに積層シートが粘着を生じ、シートにエンボス模様を付与することができなかった。
比較例３０は、比較例２９と同一組成・構成のシートに対し、後加熱処理を施したもので、該加熱処理でＢ層を形成する樹脂の結晶化が進行し、これによって加熱ドラムへの粘着性は改善されている。ただし、積層シートの状態で後加熱処理を実施したため、Ａ層を形成する樹脂も結晶化が進行してしまい、エンボス柄の転写が困難となってしまった。
これらの比較例に対し、本発明の要件を満たす実施例２０〜実施例２９では、加熱ドラムへの粘着やヒーター加熱時のシート破断を生じず、良好なエンボス柄転写性が得られている。また、Ａ層を形成する樹脂が沸騰水浸漬に耐えるだけの結晶性を有している。
実施例３０〜実施例３３及び比較例３１〜比較例３４は、同一構成・組成のシートを用い、エンボスロールを通る前のシート温度を変えたものであるが、比較例３１及び比較例３２ではラミネート時にエンボス戻りが顕著に発生した。これは歪み（エンボス柄転写）を付与する温度が低かったことにより、ラミネート時に鋼板からの熱でシート温度が歪みを付与した温度近くまで上昇し、凍結されていた残留応力が開放されたことに起因する。
比較例３３及び比較例３４は、歪みを付与する温度を比較例３１及び比較例３２より高くしたものであり、ラミネート時のエンボス戻りは改善の傾向にあるが、まだ、従来の軟質ＰＶＣシートに及ばない。また、ラミネート鋼板としてのエンボスの高温耐熱性も充分ではない。
これらに対して、実施例３０〜実施例３３においては、ラミネート時のエンボス戻りが少なく、従来の軟質ＰＶＣシートと同等以上であり、ラミネート鋼板としての高温耐熱性も実用上充分なレベルが得られている。
＜第５の発明＞
（実施例３４〜４４、及び比較例３５〜４１の積層用シートの作成）
Ａ層として表１９に示す樹脂組成を用い、Ｂ層として表２０に示す樹脂組成を用い、それぞれ単層のシートを作成した。Ａ層は厚み７０μｍで、顔料は添加されていない。Ｂ層は厚み６０μｍで、酸化チタン系の顔料が２０重量部（樹脂分重量を１００として）添加されている。シートの製膜方法は二軸混練押出機を使用したＴダイ製膜法で、Ｔダイより流出した樹脂をキャスティングロールで引き取る一般的方法に依っている。キャスティングロールは鏡面のものを使用し、温水循環により６５℃に保たれている。各実施例及び比較例に使用したＡ層とＢ層の組み合わせは表２１に示す。尚、実施例４４のＢ層に関しては、キャスティングロールでの引き取り後に、赤外ヒーターを有する加熱炉内に導入し、非接触加熱で１６０℃×４０秒間の後加熱処理を行った。
次いでＢ層の表面に無架橋のポリエステル系ビヒクルを使用した印刷インクで抽象柄の部分印刷を施した。印刷層の種類、塗布厚み、乾燥条件等は全ての実施例及び比較例について同一である。
また、表１９〜表２０で使用した各原料は以下の通りである。
・ノバデュラン ５０２０Ｓ：ホモＰＢＴ樹脂 三菱エンジニアリングプラスチック社製（ガラス転移点；４５［℃］ 結晶融解ピーク温度；２２３［℃］）
・デュラネックス ５００ＪＰ：イソフタル酸共重合ＰＢＴ樹脂 ウィンテックポリマー社製（ガラス転移点；３２［℃］ 結晶融解ピーク温度；２０４［℃］）
・ｃｏ−ＰＥＴ ＢＫ−２１８０：イソフタル酸共重合ＰＥＴ樹脂 三菱化学社製（ガラス転移点；７６［℃］ 結晶融解ピーク温度；２４６［℃］）
・コルテラ ＣＰ５０９２００：ホモＰＴＴ樹脂 シェル社製（ガラス転移点；４９［℃］ 結晶融解ピーク温度；２２５［℃］）
・イースター６７６３：ポリエチレンテレフタレートのエチレングリコール部分の約３１％を１、４−シクロヘキサンジメタノールで置換した非晶性ポリエステル系樹脂 イーストマンケミカル社製（ガラス転移点；８１［℃］ 結晶融解ピーク温度；観測されず［℃］）
・ＰＣＴＧ５４４５：ポリエチレンテレフタレートのエチレングリコール部分の約７０％を１、４−シクロヘキサンジメタノールで置換した非晶性ポリエステル系樹脂 イーストマンケミカル（株）製（ガラス転移点；８８［℃］ 結晶融解ピーク温度；観測されず［℃］）
（実施例３４〜４４、比較例３５〜４１のシートの積層一体化とエンボス模様の付与）
図３に示す軟質塩化ビニル系シートでも一般的に使用されている、連続法によるエンボス付与装置３０にて熱融着によるシートの積層一体化と、エンボス模様の付与を行った。連続法によるエンボス付与装置の概略としては、まず金属加熱ロールを用いた接触型加熱によりシートの予備加熱を行い、続いて赤外ヒーターを用いた非接触型加熱により任意の温度までシートを加熱し、エンボスロールによりエンボス模様を転写させるものである。加熱ドラムは１００℃に設定し、実施例３４〜４４、及び比較例３５〜４１に関しては、ヒーターにより、エンボス柄ロールと接する前のシートが１６５℃に加熱される。またエンボス柄ロールの温度は８０℃であり、表面平均粗さＲａ＝１０μｍの梨地ロールである。
（実施例４５〜５１、及び比較例４２、４３の積層樹脂シートの作成とエンボス模様の付与」）
Ａ層として表２３に示す樹脂組成と厚みの単層シートを用いた。また、Ｂ層として表２３に示す樹脂組成と厚みをを用い、更に一部の実施例に関してはＤ層を構成中に含んでいる。Ｄ層の組成は、酸化チタン系顔料を２０重量部（樹脂分重量を１００重量部として）含む以外はＡ層の組成Ａ−４と同一である。Ｄ層の有無と厚みに関しては表２３中に示した。
Ｄ層が介在しない場合は、Ａ層及びＢ層の製膜方法は実施例３４〜４４、比較例３５〜４１の場合と同様であり、Ｄ層が介在する場合は二機の二軸混練押出機を使用したフィードブロック方式による共押出しＴダイ製膜法で、Ｄ層とＢ層の共押出し積層シートを作成した。この場合もキャスティングロールは鏡面のものを使用し、温水循環により６５℃に保たれている。
次いでＢ層またはＤ層の表面に無架橋のポリエステル系ビヒクルを使用した印刷インクで抽象柄の部分印刷を施した。印刷層の種類、塗布厚み、乾燥条件等は全ての実施例及び比較例について同一である。またシートの積層一体化とエンボス模様の付与に関しては基本的に実施例３４〜４４、比較例３５〜４１の場合と同様であるが、エンボス柄ロールとしては平均表面粗さＲａ＝１０μｍ、及びＲａ＝２０μｍの２種類の梨地ロールを使用した。
（実施例５２〜５５、及び比較例４４〜４７の積層樹脂シートの作成とエンボス模様の付与）
Ａ層として表２５に示す樹脂組成を用い、Ｂ層として表２５に示す樹脂組成を用い、Ａ層は厚み８０μｍで、Ｂ層は厚み８０μｍで、それぞれ単層のシートを得た。印刷インキの付与、シートの積層一体化とエンボス模様の付与に関しては基本的に前述したと同一の方法であるが、加熱ドラムは１００℃に設定し、ヒーター加熱によるシート到達温度を変更したものである。この場合もエンボス柄ロールの温度は８０℃である。各実施例及び比較例に使用したＡ層とＢ層の組み合わせ、及びヒーター加熱によるシート到達温度は表７中に示した。
［被覆基材の作成］
次にポリ塩化ビニル被覆金属板用として一般的に用いられているポリエステル系熱硬化型接着剤を、金属面に乾燥後の接着剤膜厚が２〜４μｍ程度になる様に塗布し（接着剤層）、次いで熱風加熱炉および赤外線ヒーターにより塗布面の乾燥および加熱を行い、亜鉛めっき鋼板（金属板：厚み０．４５ｍｍ）の表面温度を２３５℃に設定し、直ちにロールラミネーターを用いてポリエステル系樹脂シートを被覆、水冷にて冷却することによりエンボス意匠性樹脂被覆鋼板を作製した。
（エンボス付与シート及び被覆基材の評価）
上記した各項目を評価した。結果を表２２、表２４及び表２６に示した。表２２中、エンボス付与装置の加熱ドラムに粘着を生じたものに関しては、以降の評価を行っておらず、表２４中、エンボス付与装置でシートが溶融破断したものに関しては以降の評価を行っていない。また、表２６中ラミネート時のエンボス戻りが顕著なものに関しては高温耐熱性の評価を実施していない。

比較例１０及び４１はＢ層を形成する樹脂の「（ΔＨｍ（Ｂ）−ΔＨｃ（Ｂ））／ΔＨｍ（Ｂ）」が本発明の請求の範囲より低い場合であり、エンボス付与装置の加熱ドラムに積層シートが粘着を生じ、従ってシートにエンボス模様を付与する事が出来なかった。
比較例３５はＡ層を形成する樹脂として完全非結晶性樹脂のみを用いた場合であるが、Ｂ層を形成する樹脂として本発明の請求の範囲に合致するものを用いている事により、エンボス付与装置でのシートの粘着や溶融破断は生じていない。ただ、樹脂Ａの組成自体が耐沸騰水性を有するものでは無い為、沸騰水に浸漬する事でエンボス柄は完全に消失している。
比較例３６では、Ａ層を形成する樹脂が結晶性を有しているが、ΔＨｍ（Ａ）の値が請求の範囲より低い。この場合も比較例３５と同様に沸騰水浸漬でエンボス柄が消失している。
比較例３９は、Ａ層を形成する樹脂の組成が本発明の要件を満たすが、結晶性樹脂として結晶化速度の遅いイソフタル酸共重合のポリエチレンテレフタレート樹脂を用いている事により、実質的に樹脂Ａが完全非結晶性の場合と同様の挙動を示し、比較例３５及び３６と同様に耐沸騰水性が悪い。
比較例３７は、Ａ層を形成する樹脂の「（ΔＨｍ（Ａ）−ΔＨｃ（Ａ））／ΔＨｍ（Ａ）」の値が本発明の範囲より高い場合で、エンボス柄転写性が悪くなっており、更に「（ΔＨｍ（Ａ）−ΔＨｃ（Ａ））／ΔＨｍ（Ａ）」が大きな値となる比較例３８ではエンボス柄転写が困難であった。Ａ層を形成する樹脂がエンボス柄ロールに通される前から比較的高い結晶性を有していると、ヒーターによるシート加熱を行っても、融点以下の温度ではシートの弾性率が低下せずエンボス柄ロールで押圧しても充分な歪み（エンボス柄転写）を付与できない事による。
これらに対して、本発明の実施例３４〜４４では、加熱ドラムへの粘着やヒーター加熱時のシート破断を生じず、良好なエンボス柄転写性が得られている。またＡ層を形成する樹脂が耐沸騰水浸漬に耐えるだけの結晶性を有している。
実施例４４は、比較例４１と同一のＡ層を形成する樹脂を用い、Ｂ層を形成する樹脂に関しても組成は同一であるがシート製膜後に熱処理を施した事により本発明の請求の範囲に合致するものとなり、良好なエンボス柄転写を得られている。また耐沸騰水性も良好である。
熱処理後のＢ−４のΔＨｍ（Ｂ）は２８．９（Ｊ／ｇ）、「（ΔＨｍ（Ｂ）−ΔＨｃ（Ｂ））／ΔＨｍ（Ｂ）」は０．８７であった。
実施例４５〜５１、及び比較例４２、４３は同一組成で厚みの異なるＡ層を構成する樹脂を用い、またＤ層の有無、Ｂ層を形成する樹脂の種類、厚みを変えたものであるが、比較例４２ではＡ層の厚みが厚い事によりエンボス転写性は良好であるが、エンボス付与後のＡ層のヘイズが大きく印刷層の透視性に劣る。また沸騰水に浸漬した後印刷層の透視性は更に悪化した。これは沸騰水浸漬によりＡ層の結晶化が進行し透明性が低下した事に起因する。
比較例４３はＢ層の厚みが好ましい範囲より薄い為、エンボス付与装置に通した際、Ｂ層に求められる機能が充分発現されず、ヒーターでの加熱によりシートの溶融破断を生じた。
実施例４５はＤ層を用いず、Ａ層の厚みを３０μｍとしたものだが、エンボスが付与されるべき層の厚みが薄い事からエンボス転写性がやや悪い結果となった。
実施例４６もＤ層無しでＡ層を５０μｍとしたものだが、細かい（浅い）梨地エンボスの転写は良好であったが、粗い（深い）エンボスの転写性は充分ではなかった。
実施例４７では、やはりＤ層無しで更にＡ層の厚みを厚くすることで、粗いエンボスの転写性も良好となったが、沸騰水浸漬後の印刷層の透視性がやや悪く、Ａ層を更に厚くした実施例４８では沸騰水に浸漬しない状態でもやや透視性が悪かった。
これらの印刷層透視性は、印刷柄や用途によっては実用上支障の無いものと判断され、印刷層の明瞭な透視性が求められる場合は問題となると判断された。印刷層の透視性がやや悪い原因は比較例８の場合と同様である。
実施例４９はＡ層の厚みは実施例４５と同様に３０μｍであるが、厚み５０μｍのＤ層を有しており、エンボスが付与される層としては合計８０μｍを有している。従って、実施例４７と同様に良好なエンボス転写性を得られると同時に、印刷層の透視性に関わるＡ層の厚みは実施例４５と同様である為、沸騰水浸漬後に於いても良好な印刷層の透視性が得られている。実施例５０に於いても同様である。
実施例５１は、エンボスが付与される層の構成・組成は実施例４９と同一で、Ｂ層の厚みを薄くしたものであるが、基本的なエンボス転写性や印刷層の透視性は良好であったが、エンボス付与装置でヒーター加熱された際シートの顕著な伸びが発生した。比較例４３のように溶融破断を起こす事は無かったが、Ｂ層の厚みとしては２０μｍが好ましい範囲の下限と判断された。
実施例５２〜５５、及び比較例４４〜４７は、同一構成・組成のシートを用い、エンボス柄ロールを通る前のシート温度を変えたものであるが比較例４４及び比較例４５ではラミネート時にエンボス戻りが顕著に発生した。これは歪み（エンボス柄転写）を付与する温度が低かった事により、ラミネート時に鋼板からの熱でシート表面温度が歪みを付与した温度近くまで上昇し、凍結されていた残留応力が解放された事に起因する。
比較例４６及び４７は、歪みを付与する温度を比較例４４及び４５より高くしたものであり、ラミネート時のエンボス戻りは改善の傾向にあるがまだ従来の軟質ＰＶＣ系シートに及ばない。またラミネート鋼板としてのエンボスの高温耐熱性も充分ではない。
これらに対して、実施例５２〜５５に於いてはラミネート時のエンボス戻りが少なく、従来の軟質ＰＶＣ系シートと同等以上であり、ラミネート鋼板としての高温耐熱性も実用上充分なレベルが得られている。
この実施の形態では以下の効果を有する。
［第１の発明］
（１） 実質的に非晶性あるいは低結晶性の樹脂組成物で構成されたＡ層と、実質的に結晶性の樹脂組成物で構成されたＢ層との２層構造のシートで、エンボス付与可能層Ａからエンボス付与が可能とした。従って、ＰＶＣシートへのエンボス付与に一般的に用いられるエンボス付与装置等により、エンボス付与可能層Ａからエンボス付与ができる。Ａ層がエンボス加工可能な温度に加熱された際にも、実質的に結晶性であるＢ層はシートとして剛性を持ち、加熱ロールに粘着しない。
（２） Ａ層のガラス転移温度をＴｇ（Ａ）、Ｂ層の融点をＴｍ（Ｂ）とし、エンボス加工温度をＴとしたとき、Ｔｇ（Ａ）≦Ｔ≦Ｔｍ（Ｂ）の関係にエンボス加工温度を設定可能としたので、エンボス加工が容易になる。
（３） Ａ層のガラス転移温度Ｔｇ（Ａ）［℃］と、Ｂ層の融点Ｔｍ（Ｂ）［℃］との関係を、Ｔｇ（Ａ）＋３０≦Ｔｍ（Ｂ）とした。従って、エンボス加工温度をＴとしたとき、Ｔｇ（Ａ）≦Ｔ≦Ｔｍ（Ｂ）の関係にエンボス加工温度を設定するのが容易になる。
（４） Ａ層の上にさらに印刷層及び透明な上地層を形成した場合、あるいはＡ層の上にさらに印刷層及び表面コートを形成した場合であっても、前記と同様にＡ層からエンボス付与ができ、より意匠性の高い積層樹脂シートが得られる。
（５） 積層樹脂シートの全層の総厚みが５０μｍ〜３００μｍである。従って、積層樹脂シートの金属板等の基材への貼り合わせ時あるいは、その後の穴開け加工や曲げ加工でシートが割れたりせず、また、エンボス付与も行い易くなる。
（６） Ａ層及びＢ層を無延伸の状態で積層した場合は、延伸シートを使用した場合と異なり、エンボス付与の際の加工温度の自由度が高くなる。
（７） Ａ層及びＢ層は、ともにポリエステル系樹脂で構成した場合、両層Ａ，Ｂを共押出し法で製膜する場合、押出し操作のし易さや、得られたシートの安定性が良好となるとともに、必要な物性を有する原材料を入手し易い。
（８） Ａ層を構成する非晶性樹脂組成物としてポリエチレンテレフタレートのエチレングリコールの一部（約３０〜６０モル％）を１，４−シクロヘキサンジメタノールで置換した非晶性ポリエステル系樹脂が使用され、Ｂ層を構成する結晶性樹脂組成物としてポリブチレンテレフタレートが使用されている。従って、（７）の効果がより向上する。
（９） 前記各積層樹脂シートにエンボス付与したシートを金属板、木質板、合板等の基材の少なくとも片面に被覆することにより、ＰＶＣを使用せずに、ドア、壁材、床材等の住宅内装建材、家具、調度品やエレベータ、ＡＶ製品等の家電製品の基材として好適に使用できる。
実施の形態は前記に限定されるものではなく、例えば、次のように具体化してもよい。
Ａ層の材質は実質的に非晶性で、基材層Ｂの材質は実質的に結晶性で、かつ、エンボス付与可能層Ａのガラス転移温度をＴｇ（Ａ）、Ｂ層の融点をＴｍ（Ｂ）とし、エンボス加工温度をＴとしたとき、Ｔｇ（Ａ）≦Ｔ≦Ｔｍ（Ｂ）の関係にエンボス加工温度を設定可能で、Ａ層からエンボス付与が可能であればよい。例えば、Ｂ層の材質にポリブチレンテレフタレート（ＰＢＴ）に代えてポリエチレンテレフタレート（ＰＥＴ）を使用してもよい。
Ａ層及びＢ層を構成するＰＢＴと、非晶性のポリエステル系樹脂であるＰＥＴＧとの混合比率を９／１と１／９の組合せ以外にしてもよい。
前記実施の形態から把握される技術的思想（発明）について、以下に記載する。
（１）第１の発明において、前記エンボス付与可能層を構成する非晶性樹脂組成物としてポリエチレンテレフタレートのエチレングリコールの一部（約３０〜６０モル％）を１，４−シクロヘキサンジメタノールで置換した非晶性ポリエステル系樹脂が使用され、前記基材層を構成する結晶性樹脂組成物としてポリブチレンテレフタレートが使用されている。
［第２の発明］
（１）実質非晶性のポリエステル系樹脂又は該ポリエステル系樹脂を主成分とする混合物よりなるＡ層と、実質結晶性のポリエステル系樹脂又は該ポリエステル系樹脂を主成分とする混合物よりなるＢ層とから積層樹脂シートを構成した。そして、Ｂ層はシート製膜後の示差走査熱量計（ＤＳＣ）による測定において、明確な結晶化ピークが観測されない状態まで結晶化している。従って、Ａ層がエンボス加工可能な温度に加熱された際にも、実質結晶性のＢ層はシートとして剛性を持ち、加熱ロールに粘着しない。その結果、従来、ポリエステル系樹脂シートでは対応できなかったシートの再加熱でのエンボス付与が可能になり、従来、軟質塩化ビニル系樹脂で用いられてきた種々のエンボス付与方法に対応でき、種々の方法でポリエステル系樹脂シートに対して連続的にエンボスを付与できる。
（２）Ｂ層を形成する樹脂の結晶融解ピーク温度（融点）をＴｍ（Ｂ）［℃］、樹脂Ａのガラス転位点をＴｇ（Ａ）［℃］とするとき、Ｔｍ（Ｂ）＞｛Ｔｇ（Ａ）＋３０｝の関係が成立する。従って、Ａ層に対して、Ｂ層を形成する樹脂の融点以下でエンボス付与が可能となり、エンボス付与が容易になる。
（３）Ａ層の上に、透明樹脂層を積層した場合は、透明樹脂層の存在により、深みのある意匠性の付与、表面の物性改良、ポリエステル系樹脂に添加された顔料等の添加剤の噴き出し防止が容易となる。
（４）Ａ層の上に、印刷を施して印刷層を形成し、その上に透明樹脂層を積層した場合は、種々の模様をＡ層に形成でき、意匠性を高めることができる。
（５）Ｂ層を形成する実質結晶性のポリエステルを、ポリブチレンテレフタレート又はその共重合体とした場合は、エンボス付与を良好に行うために、シート製膜時に基材層を十分に結晶化させるのが容易になり、エンボス付与を良好に行うのが容易になる。
（６）Ａ層を形成する実質非晶性のポリエステルが、ポリエチレンテレフタレートのシクロヘキサンジメタノール共重合体の場合、Ａ層を形成する樹脂を入手し易い。
（７）積層樹脂シートにエンボスを付与することにより、エンボス付与シートが得られる。従って、エンボス付与シートを得るために、従来、軟質塩化ビニル系樹脂で用いられてきた種々のエンボス付与方法を採用できる。
（８）積層樹脂シートを、Ｂ層を接着面として、熱硬化性接着剤を介して金属板の上に積層することにより、従来のエンボス付与方法でエンボス付与が容易にできる被覆基材を得ることができる。この被覆基材は、そのまま、あるいはエンボスを付与した状態で、ＡＶ器機やエアコンカバー等の家庭電化製品外装や鋼製家具、エレベータ内装、建築物内装等に好適に使用できる。
（９）エンボス付与シートを、Ｂ層を接着面として、熱硬化性接着剤を介して金属板の上に積層することにより、意匠性の高い被覆基材を容易に得ることができる。この被覆基材は、ＡＶ器機やエアコンカバー等の家庭電化製品外装や鋼製家具、エレベータ内装、建築物内装等に好適に使用できる。
（１０）積層樹脂シートの総厚みが５０〜５００μｍであるため、被覆基材用として使用した場合、金属板に対する保護層としての性能及び被覆基材としての打ち抜き加工等の二次加工性が劣るのを抑制できる。また、印刷を施した場合、印刷柄が下地金属板の色の影響を受け難い。
実施の形態は前記に限定されるものではなく、例えば、次のように具体化してもよい。
透明樹脂層を有するエンボス付与シートの製造方法は、２層構造の積層樹脂シートの状態、あるいはエンボス付与可能層上に印刷層が形成された状態でエンボス付与可能層にエンボスを付与し、その後、透明樹脂層を形成する方法に限らない。例えば、透明樹脂層が形成された積層樹脂シートに対して、透明樹脂層の上からエンボスを付与するようにしてもよい。
積層樹脂シート及びエンボス付与シートは金属板に接着剤を介して積層して被覆基材を形成する用途に限らず、木質板、合板等の基材に積層して使用してもよい。
前記実施の形態から把握される発明（技術的思想）について、以下に記載する。
（１） 第２の発明において、前記積層樹脂シートは、その総厚みが５０〜５００μｍである。
［第３の発明］
（１）Ａ層及びＢ層の少なくとも２層のポリエステル系樹脂層を積層したシートのＡ層の表面に、紫外線吸収性を有する透明被覆層が設けられている。従って、紫外線吸収性を有する厚み２μｍ〜２０μｍの範囲の透明被覆層の存在により、耐光性が良好になり、特にポリエステル系樹脂の光黄変性を改善でき、深みのある意匠性の付与、表面の物性改良、ポリエステル系樹脂に添加された顔料等の添加剤の噴き出し防止が容易となる。
（２）Ａ層を構成する樹脂が実質非晶性のポリエステル系樹脂又は該ポリエステル系樹脂を主成分とする混合物よりなり、Ｂ層を構成する樹脂が実質結晶性のポリエステル系樹脂又は該ポリエステル系樹脂を主成分とする混合物よりなる。更に、Ｂ層は、エンボス付与のために前記シートを加熱した際、金属ロールへの粘着性を示さず、かつ、樹脂成分Ｂの結晶融解ピーク温度（融点）をＴｍ（Ｂ）［℃］、樹脂成分Ａのガラス転位点をＴｇ（Ａ）［℃］とするとき、Ｔｍ（Ｂ）＞｛Ｔｇ（Ａ）＋３０｝の関係が成立する。従って、エンボス付与のためにシートを加熱した際、金属ロールへの粘着性を示さず、エンボス付与可能層に対して基材層の融点以下でエンボス付与が可能となり、加熱状態で基材層が溶融破断することが無く、エンボス付与が良好に行われる。そして、従来、軟質塩化ビニル系樹脂で用いられてきたエンボス付与装置でポリエステル系樹脂シートに対して連続的にエンボスを付与することが容易になる。
（３）透明被覆層が紫外線吸収成分を含有する架橋性樹脂のコーティング層を少なくとも一層含む場合は、透明被覆層に紫外線吸収性の他に、光沢の調整、耐傷入り性の更なる向上、耐汚染性の向上、深みのある意匠の付与等の副次的効果を付与するのが容易になる。
（４）前記紫外線吸収成分を添加型の紫外線吸収剤とした場合は、紫外線吸収剤をコーティング液に添加して塗布する一般的な方法を採用でき、透明被覆層に紫外線吸収性を付与するのが容易になる。
（５）前記紫外線吸収成分が反応型紫外線吸収剤を前記架橋性樹脂の分子中に共重合したものである場合は、紫外線吸収剤の耐揮散性や耐移行性が添加型の紫外線吸収剤に比較して良好となる。
（６）Ａ層と透明被覆層との間に印刷層が設けられている場合は、種々の模様を容易に設けることができ、意匠性を高めることができる。
（７）積層樹脂シートのＡ層にエンボス加工が施された後、透明被覆層が設けられたエンボス付与シートでは、積層樹脂シートに透明被覆層を設けた後にエンボス加工が施される構成に比較して、エンボス付与が良好に行われ易い。
（８）積層樹脂シートの透明被覆層の上からＡ層に対するエンボス加工が施されたエンボス付与シートでは、積層樹脂シートに対するエンボス付与後に透明被覆層を設ける場合に比較して、エンボス付与シートが完成するまでの工程数を少なくできる。
（９）被覆基材は前記のように構成された積層樹脂シート又はエンボス付与シートを、Ｂ層側を接着面として、熱硬化型接着剤を介して金属板の上に積層して形成した。従って、ＡＶ器機やエアコンカバー等の家庭電化製品外装や鋼製家具、エレベータ内装、建築物内装等で、比較的太陽光の照射を受け易い部位や紫外線放射量の多い人工光源の照射を受け易い部位に好適に用いることができる。
（１０）Ａ層及びＢ層の厚みの合計は、１００〜２４０μｍであり、そのうちＢ層の厚みが１０〜５０μｍであるため、従来ＰＶＣシートへのエンボス付与に用いられてきたエンボス版ロールの大部分で積層樹脂シートへのエンボス模様の付与が可能になる。
実施の形態は前記に限定されるものではなく、例えば、次のように具体化してもよい。
エンボス付与加工がなされていない状態の積層樹脂シートを金属板に積層した被覆基材に、エンボス加工を施してエンボス付与シートが被覆された被覆基材としてもよい。
積層樹脂シート及びエンボス付与シートは金属板に接着剤を介して積層して被覆基材を形成する用途に限らず、木質板、合板等の基材に積層して使用してもよい。
積層樹脂シートはそれぞれ１層のＡ層及びＢ層で構成されたものに限らず、Ａ層及びＢ層がそれぞれ少なくとも１層ずつ有ればよく、Ａ層及びＢ層が複数層、あるいはいずれかが複数層で構成されていてもよい。
前記実施の形態から把握される発明（技術的思想）について、以下に記載する。
（１）第３の発明において、前記エンボス付与可能層及び基材層の厚みの合計は、１００〜２４０μｍであり、そのうち基材層の厚みが１０〜５０μｍである。
［第４の発明］
（１）積層樹脂シートが、Ａ層及びＢ層の少なくとも２層のポリエステル系樹脂層を積層したシートから成り、Ａ層及びＢ層がエンボス付与前のシートにおいて、以下の要件を有している。即ち、Ａ層は、１０≦ΔＨｍ（Ａ）≦３５［Ｊ／ｇ］、かつ（ΔＨｍ（Ａ）−ΔＨｃ（Ａ））／ΔＨｍ（Ａ）≦０．５。Ｂ層は、１８０≦Ｔｍ（Ｂ）≦２４０［℃］、かつ０．５≦（ΔＨｍ（Ｂ）−ΔＨｃ（Ｂ））／ΔＨｍ（Ｂ）。従って、積層樹脂シートに従来から軟質ＰＶＣシートへのエンボス付与に用いられてきたエンボス付与機で連続的にエンボス付与を施す際に、加熱金属ロールへの粘着や、溶融によるシート破断を防止して円滑にエンボス模様を付与することができる。
（２）前記積層樹脂シートのＡ層にエンボス模様を付与すれば、エンボス模様の耐熱性が良好なものを得ることができる。
（３）積層樹脂シートを１６０℃以上、かつＢ層の結晶融解ピーク温度Ｔｍ−２０℃以下に加熱した後、エンボスロールと圧着ロールとの間を通過させてＡ層にエンボス模様を付与すれば、付与されたエンボス模様は耐熱性の良好なものとなる。従って、内部に発熱性の部材等を有する家電製品の外装等に用いた場合も、シートが加熱されることによるエンボス戻りの発生を抑制することができる。
（４）Ｂ層がポリブチレンテレフタレート（ＰＢＴ）系樹脂を含み、３５≦ΔＨｍ≦６０［Ｊ／ｇ］の要件を満たせば、通常の押出し製膜の時点で、結晶化速度の速いＰＢＴ系樹脂が、基材層１３が備えるべき条件を満たすことができる。従って、シート製膜後の別工程での熱処理等の特別な工程が不要となり、生産性の向上やコストの低減が図れる。
（５）Ｂ層がＰＴＴ系樹脂を含み、３５≦ΔＨｍ≦６０［Ｊ／ｇ］の要件を満たせば、通常の押出し製膜の時点で、結晶化速度の速いＰＢＴ系樹脂が、基材層が備えるべき条件を満たすことができる。この場合も、シート製膜後の別工程での熱処理等の特別な工程が不要となり、生産性の向上やコストの低減が図れる。
（６）Ａ層及びＢ層の少なくとも２層のポリエステル系樹脂層を共押出し法により積層一体化されたシートとすれば、別々に製膜したシートを後工程で積層一体化する場合に比べ、生産性の向上やコストの低減が図れる。また、Ａ層及びＢ層間の接着強度を強固なものとできるため、経時的な剥離の問題等を生じ難い。
（７）積層樹脂シートのＡ層側表面に、加熱された金属との非粘着性を有するコーティング層を付与すれば、エンボス付与機でシートが加熱された際、各種補助ロール等との粘着トラブルの危険を回避することができる。また、耐熱性の良好なエンボス意匠を付与するために、加熱されたエンボスロールを用いる場合も、該ロールとの非粘着性が良好なもの、即ち該ロールに対して粘着し難いものとなる。
（８）コーティング層の厚みを１〜１０μｍとすれば、厚みが薄すぎるための塗布ムラにより部分的に加熱金属ロールへの粘着が発生する等の問題や、厚みが厚すぎるためにコーティング層の樹脂物性が積層樹脂シートの重要な物性に影響を及ぼす等の問題を容易に回避できる。
（９）積層樹脂シートのＡ層にエンボス模様を付したエンボス付与シートのＢ層を接着面として、熱硬化性接着剤によって金属板の上に積層すれば、各種用途に好適に使用できるエンボス意匠の付与された被覆基材を軟質ＰＶＣシートを使用せずに得ることができる。
（１０）前記エンボス付与シートのＢ層を接着面として、熱硬化性接着剤を塗布焼き付けした金属板にラミネートロールを用いてラミネートした後、直ちに水冷すれば、ラミネート時のエンボス戻りを抑制することができ、深みのある意匠を有するエンボス意匠付与被覆基材を得ることができる。
（１１）前記被覆基材を、ドア材、ユニットバス壁材、ユニットバス内装材等の建築内装材に用いれば、軟質ＰＶＣシートを使用せず、かつ意匠性に優れた建築内装材を得ることができる。
実施の形態は前記に限定されるものではなく、例えば、次のように具体化してもよい。
積層樹脂シートのＡ層の上に印刷層を設けてもよい。
エンボス付与シートは、エンボス模様が付与された面がエンボス付与シートの表面となるものに限らない。例えば、内部にエンボス柄による凹凸意匠を有しながら、表面は平滑な意匠性を有する意匠シートを得たい場合や、木目柄エンボスなどで凹部を視覚的に強調するために着色インクを凹部にのみ付与する所謂ワイピング処理を施す場合は、積層樹脂シートにエンボスを付与した後、透明被覆層を積層する。
積層樹脂シート及びエンボス付与シートは金属板に接着剤層を介して積層して被覆基材を形成する用途に限らず、木質板、合板等の基材に積層して使用してもよい。
前記実施の形態から把握される発明（技術的思想）について、以下に記載する。
（１）第４の発明において、前記コーティング層は、その厚みが１〜１０μｍである。
（２）また、前記積層樹脂シートは、その総厚みが５０〜５００μｍである。
［第５の発明］
（１）積層樹脂シートが、Ａ層、Ｃ層及びＢ層の順に少なくとも３層から構成され、Ａ層及びＢ層がエンボス付与前のシートにおいて、以下の要件を有している。即ち、Ａ層は、１０≦ΔＨｍ（Ａ）≦３５、かつ（ΔＨｍ（Ａ）−ΔＨｃ（Ａ））／ΔＨｍ（Ａ）≦０．５。Ｂ層は、１８０≦Ｔｍ（Ｂ）≦２４０［℃］、かつ０．５≦（ΔＨｍ（Ｂ）−ΔＨｃ（Ｂ））／ΔＨｍ（Ｂ）。従って、積層樹脂シートに従来から軟質ＰＶＣシートへのエンボス付与に用いられてきたエンボス付与機で連続的にエンボス付与を施す際に、加熱金属ロールへの粘着や、溶融によるシート破断を防止して円滑にエンボス模様を付与することができると共に、別途、Ｃ層で印刷を付与することができる。
（２）前記Ｃ層とＢ層との間に、顔料が添加され、上記Ａ層と同様の特徴を有するＤ層を介在させることにより、前記の効果に加え、得られる積層樹脂シートに着色を程こすることができる。
（３）積層樹脂シートを１６０℃以上、かつＢ層の結晶融解ピーク温度Ｔｍ−２０℃以下に加熱した後、エンボスロールと圧着ロールとの間を通過させてＡ層にエンボス模様を付与すれば、付与されたエンボス模様は耐熱性の良好なものとなる。従って、内部に発熱性の部材等を有する家電製品の外装等に用いた場合も、シートが加熱されることによるエンボス戻りの発生を抑制することができる。
（４）Ｂ層がポリブチレンテレフタレート（ＰＢＴ）系樹脂を含み、３５≦ΔＨｍ≦６０［Ｊ／ｇ］の要件を満たせば、通常の押出し製膜の時点で、結晶化速度の速いＰＢＴ系樹脂が、基材層１３が備えるべき条件を満たすことができる。従って、シート製膜後の別工程での熱処理等の特別な工程が不要となり、生産性の向上やコストの低減が図れる。
（５）Ｂ層がＰＴＴ系樹脂を含み、３５≦ΔＨｍ≦６０［Ｊ／ｇ］の要件を満たせば、通常の押出し製膜の時点で、結晶化速度の速いＰＢＴ系樹脂が、基材層が備えるべき条件を満たすことができる。この場合も、シート製膜後の別工程での熱処理等の特別な工程が不要となり、生産性の向上やコストの低減が図れる。
（６）積層樹脂シートのＡ層側表面に、加熱された金属との非粘着性を有するコーティング層を付与すれば、エンボス付与機でシートが加熱された際、各種補助ロール等との粘着トラブルの危険を回避することができる。また、耐熱性の良好なエンボス意匠を付与するために、加熱されたエンボスロールを用いる場合も、該ロールとの非粘着性が良好なもの、即ち該ロールに対して粘着し難いものとなる。
（７）コーティング層の厚みを１〜１０μｍとすれば、厚みが薄すぎるための塗布ムラにより部分的に加熱金属ロールへの粘着が発生する等の問題や、厚みが厚すぎるためにコーティング層の樹脂物性が積層樹脂シートの重要な物性に影響を及ぼす等の問題を容易に回避できる。
（８）積層樹脂シートのＡ層にエンボス模様を付したエンボス付与シートのＢ層を接着面として、熱硬化性接着剤によって金属板の上に積層すれば、各種用途に好適に使用できるエンボス意匠の付与された被覆基材を軟質ＰＶＣシートを使用せずに得ることができる。
（９）前記エンボス付与シートのＢ層を接着面として、熱硬化性接着剤を塗布焼き付けした金属板にラミネートロールを用いてラミネートした後、直ちに水冷すれば、ラミネート時のエンボス戻りを抑制することができ、深みのある意匠を有するエンボス意匠付与被覆基材を得ることができる。
（１０）前記被覆基材を、ドア材、ユニットバス壁材、ユニットバス内装材等の建築内装材に用いれば、軟質ＰＶＣシートを使用せず、かつ意匠性に優れた建築内装材を得ることができる。
実施の形態は前記に限定されるものではなく、例えば、次のように具体化してもよい。
エンボス付与シートは、エンボス模様が付与された面がエンボス付与シートの表面となるものに限らない。例えば、内部にエンボス柄による凹凸意匠を有しながら、表面は平滑な意匠性を有する意匠シートを得たい場合や、木目柄エンボスなどで凹部を視覚的に強調するために着色インクを凹部にのみ付与する所謂ワイピング処理を施す場合は、積層樹脂シートにエンボスを付与した後、透明被覆層を積層する。
積層樹脂シート及びエンボス付与シートは金属板に接着剤層を介して積層して被覆基材を形成する用途に限らず、木質板、合板等の基材に積層して使用してもよい。
前記実施の形態から把握される発明（技術的思想）について、以下に記載する。
（１）第５の発明において、前記コーティング層は、その厚みが１〜１０μｍである。また、前記積層樹脂シートは、その総厚みが５０〜５００μｍである。
発明の効果
この発明にかかる樹脂積層シートは、ＰＶＣを使用せずに、シートへのエンボス付与工程において、シートを加温するための加熱ロールに接触させても粘着して貼り付くこともなく、エンボス付与が実施できると共に、従来から軟質塩化ビニル系樹脂シートに一般的に用いられてきた種々のエンボス付与方法に対応できる。
また、この樹脂積層シートやこの樹脂積層シートにエンボス付与をして得られるエンボス付与シートを用いることにより、住宅内装等の建築物内装、ＡＶ器機やエアコンカバー等の家電製品外装、鋼製家具、エレベータ内装等の基材として好適で、ＰＶＣを使用しない被覆シートを使用した被覆基材が得られる。
さらに、第３の発明においては、得られるエンボス付与シートの耐光性は良好である。
【図面の簡単な説明】
図１（ａ）、（ｃ）〜（ｋ）は第１の発明〜第５の発明にかかる積層樹脂シートの例を示す側面図、（ｂ）は第１の発明〜第２の発明にかかるエンボス付与シートの例を示す側面図である。
図２（ａ）〜（ｄ）は第２の発明〜第５の発明にかかる被覆基材の例を示す側面図である。
図３はエンボス付与装置の構造例を示す模式図である。TECHNICAL FIELD OF THE INVENTION
The present invention includes furniture, home appliances such as furniture, AV equipment and air conditioner covers, furniture such as plywood furniture, steel furniture, housing interior materials such as elevator interiors, doors, wall materials, flooring materials, and building interiors. The present invention relates to an embossable sheet excellent in processability and scratchability, an embossed sheet using the same, a coated substrate using the embossed sheet, and a method for producing them.
Conventional technology
Conventionally, a soft vinyl chloride resin sheet provided with an embossed design (embossed pattern) is coated with a synthetic resin molded product, a plywood board, a wood fiber board, a metal plate, or the like. Hereinafter, the vinyl chloride resin sheet is referred to as a PVC sheet. The following points can be mentioned as the characteristics of the flexible PVC sheet.
(1) Since it is excellent in embossing suitability, a coating material rich in design can be obtained.
(2) The balance between workability, which is generally a contradiction element, and surface scratch resistance is relatively good.
(3) It is easy to improve weather resistance, particularly light stability, because of excellent compatibility with various additives and studies on improving physical properties with additives for many years.
As a method of continuously embossing the long sheet of the soft vinyl chloride resin, the sheet after film formation is softened by reheating, and the pattern is continuously pressed by a roll engraved with an embossed pattern (embossed roll). In general, a method of transferring images is generally used. As a method for heating the sheet, a contact type in which the sheet is heated by being brought into contact with a heated metal roll, a non-contact type in which the sheet is heated without being brought into contact with the roll by an infrared heater, a hot air heater, or the like can be considered. In an actual production line, there may be only one of them, but in general, they are often used together, and equipment having these series of steps is called an embossing device or the like.
The flexible PVC sheet has the excellent characteristics as described above. However, in recent years, problems with heavy metal compounds caused by some stabilizers in vinyl chloride resins, VOC (volatile organic compounds) problems caused by some plasticizers and stabilizers, problems with endocrine disrupting effects, and chlorination during combustion Due to the problem of generating hydrogen gas and other chlorine-containing gases, vinyl chloride resins have come to be restricted in their use. The superiority or inferiority from the viewpoint of the total environmental impact with and without the use of vinyl chloride resin is still unclear, but users of these products are strongly required not to use vinyl chloride resin. It is coming.
For this reason, a sheet made of a polyolefin resin composition (hereinafter referred to as “PO”) or the like has been used. However, this PO sheet has a narrow optimum embossing temperature range, and it has been found that when the sheet temperature is high, the sheet sticks to the heating roll, and when it is low, the embossing hardly enters the sheet.
Further, a layer (B layer) made of polyester B having a melting point of 150 to 245 ° C. is laminated on at least one side of a layer made of polyester A having a melting point of 220 to 270 ° C. (A layer). There is disclosed an easily embossable film that is in the range of −5 ° C. or higher and the melting point of polyester A −5 ° C. or less (see Patent Document 1: Japanese Patent Laid-Open No. 9-24588).
Furthermore, a decorative sheet is disclosed in which a base film layer mainly composed of an amorphous polyester resin and a protective film layer mainly composed of a transparent amorphous polyester resin are laminated (Patent Document 2: Japanese Patent Laid-Open No. 2003-260260). 2000-233480). In this decorative sheet, the protective film layer includes a dicarboxylic acid component composed of terephthalic acid, 25-35 mol% 1,4-cyclohexanedimethanol, and a diol component composed of 65-75 mol% ethylene glycol. It is characterized by comprising 40 to 95% by weight of a polymerized amorphous polyester resin and 5 to 60% by weight of at least one crystalline polyester resin selected from polyethylene terephthalate and polybutylene terephthalate resins having crystallinity. .
Problems to be solved by the invention
However, the films and sheets disclosed in Patent Document 1 and Patent Document 2 can be embossed without using PVC by laminating polyester resin in two layers.
However, the film (sheet) disclosed in Patent Document 1 needs to be heated to the melting point of the B layer or higher when embossing is performed. If the melting point is high, the sheet temperature cannot be raised to a necessary temperature in the embossing apparatus (general apparatus) for the current PVC, and embossing cannot be performed. In addition, since the sheet melt tension rapidly changes depending on the melting point, in the case of a B / A sheet having a close difference in melting point, there is a possibility that the embossing cannot be performed or the sheet may be blown out due to temperature fluctuation.
Further, in the sheet disclosed in Patent Document 2, since the two layers are mainly composed of amorphous polyester resin, the embossing process is performed by heating and temperature fluctuation of heating, sticking to a heating roll, winding, etc. There is a problem that this problem occurs.
Therefore, the present invention generally provides an embossing apparatus for current PVC without causing any problems of sheet fusing, sticking to a heating roll, or winding even when using an embossing apparatus for current PVC. It is an object to provide an embossed sheet that can be used, and a coated substrate using the embossed sheet.
The first aspect of the invention described later has the following contents.
(1) In the embossing process to a sheet without using PVC, a laminated resin sheet that can be embossed without being adhered and stuck even if it is brought into contact with a heating roll for heating the sheet. provide.
(2) To provide a coated base material using a coating sheet that is suitable as a base material for housing interior building materials, home appliances, etc., and does not use PVC.
Next, the second content described later has the following contents.
(1) Provided is a polyester resin laminated resin sheet that can be applied to various embossing methods that have been conventionally used for soft vinyl chloride resin sheets.
(2) An embossing sheet using the laminated resin sheet is provided.
(3) Provide a coated base material on which these sheets are laminated.
Next, the third aspect of the invention, which will be described later, aims at the following contents.
(1) Provided is a polyester resin laminated resin sheet with good light resistance that can be continuously embossed by an embossing device that has been used for embossing a PVC sheet.
(2) An embossing sheet using the laminated resin sheet is provided.
(3) Provide a coated base material on which these sheets are laminated.
Next, the fourth aspect of the invention described later has the following contents.
(1) Provided is a laminated resin sheet that can be continuously embossed with an embossing device that has been used for embossing soft PVC sheets without using a soft vinyl chloride resin.
(2) To provide an embossed sheet that has been embossed.
(3) Provide the manufacturing method.
(4) An embossed design is provided without using a soft PVC sheet, and a coated base material that can be suitably used for various applications is provided.
(5) The manufacturing method is provided.
(6) To provide a building interior material that is embossed without using a soft PVC sheet and can be suitably used for various applications.
Next, the fifth invention described later has the following contents.
(1) Provided is a laminated resin sheet having a printed pattern that can be continuously embossed by an embossing device that has been used for embossing soft PVC sheets without using a soft vinyl chloride resin. .
(2) To provide an embossed sheet that has been embossed.
(3) Provide the manufacturing method.
(4) An embossed design is provided without using a soft PVC sheet, and a coated base material that can be suitably used for various applications is provided.
(5) The manufacturing method is provided.
Means for solving the problem
In order to solve the above-described problems, the respective configurations according to the following first to fifth inventions are employed.
First, the first invention employs the following configuration. The first invention refers to the invention according to claims 1 to 6, claim 27 and claim 35.
In order to achieve the object of the first invention, embossing containing a large amount of a substantially amorphous or low crystalline resin composition or the substantially amorphous or low crystalline resin composition. The emboss can be applied, comprising a possible layer (A layer) and a substrate layer (B layer) containing a large amount of the substantially crystalline resin composition or the substantially crystalline resin composition. A laminated resin sheet that can be embossed from the layer is employed.
In this invention, emboss provision can be performed from an emboss provision possible layer by the emboss provision apparatus generally used for emboss provision to a PVC sheet by the above-mentioned composition. Even when the embossable layer is heated to a temperature at which embossing can be performed, the substantially crystalline base material layer has rigidity as a sheet and does not stick to the heating roll.
When the glass transition temperature of the A layer is Tg (A), the melting point of the B layer is Tm (B), and the embossing temperature is T, the relationship of Tg (A) ≦ T ≦ Tm (B) is satisfied. Adopt a laminated resin sheet that can set the embossing temperature. In this invention, embossing becomes easy.
Furthermore, the laminated resin sheet which forms a printing layer and a transparent upper layer further on the said A layer is employ | adopted.
Furthermore, a laminated resin sheet in which a printed layer and a surface coat layer are further formed on the A layer is employed. In these inventions, embossing can be carried out from the embossable layer in the same manner as described above, even in the case of a laminated resin sheet in which a printed layer, a transparent upper layer and the like are formed to enhance the design.
Moreover, the laminated resin sheet whose total thickness of all the layers is 50 micrometers-300 micrometers is employ | adopted. In the present invention, the sheet is not broken at the time of bonding the laminated resin layer to a base material such as a metal plate or by subsequent drilling or bending, and embossing is also easily performed.
Furthermore, the laminated resin sheet which laminated | stacked the said A layer and B layer in the unstretched state is employ | adopted. When a stretched sheet is used, it shrinks when the temperature rises above the heat setting temperature, so the degree of freedom in processing temperature when embossing is low, but in this invention, the processing temperature when embossing is applied because of non-stretching. The degree of freedom increases.
Furthermore, an embossing sheet is adopted by embossing the A layer.
Further, a coated substrate in which a sheet embossed on any one of the above laminated resin sheets is coated on at least one surface of a substrate such as a metal plate, a wooden board, or a plywood is adopted. In the present invention, it can be suitably used as a base material for home interior products such as doors, wall materials, floor materials, furniture, furniture, elevators and AV products.
Next, the second invention employs the following configuration. The second invention refers to the inventions according to claims 7 to 12 and 28 and part of the invention according to claim 36.
In order to achieve the object in the second invention, the A layer and the B layer are two kinds of polyester resins having different compositions, and each of the A layer and the B layer satisfies the following conditions: A laminated resin sheet that can be embossed by various embossing methods is employed.
Layer A: From a substantially amorphous polyester-based resin or a mixture containing 50% or more by weight of the polyester-based resin in which no clear crystal melting peak is observed at the time of temperature rise in measurement with a differential scanning calorimeter (DSC) Become.
B layer: from a substantially crystalline polyester resin or a mixture containing 50% or more by weight of the polyester resin, in which a clear crystal melting peak is observed when the temperature is raised in the measurement with a differential scanning calorimeter (DSC). Furthermore, the resin layer after film formation is crystallized to a state where no clear crystallization peak is observed in the measurement with a differential scanning calorimeter (DSC).
In this invention, the A layer shares the function of imparting embossing, and the B layer shares the functions of preventing adhesion to the heating roll and preventing fusing. That is, even when the A layer is heated to a temperature at which embossing can be performed, the B layer made of a substantially crystalline polyester resin has rigidity as a sheet and does not stick to the heating roll. Therefore, embossing by reheating of a sheet that could not be handled by a polyester resin sheet conventionally becomes possible. As a result, it is possible to cope with various embossing methods conventionally used for soft vinyl chloride resins.
Further, the crystal melting peak temperature (melting point) of the polyester resin constituting the B layer is Tm (B) [° C.], and the glass transition point of the polyester resin constituting the A layer is Tg (A) [° C.]. In this case, a laminated resin sheet that satisfies the relationship Tm (B)> {Tg (A) +30} is employed.
In the present invention, embossing can be applied to the A layer below the melting point of the polyester-based resin constituting the B layer, and embossing is facilitated.
Furthermore, the laminated resin sheet which laminated | stacked the transparent resin layer on the said A layer is employ | adopted. In the present invention, due to the presence of the transparent resin layer, it is easy to impart a deep design property, improve the physical properties of the surface, and prevent ejection of additives such as pigments added to the polyester resin.
Furthermore, a laminated resin sheet in which printing is performed on the A layer and a transparent resin layer is laminated thereon is employed. In the present invention, by performing printing, various patterns can be formed on the A layer, and the design can be improved.
In addition, a laminated resin sheet in which the substantially crystalline polyester used in the B layer is polybutylene terephthalate or a copolymer thereof is employed.
In order to perform embossing satisfactorily, it is important that the B layer is sufficiently crystallized when the laminated resin sheet is formed. In the present invention, since polybutylene terephthalate or a copolymer thereof having a high crystallization speed is used as the resin constituting the B layer, it is easy to sufficiently crystallize the sheet during film formation.
Furthermore, the substantially amorphous polyester used for A layer employ | adopts the laminated resin sheet which is the cyclohexane dimethanol copolymer of a polyethylene terephthalate. In this invention, it is easy to obtain a substantially amorphous polyester system constituting the A layer.
Furthermore, the embossing sheet | seat which provided the embossing to one of the said laminated resin sheets is employ | adopted. In this invention, the effect corresponding to any one of the laminated resin sheets is obtained.
Moreover, the covering base material which laminated | stacked any one of the said laminated resin sheets on the metal plate through the thermosetting adhesive by making the said B layer into an adhesive surface is employ | adopted. The coated substrate of the present invention can be suitably used as it is or with embossing applied, for home appliance exteriors such as AV equipment and air conditioner covers, steel furniture, elevator interiors, building interiors, and the like.
Furthermore, the covering base material which laminated | stacked the said emboss provision sheet | seat on the metal plate through the thermosetting adhesive agent is employ | adopted by making the layer formed with the said polyester-type resin B into an adhesive surface. The coated substrate of the present invention can be suitably used for home appliance exteriors such as AV equipment and air conditioner covers, steel furniture, elevator interiors, building interiors, and the like.
Next, the third invention employs the following configuration. The third invention refers to the inventions according to claims 13 to 18, the inventions according to claims 29 and 30, and a part of the invention according to claim 36.
In order to achieve the object in the third aspect of the invention, the surface of the A layer of the sheet obtained by laminating at least two polyester-based resin layers of the A layer and the B layer has a thickness of 2 μm to 20 μm having ultraviolet absorptivity. A laminated resin sheet provided with a transparent coating layer in a range is employed. In this invention, due to the presence of a transparent coating layer having ultraviolet absorptivity, light resistance is improved, deep design is imparted, surface properties are improved, and additives such as pigments added to polyester resins are ejected. Prevention becomes easy.
Moreover, the laminated resin sheet which the said A layer and B layer satisfy | fill the following conditions is employ | adopted.
Layer A: The polyester resin constituting the layer A is a substantially amorphous polyester resin or a polyester resin in which no clear crystal melting peak is observed at the time of temperature rise in the measurement with a differential scanning calorimeter (DSC). It consists of a mixture containing 50% or more by weight.
B layer: The polyester resin constituting the B layer is a substantially crystalline polyester resin or a polyester resin in which a clear crystal melting peak is observed when the temperature is raised in the measurement with a differential scanning calorimeter (DSC). It consists of a mixture containing 50% or more by weight and does not show adhesiveness to the metal roll when the sheet is further heated for embossing.
Further, when the crystal melting peak temperature (melting point) of the resin component B is Tm (B) [° C.] and the glass transition point of the resin component A is Tg (A) [° C.], Tm (B)> {Tg The relationship (A) +30} is established.
In this invention, when the sheet is heated for embossing, the sheet does not exhibit adhesiveness to the metal roll, and embossing is possible below the melting point of the base material layer with respect to the embossable layer, and the base material is heated. The layer does not melt and break, and embossing is performed well.
Further, a laminated resin sheet in which the transparent coating layer includes at least one coating layer of a crosslinkable resin containing an ultraviolet absorbing component is employed. In the present invention, in addition to UV absorption, the transparent coating layer has secondary effects such as adjustment of gloss, further improvement of scratch resistance, improvement of contamination resistance, and provision of a deep design. It becomes easy.
Furthermore, a laminated resin sheet in which the ultraviolet absorbing component is an additive type ultraviolet absorber is employed. In the present invention, ultraviolet absorption can be imparted to the transparent coating layer by a general method in which an ultraviolet absorber is added to the coating solution and applied, and ultraviolet absorbance can be easily imparted.
Further, a laminated resin sheet in which the ultraviolet absorbing component is copolymerized with a reactive ultraviolet absorber in the molecule of the crosslinkable resin is employed. In this invention, the volatilization resistance and migration resistance of the ultraviolet absorber are better than those of the additive type ultraviolet absorber.
Furthermore, a laminated resin sheet in which a printing layer is provided between the A layer and the transparent coating layer is employed. In this invention, by providing a printing layer, various patterns can be provided, and the design can be improved.
Moreover, after embossing is given to the A layer of any one of the laminated resin sheets, an embossed sheet on which the transparent coating layer is formed is employed. In this invention, the effect corresponding to any one of the laminated resin sheets can be obtained. In addition, embossing is easily performed better than a configuration in which embossing is performed after providing a transparent coating layer on the laminated resin sheet.
Furthermore, the embossing sheet | seat in which the embossing with respect to the said embossing possible layer is given from the said A layer of one of the said laminated resin sheets is employ | adopted. In this invention, the effect corresponding to any one of the laminated resin sheets can be obtained.
Furthermore, a coated substrate in which any one of the above laminated resin sheets or any one of the above embossed sheets is laminated on a metal plate through a thermosetting adhesive with the B layer side as an adhesive surface is adopted. To do. The coated substrate of the present invention can be suitably used for home appliance exteriors such as AV equipment and air conditioner covers, steel furniture, elevator interiors, building interiors, and the like.
Next, the fourth invention employs the following configuration. The fourth invention refers to the inventions according to claims 19 to 22, the inventions according to claims 31 and 32, and a part of the inventions according to claims 37 to 39.
In order to achieve the object in the fourth aspect of the invention, the laminate comprises a sheet obtained by laminating at least two polyester resin layers of A layer and B layer, and the A layer and B layer have the following requirements: Adopt a resin sheet.
A layer: In the sheet before embossing, at the time of temperature rise as measured by a differential scanning calorimeter (DSC), a clear crystallization peak temperature Tc (A) [° C.] and a crystal melting peak temperature Tm (A) [° C. And δHc (A) [J / g], and the heat of crystal fusion ΔHm (A) [J / g], 10 ≦ ΔHm (A) ≦ 35, (ΔHm (A ) −ΔHc (A)) / ΔHm (A) ≦ 0.5.
B layer: In the sheet before embossing, a clear crystal melting peak temperature Tm (B) [° C.] was observed at the time of temperature rise as measured by a differential scanning calorimeter (DSC), and the heat of crystallization was ΔHc (B) [J / g], where the heat of crystal fusion is ΔHm (B) [J / g], 180 ≦ Tm (B) ≦ 240, 0.5 ≦ (ΔHm (B) −ΔHc (B)) / ΔHm ( The relational expression B) is established.
When embossing is continuously applied to the laminated resin sheet using an embossing device that has been used to emboss soft PVC sheets, the layer A is heated by the embossing device and softened, and then embossed with an embossing roll. Design is given. In addition, when the laminated resin sheet is heated by the embossing device, the B layer is applied to the A layer where the embossable layer itself is sticking to the heated metal roll or causing the sheet to break by melting ( By being laminated, it plays a role of preventing this.
The B layer includes a polybutylene terephthalate (PBT) -based resin, and a laminated resin sheet satisfying the following relational expression is adopted.
35 ≦ ΔHm ≦ 60
In this invention, at the time of normal extrusion film formation, it becomes possible for the polybutylene terephthalate-based resin having a high crystallization rate to satisfy the conditions that the B layer should have, and heat treatment in a separate process after sheet film formation. A special process such as this becomes unnecessary. Therefore, productivity can be improved and costs can be reduced.
Furthermore, the B layer includes a polytrimethylene terephthalate (PTT) resin, and a laminated resin sheet satisfying the following relational expression is adopted.
35 ≦ ΔHm ≦ 60
Even in this invention, at the time of normal extrusion film formation, it becomes possible for the polytrimethylene terephthalate-based resin having a high crystallization rate to satisfy the conditions that the B layer should have, and in a separate process after sheet film formation. No special process such as heat treatment is required. Therefore, productivity can be improved and costs can be reduced.
Furthermore, a laminated resin sheet which is a sheet in which at least two polyester resin layers of the A layer and the B layer are laminated and integrated by a co-extrusion method is employed.
In this invention, since the A layer and the B layer are formed by the co-extrusion method, productivity can be improved and costs can be reduced as compared with the case where the separately formed sheets are laminated and integrated in a subsequent process. Since the adhesive strength between the A layer and the B layer can be strengthened, it is difficult to cause a problem of peeling over time.
Moreover, the laminated resin sheet by which the coating layer which has non-adhesiveness with the heated metal was provided on the surface of the said A layer.
In this invention, when a sheet | seat is heated with an embossing provision apparatus, the danger of the adhesion trouble with various auxiliary rolls etc. can be avoided by presence of the coating layer which has the said non-adhesiveness. Also, when a heated embossing roll is used to give an embossed design with good heat resistance, the non-adhesiveness to the roll is good, that is, it is difficult to stick to the roll.
Furthermore, the embossing sheet | seat which provided the embossing pattern in the A layer of one of the said laminated resin sheets is employ | adopted. In the present invention, an embossed pattern having good heat resistance can be obtained.
Furthermore, after heating any one of the laminated resin sheets to 160 ° C. or higher and {the crystal melting peak temperature of the B layer (Tm (B))} − 20 ° C. or lower, an emboss roll engraved with an embossed pattern; An embossing sheet manufacturing method for applying an embossed pattern to the A layer by passing through a nip roll is employed.
In this invention, the applied embossed pattern has good heat resistance. Therefore, even when used for an exterior of a household electrical appliance having an exothermic member or the like inside, it is possible to suppress the occurrence of emboss return due to the heating of the sheet.
Moreover, the coating base material which laminated | stacked the said embossing sheet | seat on the metal plate with the thermosetting adhesive by making the B layer into an adhesive surface is employ | adopted. In this invention, the coating | coated base material to which the embossing design which can be used conveniently for various uses was provided can be obtained, without using a soft PVC sheet.
Furthermore, the said coating | coated base material is used as building interior materials, such as a door material, a unit bath wall material, and a unit bath interior material. In this invention, a building interior material excellent in design can be obtained without using a soft PVC sheet.
In addition, the above embossed sheet is laminated on a metal plate coated with a thermosetting adhesive and baked using a laminating roll with the B layer as the adhesive surface, and then immediately coated with a water-cooled coating method. To do.
In this invention, the coated substrate after lamination is rapidly cooled by water cooling, so that emboss return at the time of lamination can be suppressed, and an embossed design imparted coated substrate having a deep design can be obtained. .
Next, the fifth invention employs the following configuration. The fifth invention refers to the inventions according to claims 23 to 26, claims 33 and 34, and a part of the inventions according to claims 37 to 39.
In order to achieve the object of the fifth invention, the A layer, the C layer 17e, and the B layer are composed of at least three layers in this order, and each of the A layer and the B layer employs a laminated resin sheet having the following characteristics. To do.
Layer A: An unstretched polyester resin layer having a thickness of 15 μm or more and 120 μm or less, and a clear crystallization peak temperature Tc (A) when heated by a differential scanning calorimeter (DSC) in a sheet before embossing. (° C.) and a crystal melting peak temperature Tm (A) (° C.) are observed, the crystallization heat quantity is ΔHc (A) (J / g), and the crystal fusion heat quantity is ΔHm (A) (J / g) Both of the following relational expressions hold.
10 ≦ ΔHm (A) ≦ 35 (J / g)
(ΔHm (A) −ΔHc (A) / ΔHm (A) ≦ 0.5
Layer B: In the sheet before embossing, a clear crystal melting peak Tm (B) (° C.) is observed at the time of temperature rise by a differential scanning calorimeter (DSC), and the amount of crystallization is expressed as ΔHc (B) (J / g) When the amount of heat of crystal fusion is ΔHm (B) (J / g), both of the following relational expressions hold.
180 ≦ Tm (B) ≦ 240 (° C.)
0.5 ≦ (ΔHm (B) −ΔHc (B)) / ΔHm (B)
In this invention, it becomes possible to provide embossing continuously with an embossing device that has been conventionally used for embossing soft PVC sheets. At this time, the A layer is heated and softened by an embossing device, and then an embossed design is applied by an embossed pattern roll. When the sheet is heated by an embossing apparatus, the layer B has a role to prevent this by providing the layer B where the layer A alone causes adhesion to the heated metal roll or the sheet breakage due to melting.
Further, a laminated resin sheet in which a polyester resin layer (D layer) is interposed between the C layer and the B layer is employed. In this invention, since D layer contains a pigment, the obtained sheet | seat is colored with the pigment. Furthermore, since the D layer has the same characteristics as the A layer except that a pigment is included, it has embossing suitability and can transfer a deeper embossed pattern than when only the A layer has embossing suitability. . Alternatively, when an embossed pattern having the same depth is transferred, the thickness of the transparent A layer can be relatively reduced, and the sharpness of the printed pattern can be improved.
Furthermore, a laminated resin sheet that uses a polybutylene terephthalate (PBT) -based resin having a high crystallization rate in the B layer so as to satisfy “30 ≦ ΔHm (J / g) ≦ 65” is employed. In this invention, it becomes possible to satisfy the conditions that the B layer should have at the time of normal extrusion film formation, and a special process such as heat treatment in a separate process after sheet film formation becomes unnecessary. As a result, productivity can be improved and costs can be reduced.
In addition, a laminated resin sheet that uses a polytrimethylene terephthalate (PTT) -based resin with a high crystallization speed so as to satisfy “30 ≦ ΔHm (J / g) ≦ 65” is adopted for the B layer. In this invention, it becomes possible to satisfy the conditions that the B layer should have at the time of normal extrusion film formation, and a special process such as heat treatment in a separate process after sheet film formation becomes unnecessary. As a result, productivity can be improved and costs can be reduced.
Furthermore, the laminated resin sheet by which the coating layer which has non-adhesiveness with the heated metal with a thickness of 2-10 micrometers is employ | adopted for the A layer side surface is employ | adopted. In this invention, when a sheet | seat is heated with an embossing provision apparatus, the danger of the adhesion trouble with various auxiliary rolls etc. can be avoided. In addition, in order to give an embossed design with good heat resistance, even when a heated embossed pattern roll is used, the non-adhesiveness with the roll becomes good.
Furthermore, after the laminated resin sheet is heated to 160 ° C. or higher and {B layer crystal melting peak temperature (Tm (B)) − 20} ° C. or lower, an embossed plate roll engraved with an embossed pattern and a pressure-bonding roll An embossing sheet with an embossed pattern is adopted by passing between the two. In this invention, the embossed pattern imparted has good heat resistance, and therefore, emboss return due to heating of the sheet is suppressed even when used for the exterior of home appliances having a heat-generating member inside. I can do it.
Further, after heating the laminated resin sheet to 160 ° C. or higher and {B layer crystal melting peak temperature (Tm (B)) − 20} ° C. or lower, an embossed plate roll engraved with an embossed pattern and a pressure-bonding roll The manufacturing method of the embossing sheet | seat which provides an embossing pattern by passing between is employ | adopted. In this invention, the embossed pattern imparted has good heat resistance, and therefore, when used for the exterior of a household electrical appliance having an exothermic member or the like inside, the embossing return due to heating of the sheet is suppressed. I can do it. For this reason, the polyester-type design sheet with few emboss return | restorations at the time of being heated can be created.
Furthermore, the coating base material which laminated | stacked the said emboss provision sheet | seat on the metal plate with the thermosetting adhesive by making the said B layer into an adhesive surface is employ | adopted. According to the present invention, an embossed / printed design coated substrate that can be suitably used for various applications can be obtained without using a soft vinyl chloride resin sheet.
Furthermore, the coating | coated base material used as a building interior material chosen from a door material, a unit bath wall material, or a unit bath interior material is employ | adopted. In this invention, a covering base material can be used as a building interior material selected from a door material, a unit bath wall material, or a unit bath interior material.
In addition, the embossed sheet is laminated on a metal plate coated and baked with a thermosetting adhesive using the B layer as an adhesive surface, and then a coated substrate manufacturing method is adopted in which it is immediately cooled by water cooling. To do. In this invention, the return of embossing at the time of lamination can be suppressed, and an embossed / printed design coated substrate having a deep design can be obtained.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments embodying the present invention will be described. First, the invention according to the first invention will be described.
[First invention]
As shown in FIG. 1A, a laminated resin sheet 11a according to the first invention includes an embossable layer (hereinafter referred to as “A layer”) 12a and a base material layer (hereinafter referred to as “B layer”). The sheet 13a is laminated. Examples of the laminated resin sheet include those having a two-layer structure composed of the A layer and the B layer and those having a structure of three or more layers in which another layer is provided on the A layer.
[Embossing device]
By giving the embossing 14 to this laminated resin sheet 11a, an embossing giving sheet 15a as shown in FIG. 1B is obtained.
As a method for providing the emboss 14 to the laminated resin sheet 11a, the following method is employed. This embossing method is a method common to all of the first to fifth inventions. Here, the explanation will be made using the laminated resin sheet 11a, but the laminated resin sheets 11b to 11e are used. Is the same.
Embossing to the laminated resin sheet 11a is performed by using an embossing device that has been generally used to impart an embossed pattern to a soft vinyl chloride resin sheet. FIG. 3 is a schematic side view of a general embossing device. The embossing device 30 includes a preheating unit 31 for the sheet S, a heating unit 32 for heating the preheated sheet S to a temperature suitable for embossing, an embossing unit 33, and a cooling roll 34. . The preheating unit 31 includes a heating drum (heating roll) 31a and a pressure bonding roll 31b. The heating unit 32 includes an infrared heater 32a and a guide roll 32b, and can heat the sheet S to an arbitrary temperature by non-contact heating. The embossing imparting section 33 includes a nip roll 33a and an embossing roll 33b, and pressurizes the heated sheet S to impart embossing. The cooling roll 34 cools the sheet S after embossing.
In addition, when a coating layer such as a transparent resin layer is present on the A layer of the laminated resin sheets 11a to 11e, before the coating layer is provided on the A layer of the laminated resin sheets 11a to 11e, the A layer Embossing may be performed using the embossing device 30, and after the coating layer is provided on the A layer of the laminated resin sheets 11a to 11e, the embossing device 30 is used from above the coating layer. May be embossed.
When embossing is performed from above the coating layer, it cannot be generally said due to the physical properties and thickness of the coating layer, but generally, if the thickness of the coating layer is in the range of 2 μm to 20 μm, the coating Even if embossing is performed after the layer is provided, the embossing suitability is not significantly reduced. Further, when the coating layer has a non-adhesive effect with metal or various rubber guide rolls as a secondary effect, it is introduced into the embossing device 30 after the coating layer is provided. It is easier to obtain stable production conditions.
On the other hand, if you want to obtain a design-imparting sheet that has an uneven design with an embossed pattern inside, but the outermost surface has a smooth design, or if you want to visually emphasize the recesses with embossed grain, etc. In the case where a so-called wiping treatment is applied only to the resin layer, a coating layer is provided after embossing is applied to the laminated resin sheets 11a to 11e.
[Laminated resin sheet]
The A layer 12a is made of a material containing a large amount of a substantially amorphous or low crystalline resin composition or the substantially amorphous or low crystalline resin composition. The B layer 13a is made of a material containing a large amount of the substantially crystalline resin composition or the substantially crystalline resin composition. Of these, the A layer 12a can be embossed.
Here, “substantially amorphous or low crystallinity” means that a clear crystal peak is not observed at the time of temperature rise, for example, in the measurement of the transition temperature of plastic by a differential scanning calorimeter (DSC). Further, “substantially crystalline” means that a clear crystal peak is observed at the time of temperature rise in the measurement of plastic transition temperature using a differential scanning calorimeter (DSC). In addition, “containing a large amount of resin composition” means that the main component has the resin composition, but as long as the object of the present invention is not impaired, an ultraviolet absorber, an antioxidant, a lubricant, a pigment, It means that an agent, an additive, an antistatic agent, an antiblocking agent and the like may be included.
When the glass transition temperature of the A layer 12a is Tg (A), the melting point of the B layer 13a is Tm (B), and the embossing temperature is T, the embossing is in the relationship of Tg (A) ≦ T ≦ Tm (B). The material of both layers A and B is selected so that the temperature can be set and embossing can be applied from the embossable layer A.
In addition, the relationship between the glass transition temperature Tg (A) [° C.] of the A layer 12a and the melting point Tm (B) [° C.] of the base material layer B is Tg (A) + 30 ≦ Tm (B). preferable. When this relationship is satisfied, when the embossing temperature is T, it is easy to set the embossing temperature in a relationship of Tg (A) ≦ T ≦ Tm (B).
As the material of the A layer 12a and the B layer 13a, a thermoplastic resin other than the PVC resin (for example, a polyester resin, a polyolefin resin, an acrylic resin, etc.) is used, and the A layer 12a and the B layer 13a are not necessarily the same. It does not have to be a resin composition.
In general, in order to emboss the sheet, it is necessary to soften the sheet to some extent. Since the crystalline material does not soften unless it is Tm (melting point) or higher, embossing does not occur. Since amorphous and low crystalline materials soften at Tg (glass transition temperature) or higher, embossing can be performed at temperatures exceeding Tg. However, materials whose modulus of elasticity suddenly drops above Tg, Tm are heated and heated due to fluctuations in temperature, melting of the sheet due to a decrease in melt tension, sticking to a heating roll on the way to an embossing roll, winding, etc. Cause a bug.
In the present invention, the A layer 12a is embossed on the A layer 12a by forming a two-layer structure of an A layer 12a containing a substantially amorphous resin composition and a B layer 13a containing a substantially crystalline resin composition. Even if the sheet temperature rises above the temperature at which A can be put and the melt tension of the A layer 12a decreases or the temperature at which the A layer 12a sticks to the heating roll up to the embossing roll, the rigidity of the entire sheet is maintained by the B layer 13a. The As a result, the sheet can be prevented from sticking to a heating roll or the like without fusing.
The laminated resin sheet 11a is not limited to the two-layer structure of the A layer 12a and the B layer 13a, but a structure in which a printed layer, a transparent upper layer or a coat layer is laminated on the A layer 12a is opposite to the base material layer B. It is only necessary that embossing is possible from the side.
When these laminated resin sheets 11a are too thick, when they are bonded to a metal plate such as a steel plate, a wooden plate, or a plywood for constituting a coated base material, There is a problem that the sheet breaks during bending. On the other hand, if it is too thin, embossing does not enter well, the appearance and design are poor, and it is considered that the wear disappears during use. Therefore, the total thickness of the laminated resin sheet 11a is desirably 50 μm to 300 μm.
In the laminated resin sheet 11a, an embossed sheet 15a is obtained by embossing the A layer 12a by the above method.
[Print layer]
The printing layer is applied to the A layer 12a by, for example, gravure printing, offset printing, screen printing, or other known methods. The pattern of the print layer is arbitrary, such as a stone pattern, a woodgrain pattern, a geometric pattern, an abstract pattern, etc., may be partial printing or full surface printing, and may be further subjected to solid printing after partial printing. Moreover, you may use the method of giving what is called a back print to the lamination surface of the film which comprises the upper layer laminated | stacked on the A layer 12a.
[Coating substrate]
The laminated resin sheet 11a is used as a covering material for a covering base material used for home interior materials such as doors, wall materials, floor materials, furniture, furniture, elevators, AV products, and the like.
As the metal plate of the base material for coating the laminated resin sheet 11a, those generally used for this kind of coated base material can be used without particular limitation. Specific examples include various types of steel such as hot rolled steel, cold rolled steel, and stainless steel, and aluminum alloy plates. The steel plate may have a surface treated by plating or the like, and the type of plating is not particularly limited, and examples include hot dip galvanizing, electrogalvanizing, tin plating, and zinc-aluminum alloy plating. It is done. Moreover, chromate treatment, phosphoric acid coating treatment, etc. can be raised as chemical conversion treatment. These heat treatment conditions, plating thickness and the like are not particularly limited within a general range. Moreover, although the thickness of a base metal plate changes with uses of a coating base material, etc., the range of 0.1-10 mm is preferable. Moreover, a base material is not restricted to a metal plate, A plywood and a wooden board may be sufficient.
[Manufacturing method of laminated resin sheet and coated substrate]
Examples of the method of laminating the laminated resin sheet 11a include a coextrusion method in which the resin composition of each layer is coextruded and laminated, a laminating method in which each layer is formed into a sheet shape, and then laminated with an adhesive or the like, or crystallinity Lamination can be performed by a push-lamination method in which a molten resin is placed on a resin sheet.
Further, it is more preferable that the A layer 12a and the B layer 13a are laminated in an unstretched state because the degree of freedom in processing temperature at the time of embossing is increased.
And the said coating | coated base material can be manufactured by coat | covering the said laminated resin sheet on the at least single side | surface of the said base material.
[Second invention]
Next, the second invention will be described.
As shown in FIG. 1A, the laminated resin sheet 11b according to the second invention is a sheet in which the A layer 12b and the B layer 13b are made of two kinds of polyester resins having different compositions.
[A layer]
The polyester resin constituting the A layer 12b is mainly a substantially amorphous polyester resin or a polyester resin in which no clear crystal melting peak is observed at the time of temperature rise in the measurement with a differential scanning calorimeter (DSC). It consists of a mixture as a component. Here, “main component” means that it is contained by 50% or more by weight.
As this substantially amorphous polyester-based resin, the above conditions are selected from copolymers of diol components such as ethylene glycol, propylene glycol, butanediol, and cyclohexanedimethanol, and dicarboxylic acid components such as terephthalic acid and isophthalic acid. Any resin that satisfies the above can be used. Examples of this copolymer include a cyclohexanedimethanol copolymer of polyethylene terephthalate.
Since the polyester resin which is the main component of the polyester resin constituting the A layer 12b is substantially amorphous, the A layer 12b becomes substantially amorphous or low crystalline. Such a polyester-based resin has physical properties of a substantially amorphous resin that gradually softens from a temperature in the vicinity of Tg (glass transition point), and exhibits optimum characteristics for embossing.
Further, the resin blended with the polyester resin constituting the A layer 12b may have crystallinity. However, when the blending ratio of the crystalline resin is increased, the resin A exhibits the physical properties of the crystalline resin, and is not necessarily suitable for embossing.
[B layer]
The polyester resin constituting the B layer 13b is mainly a substantially crystalline polyester resin or a polyester resin in which a clear crystal melting peak is observed at the time of temperature rise as measured by a differential scanning calorimeter (DSC). It consists of a mixture as a component (that is, contained by 50% or more by weight). In the polyester resin constituting the B layer 13b, the resin layer after sheet formation is further crystallized to a state where no clear crystallization peak is observed in the measurement with a differential scanning calorimeter (DSC).
Examples of the substantially crystalline polyester resin that is the main component of the polyester resin constituting the B layer 13b include diol components such as ethylene glycol, propylene glycol, butanediol, and cyclohexanedimethanol, and terephthalic acid and isophthalic acid. Any resin satisfying the above conditions can be used from the copolymer with the dicarboxylic acid component.
The resin blended with the polyester resin constituting the B layer 13b may not have crystallinity, but the polyester resin constituting the B layer 13b is sufficiently crystallized at the time of film formation. It must be converted. Here, “sufficiently crystallized” means that a clear crystallization peak is not observed at the time of temperature rise in the measurement by DSC.
A polyester resin in which a crystallization peak is observed by DSC is not sufficiently crystallized, and for example, crystallization may occur in a heating step before embossing. In general, since a polyester-based resin exhibits adhesiveness during crystallization, if the resin B is not sufficiently crystallized, the effect of preventing adhesion to a heating roll intended in the present invention cannot be obtained.
In order to sufficiently crystallize the polyester resin constituting the B layer 13b at the time of forming the sheet, it is preferable to control the casting temperature and the like at the time of film formation, but the main component of the polyester resin constituting the B layer 13b As the crystalline polyester resin to be obtained, polybutylene terephthalate having a high crystallization speed or a copolymer thereof is suitable.
In addition, in order for the polyester resin constituting the B layer 13b to fulfill the function of preventing fusing, the polyester resin constituting the B layer 13b even at a temperature at which the polyester resin constituting the A layer 12b softens. The resin needs to retain the elastic modulus. In general, in the case of an amorphous resin, Tg + 30 [° C.] is a standard for starting softening. Accordingly, when the crystal melting peak temperature (melting point) of the B layer 13b is Tm (B) [° C.] and the Tg of the A layer 12b is Tg (A) [° C.], Tm (B)> Tg (A) +30 [ If it is [degreeC], embossing can be given to A layer 12b below Tm (B), and it is preferred.
The polyester resin used in the present invention shields the base metal plate that is the base of the coated base material, that is, visually shields the base metal plate (prevents see-through), imparts design properties, and colors the printing ink layer. A pigment is added for the purpose of improving properties. The pigment to be used may be one conventionally used for coloring a resin, and the addition amount thereof may be an amount generally added for the above purpose.
[Embossing sheet]
Embossing sheet 15b in which embossing 14 is formed on the surface of layer A 12b as shown in FIG. 1B by embossing the laminated resin sheet 11b configured as described above by the above method. Is obtained.
[Coating layer]
As shown in FIG. 1C, the laminated resin sheet 11b may have a configuration in which a transparent resin layer 16b is formed as a coating layer on the A layer 12b. The transparent resin for forming the transparent resin layer 16b has the same purpose as that for a soft vinyl chloride resin-coated steel sheet or an olefin resin-coated steel sheet, that is, protection of the printed layer, imparting a deep design, and additives such as pigments. Resins similar to those used for the purpose of preventing ejection and improving various physical properties of the surface can be used. For example, acrylic resin, ethylene vinyl alcohol copolymer, polyester resin and the like can be mentioned. As a method for laminating the transparent resin, a commonly used method such as a co-extrusion method, extrusion lamination, heat fusion method, dry lamination, or solution coating can be used.
Moreover, as shown in FIG.1 (d), the laminated resin sheet 11b is printed on the A layer 12b to form the printed layer 17b, and the transparent resin layer 16b is laminated thereon. Also good. The printing on the A layer 12b is performed by, for example, gravure printing, offset printing, screen printing, or other known methods to form the printing layer 17b. The pattern of the printed layer 17b is arbitrary, such as a stone tone, a woodgrain tone, a geometric pattern, an abstract pattern, etc., and may be partially printed or entirely solid printed, or may be further subjected to solid printing after partial printing. .
To the A layer 12b, the B layer 13b, and the transparent resin layer 16b, additives such as a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a nucleating agent, a colorant, Various additives such as antibacterial and antifungal agents, antistatic agents, lubricants, flame retardants and fillers may be appropriately blended.
[Coating substrate]
By laminating the laminated resin sheet 11b or the embossed sheet 15b on a metal plate via an adhesive, for example, as shown in FIG. 2 (a), the laminated resin sheet 11b shown in FIG. A coated substrate 20b laminated on the metal plate 18b via the adhesive layer 19b is obtained.
As said metal plate 18b, various steel plates and aluminum plates, such as a hot-rolled steel plate, a cold-rolled steel plate, a hot dip galvanized steel plate, an electrogalvanized steel plate, a tin-plated steel plate, a stainless steel plate, can be used, for example, and a normal chemical conversion treatment was performed. It may be used later. Although the thickness of the metal plate 18 changes with uses of the coating | coated base material 20, it can select in the range of 0.1 mm-10 mm.
[Manufacturing method of laminated resin sheet and coated substrate]
Next, the manufacturing method of the laminated resin sheet 11b and the covering base material 20b will be described. As a method for forming the laminated resin sheet 11b, a known method, for example, an extrusion casting method using a T die, an inflation method, or the like can be adopted. From the viewpoint of productivity and the like, an extrusion casting method using a T die is preferable.
The molding temperature in the extrusion casting method using a T-die is appropriately adjusted depending on the flow characteristics and film-forming properties of the composition, but is generally in the range of the melting point to 280 ° C., preferably 240 to 270 ° C.
The thickness of the laminated resin sheet 11b is usually 50 to 500 μm. When the thickness of the laminated resin sheet 11b is less than 50 μm, the performance as a protective layer for the metal plate 18 is inferior when used for the covering substrate 20. Further, since the foundation metal plate shielding ability, that is, the visual shielding ability (prevention of see-through) of the foundation metal plate is low, the printed pattern is unfavorable due to the influence of the color of the foundation metal plate. On the other hand, when the thickness exceeds 500 μm, secondary workability such as punching as the coated substrate 20 tends to be poor.
Further, the thickness ratio of each layer is not particularly limited, but in order to give a deep embossed pattern, the thickness of the embossable layer 12 is preferably 80 μm or more.
Examples of the adhesive used when laminating the laminated resin sheet 11b on the metal plate 18b include generally used thermosetting adhesives such as epoxy adhesives, urethane adhesives, and polyester adhesives.
As a method for obtaining the coated substrate 20b, a commonly used coating facility such as a reverse roll coater or a kiss roll coater is used for the metal plate 18b, and the metal surface to which the laminated resin sheet 11a or the embossed sheet 15b is bonded is used. The said thermosetting adhesive is apply | coated so that the adhesive film thickness after drying may be set to about 2-10 micrometers. Next, using at least one of an infrared heater and a hot air heating furnace, the coated surface is dried and heated, and while maintaining the surface temperature of the metal plate 18 at a predetermined temperature, the laminated resin sheet 11b or immediately using a roll laminator The coated base material 20b is obtained by coating and cooling the B layer of the embossed sheet 15b as an adhesive surface. Moreover, in order not to erase the embossed pattern imparted to the embossing imparting sheet 15b, it must be cooled immediately after the embossing imparting sheet 15b is covered.
[Third invention]
Next, the third invention will be described.
As shown in FIG. 1 (c), the laminated resin sheet 11c according to the third invention is formed on the surface of the A layer 12c of the sheet obtained by laminating at least two polyester resin layers of the A layer 12c and the B layer 13c. This is a sheet provided with a transparent coating layer 16c having ultraviolet absorptivity as a coating layer.
In the laminated resin sheet 11c shown in FIG. 1 (d), in addition to the configuration of FIG. 1 (c), a printing layer 17c is provided between the A layer 12c and the transparent coating layer 16c. In the laminated resin sheet 11c shown in FIG. 1 (e), the transparent coating layer 16c is composed of two layers of transparent coating layers 16′c and 16 ″ c.
By embossing the laminated resin sheet 11c configured as described above by the method described above, an embossed sheet in which embossing (not shown) is imparted to the A layer 12c is obtained.
FIG. 2B shows an example of the coated base material 20c, and the laminated resin sheet 11c having the configuration shown in FIG. 1C is formed of a metal plate through the thermosetting adhesive 19c with the B layer as an adhesive surface. It is laminated on 18c. Further, an embossed sheet obtained by embossing the A layer 12c of the laminated resin sheet 11c configured as shown in FIG. 1D or FIG. 1E is used as a thermosetting adhesive 19c with the B layer as an adhesive surface. The coated substrate 20c may be manufactured by laminating on the metal plate 18c via
The A layer 12c and the B layer 13c are formed of polyester resins having different compositions.
[A layer]
The polyester resin constituting the A layer 12c is composed mainly of a substantially amorphous polyester resin or a polyester resin in which a clear crystal melting peak is not observed at the time of temperature rise as measured by a differential scanning calorimeter (DSC). A mixture of Here, “main component” means that it is contained by 50% or more by weight.
The substantially amorphous polyester resin includes terephthalic acid, isophthalic acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, etc. as the acid component, ethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedi as the alcohol component. It is arbitrarily selected from copolymers using methanol or the like. However, it is necessary to satisfy the above condition, and in the measurement with a differential scanning calorimeter (DSC), a clear crystal melting peak should not be observed at the time of temperature rise.
An example of this copolymer is “Easter” 6763 from Eastman Chemical Co., but is not limited thereto. Resin A becomes substantially amorphous or low crystalline because the polyester-based resin that is the main component of resin A is substantially amorphous. Such a polyester-based resin has physical properties of a substantially amorphous resin that gradually softens from a temperature in the vicinity of Tg (glass transition point), and exhibits optimum characteristics for embossing.
Further, the resin blended with the polyester resin constituting the A layer 12c may have crystallinity. However, when the compounding ratio of the crystalline resin is increased, the polyester resin constituting the A layer 12c starts to exhibit the physical properties of the crystalline resin, and is not necessarily suitable for embossing. Disappear.
For the A layer 12c, when the coated substrate 20c is manufactured, the base metal plate 18c is shielded, that is, the base metal plate 18c is visually shielded (prevention of see-through), design is imparted, and the color development of the printing ink is improved. A pigment is added for the purpose. The pigment to be used may be one conventionally used for coloring a resin, and the addition amount thereof may be an amount generally added for the above purpose.
The A layer 12c has additives such as a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a nucleating agent, a colorant, an antibacterial / antifungal agent to the extent that the object of the present invention is not impaired. Various additives such as an antistatic agent, a lubricant, a flame retardant, and a filler may be appropriately blended.
[B layer]
The polyester resin constituting the B layer 13c is composed mainly of a substantially crystalline polyester resin or a polyester resin in which a clear crystal melting peak is observed at the time of temperature rise as measured by a differential scanning calorimeter (DSC). (That is, a mixture containing 50% or more by weight). Further, the resin B does not exhibit adhesiveness to the metal roll when the laminated resin sheet 11 is heated for embossing.
The substantially crystalline polyester resin that is the main component of the polyester resin constituting the B layer 13c includes diol components such as ethylene glycol, propylene glycol, butanediol, and cyclohexanedimethanol, and dicarboxylic acids such as terephthalic acid and isophthalic acid. It is arbitrarily selected from copolymers with an acid component. However, it is necessary to satisfy the above conditions, and in the measurement with a differential scanning calorimeter (DSC), it is necessary to observe a clear crystal melting peak when the temperature is raised.
Further, the resin blended with the polyester resin constituting the B layer 13c may not have crystallinity, but the B layer 13c as a whole is an apparatus for embossing at the time of film formation or continuously. It must be fully crystallized before it is introduced into the process. Here, “sufficiently crystallized” means that a clear crystallization peak is not observed at the time of temperature rise in the measurement by DSC.
A polyester resin in which a crystallization peak is observed by DSC is not sufficiently crystallized, and for example, crystallization may occur in a heating process of an embossing device. Generally, since a polyester-based resin exhibits adhesiveness during crystallization, if the polyester-based resin constituting the B layer 13c is not sufficiently crystallized, the effect of preventing adhesion to a heating roll intended in the present invention is achieved. Cannot be obtained.
In addition, in order for the polyester resin 13c constituting the B layer 13c to perform a fusing prevention function when the laminated resin sheet 11c is heated, the B layer 13c has an elastic modulus even at a temperature at which the A layer 12c is softened. It is necessary to hold. In general, in the case of an amorphous resin, Tg + 30 [° C.] is a standard for starting softening. Therefore, when the crystal melting peak temperature (melting point) of the polyester resin constituting the B layer 13c is Tm (B) [° C.] and the Tg of the polyester resin constituting the A layer 12 c is Tg (A) [° C.]. If Tm (B)> Tg (A) +30 [° C.], embossing can be applied to the A layer 12c at a temperature at which the base layer 13 below Tm (B) does not melt.
As a resin component that constitutes the polyester resin constituting the B layer 13c, or the main component of the polyester resin that constitutes the B layer 13c, for example, terephthalic acid and 1,4-butanediol are used as individual components. Mention may be made of polybutylene terephthalate obtained by condensation. In this case, since the crystallization speed is high, it can be in a state of being sufficiently crystallized at the time of extrusion casting, which is preferable because a crystallization process in a separate step is not required. Moreover, since the melting point is lower than that of polyethylene terephthalate, it is also preferable that a strong adhesive force can be obtained at a relatively low lamination temperature when laminating the metal plate 18. However, the present invention is not limited to this, and does not deviate from the range of Tm (B)> Tg (A) +30 [° C.], and is sufficiently crystallized at the stage before being introduced into the embossing device. Any resin component can be used.
Also regarding the polyester resin constituting the B layer 13c, various additives may be appropriately blended depending on the purpose, as with the polyester resin constituting the A layer 12c.
[Transparent coating layer]
The main purpose of providing the transparent coating layer 16c having ultraviolet absorptivity is to suppress light yellowing of the polyester resin. And it has ultraviolet absorptivity means absorbing an ultraviolet-ray to such an extent that the light yellowing of the laminated resin sheet 11c is clearly improved compared with the case where there is no transparent coating layer 16c. Further, the transparent coating layer 16c itself needs to have good weather resistance, particularly yellowing resistance, to some extent.
The transparent coating layer 16c may be imparted with secondary effects such as adjustment of gloss, further improvement of scratch resistance, improvement of stain resistance, and application of a deep design. Further, when embossing is performed on the A layer 12c after the transparent coating layer 16c is provided on the laminated resin sheet 11c, a non-adhesive effect on the embossing roll may be imparted.
Depending on the combination of the main purpose and the secondary purpose, the transparent coating layer 16c may be a single layer or may be composed of two or more layers as shown in FIG. Also good.
The thickness of the transparent coating layer 16c is preferably in the range of 2 μm to 20 μm, more preferably in the range of 4 μm to 10 μm. If the thickness is less than 2 μm, although it has ultraviolet absorptivity, it cannot be said that its ultraviolet shielding ability is sufficient, and the effect of improving the light yellowing of the polyester resin cannot be obtained, which is not preferable. When the thickness is greater than 20 μm, as described as a problem in the prior art, the resin physical properties of the transparent coating layer 16c affect the important physical properties of the embossed sheet. That is, depending on the material of the transparent coating layer 16c, the processability or scratch resistance may be deteriorated or the emboss transfer property may be deteriorated.
A method for providing the transparent coating layer 16c having the above-described properties and having the above thickness on the surface of the A layer 12c of the laminated resin sheet 11c is not particularly limited. For example, three-layer coextrusion in the configuration of the transparent coating layer 16c + A layer 12c + B layer 13c, or four-layer coextrusion through an adhesive resin layer between the transparent coating layer 16c and the A layer 12c may be used. However, it is generally preferable to depend on the coating method from the viewpoint that the transparent coating layer 16c having a relatively thin thickness can be stably formed.
Among the coating methods, it is preferable to use a crosslinkable resin coating because the secondary effect can be imparted. The crosslinkable resin referred to here is a thermosetting resin such as cyanate curable type and epoxy curable type, moisture curable resin such as cyanoacrylate resin and silanol condensation type resin, ultraviolet curable resin, electron beam curable resin, etc. Is included in the category, and a three-dimensional molecular structure is formed by a crosslinking reaction. Ionomer resins that form a three-dimensional structure by ionic crosslinking are not included.
Among these crosslinkable resins, thermosetting resins such as a cyanate curable type and an epoxy curable type that can be applied and cured relatively easily and can obtain various coating film properties by selecting a crosslinkable resin and a curing agent. It can be preferably used. From the viewpoint that the resin itself has good weather resistance, a cyanate-crosslinked acrylic resin, a cyanate-crosslinked acrylic silicone resin, and a cyanate-crosslinked fluoroolefin vinyl ether copolymer resin are particularly preferable. However, the resin type is not limited to these, and the resin type can be appropriately selected according to the balance between the required light resistance stability and other required physical properties. As described above, the transparent coating layer 16c may have a laminated structure including two or more layers. In the case of a cyanate curable resin, the improvement of light yellowing, which is the main purpose of the transparent coating layer 16c of the present invention, cannot be achieved unless a non-yellowing cyanate is used as a curing agent.
The method for applying a crosslinkable resin coating layer on the A layer 12c as the transparent coating layer 16c is not particularly limited, and can depend on a general coating and curing method. Various solvents may be used to lower the viscosity of the coating solution, and it can be applied as a solution type, a dispersion type or an emulsion type.
As a method for imparting ultraviolet absorptivity to the transparent coating layer 16c, a method in which an additive type ultraviolet absorber is added to the coating liquid and applied is generally used. Among various commercially available ultraviolet absorbers such as benzotriazole type, benzophenone type, and triazine type, those that are solvent-soluble, those that are finely dispersed in an aqueous emulsion, aqueous dispersion, and the like can be used as appropriate. .
The preferable addition amount of the ultraviolet absorber can vary depending on the coating thickness of the transparent coating layer 16c, the required yellowing resistance, etc., and thus cannot be defined unconditionally, but generally 0.5 to 5.0 parts by weight It is preferable to add about (resin solid content is 100). When the added amount is less than 0.5 parts by weight, the transparent coating layer 16c may be thin, and it is not preferable because an effective ultraviolet shielding property cannot be secured. When the addition amount is more than 5.0 parts by weight, there is a possibility that the ultraviolet absorber may be ejected from the surface of the transparent coating layer 16c, which is not preferable.
Further, as a method for imparting ultraviolet absorptivity, a method in which a crosslinkable resin component constituting the transparent coating layer 16c is copolymerized with a reactive monomer having an ultraviolet absorbing group such as a benzotriazole type or a benzophenone type is used. Good. Alternatively, it may be blended with a non-crosslinkable acrylic resin copolymerized with a reactive monomer having a UV-absorbing group such as a benzotriazole type or a benzophenone type while having a crosslinkable resin component as a main component. Good.
These so-called polymer type ultraviolet absorbers have good volatilization resistance and migration resistance, and in a configuration in which a thin layer is laminated on another layer like the transparent coating layer 16c of the present invention, the thin layer is shielded from ultraviolet rays. It can be suitably used when it is desired to impart the properties.
Further, instead of an organic ultraviolet absorber, a so-called inorganic ultraviolet absorber such as fine particle titanium oxide having substantially sealed catalytic activity may be added. In addition to the ultraviolet absorber, additives generally used for crosslinkable resins such as general antioxidants, matting agents, dyes, and curing accelerators can be added to the transparent coating layer 16c. . In addition, although there is no particular rule regarding the “transparency” of the transparent coating layer 16c, it is possible to visually recognize the A layer 12 or the printed layer 17c colored by adding a pigment as a base through the transparent coating layer 16c. If there is, it is possible to call it “transparent” and there is no problem, and it does not necessarily coincide with the commonly used definition of “transparent”.
[Print layer]
The printing layer 17c can be applied by gravure printing, offset printing, screen printing, or other known methods. The pattern of the printed layer 17c is arbitrary, such as a stone tone, a woodgrain tone, a geometric pattern, an abstract pattern, etc., may be partial printing or full-surface solid printing, and may be further subjected to solid printing after partial printing. .
[Method for producing laminated resin sheet]
As a method for forming the laminated resin sheet 11c, a known method, for example, a coextrusion casting method or an inflation method using a feed block method or a multi-manifold method can be employed, and the method is not particularly limited. The coextrusion casting method using a T die is preferable from the viewpoints of film forming property and stable productivity.
The thickness of the laminated resin sheet 11c is usually 50 to 500 μm. In order to impart a deep embossed pattern, the thickness of the laminated resin sheet 11c is preferably 80 μm or more. When the thickness of the laminated resin sheet 11c is less than 50 μm, the performance as a protective layer for the metal plate 18c is inferior when used for the covering substrate 20c. Further, since the shielding ability of the base metal plate is low, when the print layer 17c is provided, the printed pattern is not preferable because of the influence of the color of the base metal plate. On the other hand, when the thickness exceeds 500 μm, secondary workability such as punching as the coated substrate 17 tends to be inferior.
Moreover, the preferable thickness of each of the A layer 12c and the B layer 13c cannot be defined unconditionally depending on the type of embossed pattern to be applied, the temperature condition of the embossing apparatus to be used, the tension condition, and the like. However, since the thickness of the soft vinyl chloride resin sheet for conventional use has been about 80 to 200 μm, the total thickness is 100 to 240 μm, of which the thickness of the B layer 13c is 10 to 50 μm. Therefore, the thickness of the A layer 12c is About 50-230 micrometers is preferable. With this thickness, it is possible to give an embossed pattern to the laminated resin sheet 11c of the present invention with most of the embossed plate rolls that have been used for embossing to a conventional PVC sheet.
[Metal plate]
As the metal plate 18c, for example, various steel plates such as hot-rolled steel plate, cold-rolled steel plate, hot-dip galvanized steel plate, electrogalvanized steel plate, tin-plated steel plate, stainless steel plate and the like, aluminum plates, and aluminum-based alloy plates can be used. It may be used after the treatment. The thickness of the metal plate 18c varies depending on the use of the coated base material 20c and the like, but can be selected in the range of 0.1 mm to 10 mm.
[Method for producing coated substrate]
Next, the manufacturing method of the covering base material 20c coated with the embossing sheet will be described.
As an adhesive used when laminating the laminated resin sheet 11c provided with the transparent coating layer 16c and embossed by the embossing device 30 on the metal plate 18c, an epoxy-based adhesive, a urethane-based adhesive, a polyester-based adhesive is used. Examples of the thermosetting adhesive generally used include an adhesive. As a method of obtaining the coated substrate 20c, a commonly used coating facility such as a reverse roll coater or a kiss roll coater is used for the metal plate 18c, and the adhesive after drying on the metal surface to which the laminated resin sheet 11c is bonded. The thermosetting adhesive is applied so that the film thickness is about 2 to 10 μm.
Next, the coated surface is dried and heated using at least one of an infrared heater and a hot-air heating furnace, and the surface temperature of the metal plate 18c is maintained at a predetermined temperature, and immediately using the roll laminator, the laminated resin sheet 11c is heated. The coated substrate 20c is obtained by coating and cooling so that the B layer 13c side becomes the adhesive surface. Moreover, in order not to erase the embossed pattern imparted to the laminated resin sheet 11c, it is necessary to cool immediately after coating the laminated resin sheet 11c.
[Fourth Invention]
Next, the fourth invention will be described.
A laminated resin sheet 11d according to the fourth invention is a sheet in which an A layer 12d and a B layer 13d are laminated as shown in FIG.
Moreover, in the laminated resin sheet 11d shown in FIG. 1 (f), an adhesive layer 21d is provided between the A layer 12d and the B layer 13d in addition to the configuration shown in FIG. 1 (a). Further, in the laminated resin sheet 11d shown in FIG. 1 (g), in addition to the configuration of FIG. 1 (a), a coating layer 22d having non-adhesiveness with a heated metal is provided on the surface of the A layer 12d as a coating layer. It has been.
Furthermore, FIG. 2C is a schematic diagram showing an example of the coated substrate 20d. As shown in FIG.2 (c), as for the coating | coated base material 20d, the laminated resin sheet 11d shown to Fig.1 (a) is laminated | stacked through the thermosetting adhesive bond layer 19d on the single side | surface of the metal plate 18d. .
In addition, the laminated resin sheet 11d having the configuration shown in FIGS. 1 (f) and 1 (g) may be similarly laminated on the metal plate 18d.
[A layer]
The A layer 12d and the B layer 13d are formed of polyester resins having different physical properties.
The polyester-based resin constituting the A layer has a clear crystallization peak temperature Tc (A) [° C.] and a crystal melting peak in the sheet before embossing, at the time of temperature rise measured by a differential scanning calorimeter (DSC). When the temperature Tm (A) [° C.] is observed, the heat of crystallization is ΔHc (A) [J / g], and the heat of crystal fusion is ΔHm (A) [J / g], the following relational expression holds: To do.
10 ≦ ΔHm (A) ≦ 35
(ΔHm (A) −ΔHc (A)) / ΔHm (A) ≦ 0.5
The observation of a clear crystal melting peak temperature Tm (A) [° C.] means that the polyester resin constituting the A layer is not an amorphous resin. Even when a completely non-crystalline resin is used as the polyester-based resin constituting the A layer, the embossed design can be imparted by the embossing imparting device by using the laminated configuration of the present invention.
However, generally, the glass transition temperature (Tg) of the non-crystalline polyester resin is lower than 100 ° C., and therefore, when the boiling water immersion test which is an item of the unit bath standard test is performed, the A layer is formed. This is not preferable because the polyester resin to be softened and the embossed design imparted disappears. In addition, when the A layer 12 and the B layer 13 are not co-extruded and are laminated and integrated using the adhesive layer 21d, when the non-crystalline resin is used as the polyester resin constituting the A layer, boiling occurs. In the water immersion test, problems such as peeling are likely to occur between the A layer 12d and the adhesive layer 21d, which is not preferable.
When (ΔHm (A) −ΔHc (A)) / ΔHm (A) is larger than 0.5, this is a case where the crystallization of the resin A before embossing is in progress, and “the invention is to be solved” As described in "Problem", emboss transfer becomes difficult because a high elastic modulus is maintained up to the melting point of the polyester resin constituting the A layer.
Moreover, when ΔHm (A) is larger than 35 [J / g], it means that the resin composition has a relatively high crystallinity. In this case, even in the case where (ΔHm (A) −ΔHc (A)) / ΔHm (A) ≦ 0.5 is satisfied in the sheet before passing through the embossing device, the heated metal roll of the embossing device is used. While the sheet is heated, crystallization of the polyester-based resin constituting the A layer proceeds, and as a result, embossing tends to be difficult, which is not preferable. On the other hand, when ΔHm (A) is smaller than 10 [J / g], the same problem as in the case of using a completely non-crystalline resin as the polyester resin constituting the A layer occurs, which is not preferable.
By making these values relating to the polyester-based resin constituting the A layer within the scope of the present invention, embossing design can be imparted with an embossing device, and the embossing design disappears even after the boiling water immersion test. Or an embossed design that does not cause problems such as a shallow embossed pattern.
This is because, within the scope of the present invention, the polyester-based resin constituting the A layer is in a state where crystallization is not progressing even though it is a composition of a crystalline resin before being passed through the embossing device. Therefore, it has the same property as an amorphous resin. In addition, when it is passed through an embossing device and heated by a heated metal roll, crystallization is unlikely to proceed because of its composition that is not so high, and also exhibits the same properties as an amorphous resin. . Therefore, it is considered that a good embossed design can be applied, and crystallization proceeds immediately after the embossing cooling process or immediately after being immersed in boiling water, so that an embossing with good boiling water resistance can be obtained. .
As a polyester-type resin which comprises A layer, it is possible to obtain the physical property which satisfy | fills Claim 1 of this invention by various copolymerization, blend, alloying, etc. Among them, a so-called homo-polybutylene terephthalate resin using a single component for each of an acid component and an alcohol component, or a homo-polytrimethylene terephthalate resin as a crystalline resin component, which is a non-crystalline copolymer polyester type The method of blending the resin is preferable from the viewpoint of easily adjusting desired physical properties.
As the non-crystalline copolyester, so-called PET-G, which is low in cost because of the stable supply of raw materials and a large amount of production, can be used, such as “Easter 6863” manufactured by Eastman Chemical Co., Ltd. It is preferable to use a similar resin. However, the present invention is not limited to this, and neopentyl glycol copolymerized PET does not show crystallinity, or shows crystallinity under specific conditions, but can be handled as an amorphous resin under normal conditions. “PCTG 5445” manufactured by Eastman Chemical Co. can also be used.
Even in the case of using a resin with a high crystallization speed such as a homo-polybutylene terephthalate (PBT) resin or a homo-polytrimethylene terephthalate (PTT) resin, by blending an amorphous resin, Since the crystallization speed becomes slow, it becomes possible to obtain a sheet in a state satisfying the requirements of the present invention.
Furthermore, when these crystalline resins are used, it is preferable from the viewpoint of easily obtaining a sheet excellent in boiling water resistance of an embossed design. This is when the blend ratio of the crystalline resin and the non-crystalline resin is the same, and when the copolymer resin such as homo-polyethylene terephthalate (PET) resin or isophthalic acid copolymer polyester resin is blended as the crystalline resin This is because the crystallization speed in the blend composition is relatively fast. That is, it is considered that the PBT resin and the PTT resin satisfy the requirements of the present invention, and when they are immersed in boiling water, crystallization progresses relatively quickly and is excellent in ability to retain the shape.
When the coated base material 20d is manufactured, a pigment is added to the polyester resin constituting the A layer for the purpose of concealing the underlying metal plate 18c, imparting design properties, and improving the color developability of the printing ink layer. The pigment to be used may be one conventionally used for coloring a resin, and the addition amount thereof may be an amount generally added for the above purpose.
An appropriate amount of additives may be added to the A layer 12d so as not to impair the object of the present invention. Additives include phosphorous and phenolic antioxidants, heat stabilizers, UV absorbers, light stabilizers, nucleating agents, metal deactivators, residual polymerization catalyst deactivators, nucleating agents, antibacterials, Examples thereof include those generally used for a wide range of resin materials such as fungicides, antistatic agents, lubricants, flame retardants, fillers and the like. Moreover, what is marketed for polyester resins, such as a carbodiimide type | system | group, an epoxy type other terminal carboxylic acid sealing agent, or a hydrolysis inhibitor, can also be mentioned.
[B layer]
In the polyester resin constituting the B layer, a clear crystal melting peak temperature Tm (B) [° C.] is observed in the sheet before embossing at the time of temperature rise as measured by a differential scanning calorimeter (DSC). When the heat of formation is ΔHc (B) [J / g] and the heat of crystal fusion is ΔHm (B) [J / g], the following relational expression is established.
180 ≦ Tm ≦ 240
0.5 ≦ (ΔHm−ΔHc) / ΔHm
The observation of a clear crystal melting peak temperature Tm (B) “° C.” means that the polyester resin constituting the B layer is not an amorphous resin, and at the same time before passing through the embossing device. The sheet must be crystallized to some extent, even if the polyester resin constituting the layer B has a crystalline composition, but the crystallinity is low, the heated metal roll of the embossing device When the crystallization state of the polyester resin constituting the B layer satisfies the above requirements, it is possible to prevent adhesion to the heated metal roll and to serve as the B layer 13d. It becomes.
In addition, the melting point of the polyester-based resin constituting the B layer needs to be in the range of 180 ° C. to 240 ° C. This is the same as the laminating equipment that has been used for laminating a conventional soft PVC sheet to a metal plate. This is because it can be used. When the melting point of the resin B is lower than this, it is preferable in that the adhesive force can be secured at a low temperature when laminating to a metal plate, but when the sheet is heated under the same conditions as a conventional soft PVC sheet with an embossing device, The sheet temperature is close to the melting point of the polyester resin constituting the B layer, and there is a risk of sticking to the heated metal roll or melt fracture, which is not preferable. Although it is conceivable to lower the sheet heating temperature in the embossing apparatus, it is not preferable because the heat resistance of the embossing is lower than that of the soft PVC sheet provided with an embossed pattern under normal conditions.
The heat resistance of embossing indicates whether the embossing return is large or small when the embossed design-coated substrate is exposed to high heat in use, and the embossing heat resistance is good when the return is small. When the embossing heat resistance is poor, there is a case where emboss return is caused by heating at the time of laminating with a steel plate.
Since embossing on the sheet is basically an operation for imparting strain to the viscoelastic body, the higher the temperature at which the strain is imparted, the better the embossing heat resistance of the embossed design steel plate. In other words, it is conceivable that the sheet heating temperature in the embossing device is as high as possible and then passed through the embossing roll, or the temperature of the embossing roll itself is set high. In the latter case, the adhesion of the sheet to the embossing roll is considered. The current situation is that it is implemented in balance with the former. When a conventional soft PVC sheet is passed through an embossing device under conventional conditions, embossing heat resistance that is satisfactory in practice is obtained.
If the melting point of the polyester resin constituting the layer B is higher than this, it is necessary to laminate the steel sheet surface temperature higher than the conventional laminating temperature condition, causing problems of thermal discoloration / thermal discoloration of the back surface coating, cooling of the edges. Is not preferable because it causes problems such as non-uniform adhesion strength due to non-uniformity in the width direction of the steel sheet.
Further, when (ΔHm (B) −ΔHc (B)) / ΔHm (B) of the resin B in a state before passing through the embossing device is smaller than 0.5, crystals of the polyester resin constituting the B layer However, the embossing device does not adhere to the heated metal roll, melts and breaks the sheet, and cannot play the role of the B layer 13d. When the value is 0.5 or more, these problems can be avoided.
As the polyester-based resin constituting the B layer, it is possible to obtain a physical property satisfying the requirements of the present invention by various copolymerization, blending, alloying and the like. Among these, it is preferable to use a so-called homo-polybutylene terephthalate (PBT) resin or a homo-polytrimethylene terephthalate (PTT) resin using a single component for each of the acid component and the alcohol component as the crystalline resin component. Among these resins, a polyethylene terephthalate resin having a melting point in a preferable melting point range of 180 ° C. to 240 ° C. has a high crystallization speed and a glass transition temperature (Tg) of polyethylene terephthalate (PET) resin. Lower. Accordingly, (ΔHm (B) −ΔHc (B)) / ΔHm (B) can be set to 0.5 or more by appropriately adjusting the temperature of the take-up roll during extrusion film formation. No special processing steps are required. Isophthalic acid copolymerized PET can also be obtained by adjusting the copolymerization ratio of isophthalic acid to have a melting point in the temperature range. This is not preferable because a separate crystallization treatment step is required. If you want to obtain strong adhesive strength at a slightly lower temperature than the melting point of homo-polybutylene terephthalate (PBT) resin depending on the conditions of the laminating equipment, use a PBT resin whose melting point has been lowered by isophthalic acid copolymerization or the like. Also good. Also in that case, it is preferable to set it as the copolymerization ratio of the range which can obtain 0.5 or more as a value of ((DELTA) Hm (B)-(DELTA) Hc (B)) / (DELTA) Hm (B) at a sheet | seat film forming process.
In addition, a homo-PBT resin or a homo-PTT resin may be used as a main component, and an amorphous resin may be blended. In this case, crystallization proceeds to such an extent that it does not stick to the heated metal roll during extrusion film formation. In order to obtain the resin B, the value of 35 ≦ ΔHm (B) needs to be secured as the blend composition of the resin B. If ΔHm (B) is smaller than this, it means that the blend ratio of the amorphous resin is high, and the crystallization speed of the blend composition becomes slow, making it difficult to obtain a crystallized sheet during film formation. Is not preferable. In addition, ΔHm (B) is about 60 [J / g] or less in a generally available crystalline polyester resin. Also for the resin B, various necessary additives may be appropriately added in the same manner as the polyester resin constituting the A layer.
[Method for producing laminated resin sheet]
As a method for producing the laminated resin sheet 11d, a known method such as a co-extrusion casting method or an inflation method using a feed block method or a multi-manifold method can be adopted, and it is not particularly limited. A sheet is independently formed using the polyester resin constituting the A layer and the polyester resin constituting the B layer, and the polyester resin sheet constituting the A layer is not crystallized. The polyester resin sheet that constitutes a laminated resin sheet (design) with excellent embossability in an embossing device can be obtained by subjecting it to a crystallization treatment in a later step and then laminating and integrating with an adhesive or the like. Sheet) 11d can be obtained.
However, in general, it is preferable that the polyester-based resin constituting the A layer and the polyester-based resin constituting the B layer are coextruded to form a laminated resin sheet 11d from the viewpoint of fewer necessary steps. In this case, the physical properties required for the B layer 13 can be imparted at the time of extrusion film formation by using a polyester-based resin that satisfies the above-described conditions.
The total thickness of the laminated resin sheet 11d is usually 50 to 500 μm. In order to give a deep embossed pattern, the thickness of the laminated resin sheet 11d is preferably 80 μm or more. When the thickness of the laminated resin sheet 11d is less than 50 μm, the performance as a protective layer for the metal plate 18d is inferior when used for the covering substrate 20d. Further, when the sheet is thin, it is necessary to add a large amount of pigment in order to prevent the base metal plate from being seen through, and a thickness of 50 μm or more is required from the viewpoint that workability may be deteriorated.
On the other hand, when the thickness exceeds 500 μm, secondary workability such as punching as the coated base material 20d is deteriorated, which is not preferable. Further, it is difficult to use a mold that has been used for a conventional soft vinyl chloride-coated substrate, which is not preferable because a new mold needs to be produced.
Moreover, the preferable thickness of each of the A layer 12d and the B layer 13d cannot be defined unconditionally depending on the type of embossed pattern to be applied, the temperature condition of the embossing apparatus to be used, the tension condition, and the like. However, since the thickness of the flexible PVC sheet for conventional use has been about 80 to 200 μm, the total thickness is 100 to 240 μm, of which the thickness of the B layer 13d is 10 to 50 μm. Therefore, the thickness of the A layer 12d is 50 to 230 μm. The degree is preferred. With this thickness, it is possible to apply an embossed pattern to the laminated resin sheet 11d of the present invention with most of the embossing rolls that have been used for embossing of a conventional soft PVC sheet.
[Embossing on laminated resin sheet]
By embossing the laminated resin sheet 11d by the above method, an embossed sheet having an embossed pattern on the A layer can be produced.
In the laminated resin sheet 11d, the polyester resin that forms the A layer 12d and the B layer 13d has the above-described characteristics. Therefore, the embossing device 30 provides an embossed pattern in the same manner as a conventional soft PVC sheet. can do. Furthermore, since the melting point (Tm (B)) of the polyester-based resin constituting the B layer is in the range of 180 ° C. to 240 ° C., the sheet heating temperature in the embossing device 30 is 160 ° C. or higher. Even when the melting peak temperature (Tm (B)) is set to -20} ° C. or lower, adhesion to the heated metal roll and sheet melt fracture do not occur. And the embossing heat resistance equivalent to or more than the soft PVC which gave the embossing design with the embossing provision apparatus 30 is obtained.
[Applying a metal non-adhesive coating layer]
By transferring the embossed pattern at the above-mentioned sheet heating temperature, it is equivalent to soft PVC, and practically sufficient embossing heat resistance can be obtained, but depending on the application, even higher embossing heat resistance is required There is. In this case, the embossing heat resistance can be improved by increasing the temperature of the embossing roll together with setting the sheet heating temperature high. However, in the configuration of the present invention, although the heated layer non-adhesiveness is given to the B layer 13d by crystallization, the heated layer non-adhesive sufficient for the necessary properties of the A layer 12d. Does not have sex. Therefore, the non-adhesiveness to the hot embossing roll and other auxiliary rolls may be improved by providing a heated metal non-adhesive coating layer 22d on the surface of the A layer 12d.
The application of the coating layer 22d needs to be performed before the laminated resin sheet 11d is passed through the embossing apparatus, and can be performed by various ordinary coating techniques. Examples of the composition of the coating layer 22d include, but are not limited to, silicone-based, acrylic silicone-based, fluorine-based, and the like. Any non-adhesive material can be used without particular limitation. Alternatively, the coating layer 22d may be composed of two or more layers, the outermost layer may be a metal non-adhesive layer, and a layer having the function of an adhesive layer between the layer and the A layer 12d may be interposed. Further, secondary effects such as improvement of ultraviolet absorption and scratch resistance, improvement of contamination resistance, and application of a deep design may be imparted to the coating layer 22d.
The preferable thickness of the coating layer 22d is in the range of 1 to 10 μm, and if it is thinner than this, there is a possibility that problems such as partial adhesion to the heated metal roll may occur due to uneven coating, which is not preferable. If it is thicker than this, the resin physical properties of the coating layer 22d will affect the important physical properties of the laminated resin sheet 11d. That is, depending on the material of the coating layer 22d, the processability and scratch resistance are deteriorated or the embossing transferability itself is easily deteriorated, which is not preferable.
[Metal plate]
As the metal plate 18d, for example, various steel plates such as hot-rolled steel plate, cold-rolled steel plate, hot-dip galvanized steel plate, electrogalvanized steel plate, tin-plated steel plate, and stainless steel plate, aluminum plates, and aluminum alloy plates can be used. It may be used after the treatment. The thickness of the metal plate 18d varies depending on the application of the coated base material 20d and the like, but can be selected in the range of 0.1 mm to 10 mm.
[Method for producing coated substrate]
Next, a manufacturing method of the coated base material 20d coated with the embossing sheet will be described.
As an adhesive used when laminating the laminated resin sheet 11d to which the embossing pattern is imparted by the embossing device 30 on the metal plate 18d, an epoxy adhesive, a urethane adhesive, a polyester adhesive or the like that is generally used is used. A curable adhesive can be mentioned. First, using commonly used coating equipment such as a reverse roll coater and a kiss roll coater, the adhesive film thickness after drying is about 2 to 10 μm on the surface of the metal plate 18d on which the laminated resin sheet 11 is bonded. Then, the thermosetting adhesive is applied.
Next, the coated surface is dried and heated using at least one of an infrared heater and a hot-air heating furnace, and the surface temperature of the metal plate 18d is maintained at a predetermined temperature, and immediately, the roll resin laminator 11d is used. The coated substrate 16 is obtained by coating and cooling so that the B layer 13d side becomes the adhesive surface. According to the present invention, since the melting point (Tm (B)) of the polyester resin constituting the B layer located on the bonding surface side with the metal plate 18d is in the range of 180 to 240 ° C., the surface temperature of the metal plate 18d. It is possible to obtain a strong adhesive force by making it equivalent to the case of a conventional soft PVC sheet laminate-coated metal plate.
According to the present invention, a coated base material 20d having relatively good embossing heat resistance can be obtained. Immediately after lamination, water cooling is performed to reduce the return of embossing due to heating of the sheet during lamination. It is preferable.
The covering base material 20d can be used as a building interior material such as a door material, a unit bath wall material, or a unit bath interior material.
[Fifth Invention]
Next, a fifth invention will be described.
As shown in FIG. 1 (h), the laminated resin sheet 11e according to the fifth invention comprises at least an A layer 12e, a printed layer (hereinafter referred to as “C layer”) 17e, and a B layer 13e in this order. It is a sheet composed of three layers.
1 (i), in addition to the configuration of FIG. 1 (h), a C layer 17e and an adhesive layer 21e are provided between the A layer 12e and the B layer 13e in this order from the B layer 13e side. ing. Further, in FIG. 1 (j), a colored polyester resin layer (hereinafter referred to as "D layer") 23e is disposed between the C layer 17e and the B layer.
Further, in FIG. 1 (k), in addition to the configuration of FIG. 1 (h), a coating layer 22e having non-adhesiveness with a heated metal is provided on the surface of the A layer.
FIG. 2 (d) shows an example of the coated substrate 20e, and the laminated resin sheet 11e having the configuration shown in FIG. 1 (h) is laminated on the metal plate 18e via a thermosetting adhesive 19e. ing. Moreover, the laminated resin sheet 11e having the configuration shown in FIGS. 1 (i), 1 (j), and 1 (k) may be similarly laminated on the metal plate 18e.
[A layer]
The A layer 12e and the B layer 13e are formed of polyester resins having different physical properties.
In the sheet before embossing, a clear crystallization peak temperature Tc (A) (° C.) and a crystal melting peak temperature Tm (A) (° C.) are observed at the time of temperature rise by a differential scanning calorimeter (DSC). When the heat of crystallization is ΔHc (A) (J / g) and the heat of crystal fusion is ΔHm (A) (J / g), both of the following relational expressions hold.
10 ≦ ΔHm (A) ≦ 35 (J / g)
(ΔHm (A) −ΔHc (A)) / ΔHm (A) ≦ 0.5
The fact that a clear crystal melting peak temperature Tm (° C.) is observed means that the polyester resin constituting the A layer is not an amorphous resin. Even when a completely non-crystalline resin is used as the polyester resin constituting the A layer 12e, it is possible to give an embossed design with an embossing device by using the laminated structure of the present invention. Due to the glass transition temperature (Tg) of the reactive polyester resin being lower than 100 ° C., the polyester resin constituting the A layer 12e is softened when the boiling water immersion test, which is an item of the unit bath standard test, is performed. In addition, the embossed design imparted disappears, which is not preferable. In addition, when the A layer and the B layer are not co-extruded and are laminated and integrated using the C layer 17e, when a non-crystalline resin is used as the polyester resin constituting the A layer, a boiling water immersion test is performed. At this time, problems such as peeling are likely to occur between the A layer 12e and the C layer 17e, which is not preferable.
When (ΔHm (A) −ΔHc (A)) / ΔHm (A) is larger than 0.5, it is a case where crystallization of the polyester resin constituting the A layer 12e before embossing is in progress, As described in “Problems to be Solved by the Invention”, emboss transfer becomes difficult because a high elastic modulus is maintained up to the melting point of the polyester resin constituting the A layer 12e.
Further, when ΔHm (A) (J / g) is larger than 35 (J / g), it means that the resin composition has a relatively high crystallinity, and in the sheet before passing through the embossing device, Even when (ΔHm (A) −ΔHc (A)) / ΔHm (A) ≦ 0.5 is satisfied, the A layer 12e is formed while the sheet is heated by the heated metal roll of the embossing device. The crystallization of the polyester resin to proceed proceeds, and as a result, embossing tends to be difficult, which is not preferable. On the other hand, when ΔHm (A) (J / g) is smaller than 10 (J / g), the same problem appears as when a completely non-crystalline resin is used as the polyester resin constituting the A layer 12e. After all, it is not preferable.
By making these values relating to the polyester-based resin constituting the A layer 12e within the scope of the present invention, embossing design can be imparted with an embossing device, and the embossing design disappears even after the boiling water immersion test. Alternatively, an embossed design that does not cause problems such as a shallow embossed pattern can be obtained.
This is because, in the scope of the present invention, the polyester resin constituting the A layer 12e is in a state in which crystallization is not progressing in a state before passing through the embossing device 30, although it is a composition of the crystalline resin. Due to the fact that it has the same properties as an amorphous resin, crystallization progresses because the crystallinity is not so high when it is passed through an embossing device and heated by a heated metal roll. However, it exhibits the same properties as non-crystalline resin, so that it is possible to impart a good embossed design, and at the same time, crystallization proceeds immediately after the embossing process or immediately after being immersed in boiling water. It is thought that embossing with good boiling water resistance can be obtained.
As the polyester resin forming the polyester resin constituting the A layer 12e, it is possible to obtain a physical property satisfying claim 1 of the present invention by various copolymerization, blending, alloying, etc. So-called homo-polybutylene terephthalate (PBT) resin or homo-polytrimethylene terephthalate (PTT) resin, which uses a single component for each alcohol component, is used as a crystalline resin component. A method of blending a polymerized polyester resin is preferred from the viewpoint of easily adjusting desired physical properties.
As the non-crystalline copolyester, so-called PET-G, which is reduced in cost because of the stable supply of raw materials and the large amount of production, can be used, such as “Easter 6863” of Eastman Chemical Co., Ltd. It is preferable to use a similar resin. However, the present invention is not limited to this, and yeast that does not show crystallinity with neopentyl glycol copolymerized PET, or yeast that shows crystallinity under specific conditions but can be handled as an amorphous resin under normal conditions. “PCTG 5445” manufactured by Man Chemical Co., Ltd. can also be used.
Even when using a resin with a high crystallization speed, such as homo-polybutylene terephthalate (PBT) resin or homo-polytrimethylene terephthalate (PTT) resin, by blending the non-crystalline resin, Since the crystallization speed becomes slow, it is possible to obtain a sheet in a condition satisfying the conditions of the present invention.
Furthermore, when these crystalline resins are used, it is preferable also from the point which is easy to obtain the sheet | seat excellent in the boiling water of the embossing design. This is when the blend ratio of the crystalline resin and the non-crystalline resin is the same, and when the copolymer resin such as homo-polyethylene terephthalate (PET) resin or isophthalic acid copolymer polyester resin is blended as the crystalline resin Compared to the above, the crystallization rate in the blend composition is relatively fast, and while satisfying the conditions of the present invention, when immersed in boiling water, crystallization proceeds relatively quickly and has an excellent ability to retain the shape. It is thought that.
An appropriate amount of an additive may be added to the polyester resin constituting the A layer 12e in such a range that does not impair the transparency of the printed layer and does not impair other properties. Additives include phosphorous and phenolic antioxidants, heat stabilizers, UV absorbers, light stabilizers, nucleating agents, metal deactivators, residual polymerization catalyst deactivators, nucleating agents, antibacterials, Commonly used in a wide range of resin materials such as fungicides, antistatic agents, lubricants, flame retardants, fillers, carbodiimide-based and epoxy-based other terminal carboxylic acid sealing agents, or hydrolysis prevention The thing marketed as an object for polyester resins, such as an agent, can be mentioned.
The preferred thickness of the A layer 12e is in the range of 15 μm to 120 μm, and if it is thinner than this, the handleability of the formed film is poor, and since it is an unstretched film, it is not preferred because it tends to cause a problem in uniformity of thickness. When the B layer 13e is composed of a single layer, a thickness smaller than this is not preferable because only the A layer can impart deformation corresponding to the embossed pattern. When the thickness of the A layer 12e is thicker, the embossing transferability is improved, but since the A layer 12e is a resin composition having crystallinity, an increase in initial haze or an increase in haze over time becomes significant. This is not preferable because the transparency of the printed design deteriorates. Moreover, it is not preferable from the viewpoint that the yellowing of the A layer 12e becomes conspicuous when used indoors where ultraviolet irradiation is relatively strong. Depending on the embossed pattern to be transferred, it is necessary to give a deformation larger than the preferred thickness of the A layer. In this case, the D layer 23e is provided between the B layer 13e and the C layer 17e, and only the A layer 12e is used. The D layer 23e is also preferably deformed by pressing with an embossed pattern roll, and the thickness of the A layer 12e is preferably in the above range, more preferably in the range of about 25 μm to 80 μm.
[B layer]
In the sheet before embossing, a clear crystal melting peak Tm (B) (° C.) is observed at the time of temperature rise by a differential scanning calorimeter (DSC), and the heat of crystallization is ΔHc (B) (J / g), When the amount of heat of crystal melting is ΔHm (B) (J / g), the following relational expression needs to be satisfied.
180 ≦ Tm (B) ≦ 240 (° C.)
0.5 ≦ (ΔHm (B) −ΔHc (B)) / ΔHm (B)
The fact that a clear crystal melting peak temperature Tm (B) (° C.) is observed means that the polyester resin constituting the B layer 13e is not an amorphous resin, and at the same time before passing through the embossing device. It is necessary that crystallization has progressed to some extent. This is because even if the polyester-based resin constituting the B layer 13e has a crystalline composition, if the crystallinity is low, the embossing device sticks to the heated metal roll. When the crystallization state of the polyester resin constituting the B layer 13e satisfies the conditions of the present invention, the adhesion to the heated metal roll is prevented, and the B layer 13e can play a role.
Further, the melting point of the polyester resin constituting the B layer 13e needs to be in the range of 180 ° C. to 240 ° C., which is a laminate that has been used for laminating a conventional soft vinyl chloride sheet to a metal plate. This is because the equipment can be used as it is. When the melting point of the polyester-based resin constituting the B layer 13e is lower than this, it is preferable in terms of securing adhesive force at a low temperature when laminating to the metal plate 18e, but with an embossing device, a conventional soft vinyl chloride sheet and When the sheet is heated under the same conditions, the sheet temperature becomes close to the melting point of the polyester resin constituting the B layer 13e, which is not preferable because there is a risk of sticking to the heated metal roll or melt fracture. Although it is conceivable to lower the sheet heating temperature in the embossing device 30, this is also not preferable because the heat resistance of the embossing is lower than that of the soft vinyl chloride sheet provided with an embossed pattern under normal conditions.
The heat resistance of the emboss indicates whether the emboss return is large or small when the embossed design-coated substrate is exposed to high heat in use.
Since embossing to the sheet by the embossing device 30 is basically an operation of freezing the strain by cooling after imparting the strain to the viscoelastic body, the higher the temperature at which the strain is applied, the higher the embossing heat resistance of the coated substrate 20e. The property is also good. That is, it is considered that the sheet heating temperature in the embossing device 30 is made as high as possible and then passed through the embossed pattern roll, or the temperature of the embossing roll itself is set high. In the latter case, the sheet is transferred to the embossing roll. There are concerns about sticking, and the current situation is that it is carried out in balance with the former. When a conventional soft vinyl chloride sheet is passed through an embossing apparatus under conventional conditions, embossing heat resistance that is satisfactory in practice is obtained.
If the melting point of the polyester resin constituting the B layer 13e is higher than this, it is necessary to laminate the steel sheet surface temperature higher than the conventional laminating temperature condition, and there is a problem of thermal discoloration / thermal discoloration of the back coating, Since the cooling becomes prominent, problems such as non-uniform adhesive strength due to non-uniform width of the steel sheet temperature are undesirable.
Further, when (ΔHm (B) −ΔHc (B)) / ΔHm (B) in a state before passing through the embossing device 30 of the polyester resin constituting the B layer 13e is smaller than 0.5, the B layer 13e The crystallization of the polyester resin constituting the material does not proceed, and the embossing device cannot adhere to the heated metal roll, melt breakage of the sheet, etc., and cannot play the role of the polyester resin constituting the B layer 13e. . When the value is 0.5 or more, these problems can be avoided.
As the polyester-based resin constituting the B layer 13e, it is possible to obtain physical properties satisfying the conditions that the resin B of the present invention should have by various copolymerization, blending, alloying, etc., but an acid component, an alcohol component It is preferable to use so-called homo-polybutylene terephthalate (PBT) resin or homo-polytrimethylene terephthalate (PTT) resin using a single component for each of these as the crystalline resin component. These polyesters have a high crystallization rate and a lower glass transition temperature (Tg) than polyethylene terephthalate (PET) resins among polyester resins having a melting point between 180 ° C. and 240 ° C. which is a preferable melting point range. Therefore, (ΔHm (B) −ΔHc (B)) / ΔHm (B) can be set to 0.5 or more by appropriately adjusting the take-up roll temperature during extrusion film formation, and post-treatment for crystallization. This is because no process is required. Isophthalic acid copolymerized PET can be obtained by adjusting the copolymerization ratio of isophthalic acid to obtain a melting point in the temperature range, but in that case, the crystallization speed is slowed down, and the crystal is separated separately in the subsequent process of sheet film formation. This is not preferable because it requires a chemical treatment step. If you want to obtain strong adhesive strength at a slightly lower temperature than the melting point of homo-polybutylene terephthalate (PBT) resin depending on the conditions of the laminating equipment, use a PBT resin whose melting point has been lowered by isophthalic acid copolymerization, etc. In this case as well, it is preferable to set the copolymerization ratio within a range in which 0.5 or more can be obtained as the value of (ΔHm (B) −ΔHc (B)) / ΔHm (B) in the sheet film forming step.
A homopolybutylene terephthalate (PBT) resin or a homopolytrimethylene terephthalate (PTT) resin as a main component may be blended with an amorphous resin, but in this case as well, heating is performed during extrusion film formation. It is necessary that crystallization has progressed to such an extent that it does not stick to the metal roll.
In order to obtain the polyester resin constituting the B layer 13e, it is necessary to ensure a value of 35 ≦ ΔHm (B) as the blend composition of the polyester resin constituting the B layer 13e. If ΔHm (B) is smaller than this, this means that the blend ratio of the amorphous resin is high, and the crystallization speed of the blend composition becomes slow, making it difficult to obtain a crystallized sheet during film formation. It is not preferable. Further, in a generally available crystalline polyester resin, ΔHm (B) is about 65 (J / g) or less.
When the D layer 23e is not interposed, a color pigment is added to the polyester resin constituting the B layer 13e in order to conceal the base metal, improve the color of the C layer 17e, and improve the design. As the pigment that can be used, those generally used for coloring polyester resins can be used. Moreover, you may add suitably various required additives similarly to the polyester-type resin which comprises A layer 12e also with respect to the polyester-type resin which comprises B layer 13e.
[D layer]
When the D layer 23e is interposed between the C layer 17e and the B layer 13e, it is preferable that the D layer 23e basically has the same characteristics as the A layer 12e except that a pigment is added. At this time, the B layer 13e needs to have the same characteristics as the B layer 13e when the D layer 23e is not interposed, except that pigment addition is not always necessary. This configuration has an upper limit on the preferred thickness of the A layer 12e as described above, and can be suitably used when it is desired to transfer a deeper embossed pattern. In other words, the layer that undergoes deformation by pressing with the embossed pattern roll is made the A layer + D layer, thereby avoiding the problems that occur when the A layer is thickened, while enabling the transfer of a deep embossed pattern.
That is, the D layer 23e has a clear crystallization peak temperature Tc (D) (° C.) and a crystal melting peak temperature Tm (D) when heated by a differential scanning calorimeter (DSC) in the sheet before embossing. When (° C.) is observed, the heat of crystallization is ΔHc (D) (J / g), and the heat of crystal fusion is ΔHm (D) (J / g), both of the following relational expressions hold.
10 ≦ ΔHm (D) ≦ 35 (J / g)
(ΔHm (D) −ΔHc (D)) / ΔHm (D) ≦ 0.5
The reason why the D layer 23e requires these requirements is the same as in the case of the A layer 12e described above.
The total thickness of the laminated sheet including the A layer 12e is preferably 400 μm or less. If the thickness is larger than this, the workability of the metal plate covering the laminated sheet is deteriorated. In addition, when the thickness of the design effect of the laminated sheet, the protective effect on the base metal plate, etc. is increased, the thickness is preferably set to the above thickness or less from the viewpoint of saturation.
The lower limit of the preferable thickness range of the B layer 13e is 50 μm when the D layer 23e is not interposed. If the thickness is thinner than this, the underlayer is prevented from seeping through, so that a so-called concealing effect is imparted to the B layer 13e. It is necessary to add a pigment at a concentration, which tends to cause problems in processability and the like. When the D layer 23e is interposed, the concealing effect can be shared with the D layer 23e, or can be imparted exclusively to the D layer 23e. Therefore, the lower limit of the preferable thickness range of the B layer 13e is 20 μm. If it is thinner than this, when heated by the heater of the embossing device 30, the melt tension of the sheet is insufficient, wrinkles into the sheet, extreme elongation of the sheet, etc., and further embossing is difficult due to melt fracture. This is not preferable.
The D layer 23e is a layer intended to transfer a deep embossed pattern to the laminated resin sheet 11e, and the preferred thickness may vary depending on the thickness of the A layer 12e and the depth of the embossed pattern desired to be applied. In order to suppress an increase in haze, it is preferable to obtain a relatively thin sheet within a preferable thickness range. Therefore, the thickness of the D layer 23e is preferably set to 25 μm or more. Further, in the case where only the D layer 23e is provided with a base concealing property by a pigment, the thickness of the D layer 23e is preferably 50 μm or more.
Embossing that has been used in the past by setting the total thickness of the A layer 12e and the D layer 23e to 100 to 250 μm because the soft vinyl chloride sheet having a conventional embossed design was about 100 to 250 μm in thickness. It is possible to handle most of the pattern rolls.
Coloring with the pigment may depend solely on the D layer 23e, but coloring both the D layer 23e and the B layer 13e can reduce the pigment concentration, and causes less problems in the processability of the D layer 23e. It is preferable from the point.
[C layer]
The C layer 17e is applied by gravure printing, offset printing, screen printing, or other known printing methods. The pattern of the print layer is arbitrary, such as a stone pattern, a woodgrain pattern, a geometric pattern, and an abstract pattern. After printing on the surface on which the A layer is laminated, the layer may be laminated with the B layer 13e or the D layer 23e, or after printing on the surface of the B layer 13e or the D layer 23e, the layer may be laminated with the A layer 12e. Also good.
In the case where the A layer 12e and the B layer 13e or the D layer 23e are laminated and integrated using an adhesive, the type of the resin binder in the printing layer is not particularly limited, but the resin binder in the printing layer is not crosslinked or is low. By having heat-bonding properties such as a cross-linked polyester, the printed layer can also act as a heat-bonding adhesive layer when the sheets stacked by the embossing device are heated. . In addition to this, the non-printing portion of the A layer 12e and the B layer 13e or the A layer 12e and the D layer 23e is in direct contact with the C layer 17e by partial printing or rough dot printing. As a result, it is possible to obtain stronger heat-fusibility. The A layer 12e is in an amorphous state or a low crystal state until it is passed through the embossing device, and has a characteristic of exhibiting fusion properties when heated by the embossing device.
[Method for producing laminated resin sheet]
As a method for forming the laminated resin sheet 11e of the present invention, a known method, an extrusion casting method, an inflation method, or the like can be adopted, and it is not particularly limited. Each of the polyester resin constituting the A layer 12e and the polyester resin constituting the B layer 13e is formed into a single layer using the same or similar composition, and the A layer 12e is not crystallized. The laminated resin sheet 11e can also be obtained by subjecting the layer 13e to a crystallization process in a later step and then laminating and integrating with an adhesive or the like.
However, in general, it is preferable to obtain a B layer 13e that is crystallized at the time of extrusion film formation, rather than subjecting the polyester resin constituting the B layer 13e to a separate crystallization treatment after extrusion film formation. It is preferable that the resin composition of the B layer 13e is different. In addition, when the D layer 23e having the same basic physical properties as the A layer 12e is interposed, the composition of the D layer 23e and the B layer 13e is different, and the D layer 23e and the B layer 13e are coextruded. It is preferable also from the point which can create by film forming and can provide a required physical property to each layer.
[Embossing on laminated resin sheet]
The laminated sheet 11e can be provided with an embossed pattern by the embossing applying device 30 in the same manner as a conventional soft PVC sheet. Further, since the melting point (Tm) of the polyester resin constituting the B layer 13e is in the range of 180 ° C. to 240 ° C., the sheet heating temperature in the embossing device is 160 ° C. or higher, {the crystal melting peak temperature of the B layer Even if it is set to (Tm (B) -20} ° C. or lower, it does not cause adhesion to the heated metal roll or sheet melt fracture, and is equivalent to or equivalent to the soft PVC sheet to which the embossing design is imparted by the embossing device 30. The above embossing heat resistance is obtained.
[Application of metal non-adhesive coating layer]
By transferring the embossed pattern at the above-mentioned sheet heating temperature, it is equivalent to a soft PVC sheet, and a practically sufficient embossing heat resistance can be obtained, but higher embossing heat resistance is required depending on the application. There is a case. In this case, it is possible to improve the embossing heat resistance by increasing the temperature of the embossed pattern roll together with setting the sheet heating temperature high, but in the configuration of the present invention, the B layer Although sufficient heating metal non-stickiness is imparted by crystallizing 13e, the polyester-based resin constituting the A layer 12e does not have sufficient heating metal non-stickiness due to its necessary properties. Therefore, the non-adhesiveness to the hot embossed pattern roll and other auxiliary rolls may be improved by providing a heated metal non-adhesive coating layer 22e on the surface of the A layer 12e.
The application of the coating layer 22e needs to be performed before the laminated sheet is passed through the embossing apparatus, and can be performed by various ordinary coating techniques. Coating may be applied to the single layer sheet of the A layer 12e, or after the A layer 12e and the B layer 13e are laminated and integrated.
Examples of the composition of the coating layer 22e include, but are not limited to, silicones, acrylic silicones, and fluorines. The coating layer 22e is not limited to these, and has an adhesive property with the polyester resin constituting the A layer 12e. And if it has non-adhesiveness with a heating metal, it can be used without a restriction | limiting in particular. Further, the coating layer 22e is composed of two or more layers, the outermost layer is a non-tacky metal layer, and a layer having a function as an adhesive layer between the layer and the polyester resin constituting the A layer 12e. May be interposed. Further, secondary effects such as improvement of ultraviolet absorption and scratch resistance, improvement of contamination resistance, and application of a deep design may be imparted together with the coating layer.
The preferable thickness of the coating layer 22e is in the range of 1 to 10 μm, and if it is thinner than this, there is a possibility that problems such as partial adhesion to the heated metal roll may occur due to coating unevenness. On the other hand, if it is thicker than this, the resin physical properties of the coating layer 22e affect the important physical properties of the laminated sheet. That is, depending on the material of the coating layer 22e, it is not preferable because the processability and scratch resistance are deteriorated, or the embossing transferability itself is easily deteriorated.
[Metal plate]
As the metal plate 18e subject to the present invention, various steel plates such as hot-rolled steel plate, cold-rolled steel plate, hot-dip galvanized steel plate, electrogalvanized steel plate, tin-plated steel plate, stainless steel plate, aluminum plate, and aluminum-based alloy plate can be used. Alternatively, it may be used after the usual chemical conversion treatment. Although the thickness of a base metal plate changes with uses of a coating base material, etc., it can select in the range of 0.1 mm-10 mm.
[Method for producing coated substrate]
Next, the manufacturing method of the coating base material 20e of this invention is demonstrated.
As the adhesive 19e used when laminating the laminated resin sheet 11e provided with the embossed pattern by the embossing device 30 to the base metal plate, an epoxy adhesive, a urethane adhesive, a polyester adhesive, or the like is generally used. Can be mentioned. As a method for obtaining the coated base material 20e, the coating thickness of the adhesive after drying is applied to a metal surface on which a commonly used coating facility such as a reverse coater or a kiss coater is applied to a metal plate, and a laminated sheet is laminated. The above-mentioned epoxy type, urethane type, polyester type, etc. thermosetting adhesive is applied so that is about 2 to 10 μm.
Next, the coated surface is dried and heated by an infrared heater and / or a hot-air heating furnace, and the surface temperature of the metal plate is maintained at an arbitrary temperature, and immediately using the roll laminator, the B layer side of the laminated sheet becomes the adhesive surface. The coated substrate 20e is obtained by coating and cooling as described above. According to the present invention, since the melting point (Tm (B)) of the polyester resin constituting the A layer 12e located on the bonding surface side with the metal plate 18e is in the range of 180 to 240 ° C., the surface temperature of the metal plate is It is possible to obtain a strong adhesive force by making it equivalent to the case of a conventional soft PVC sheet laminate-coated metal plate.
According to the present invention, a coated base material having relatively good embossing heat resistance can be obtained, but after lamination, it is preferable to immediately reduce the embossing due to heating of the sheet during lamination by performing water cooling. .
The said covering base material 20e can be used as building interior materials, such as a door material, a unit bath wall material, and a unit bath interior material.
Example
Hereinafter, although an Example and a comparative example demonstrate in more detail, this invention is not limited to these. In addition, the measurement standard of the physical property of the coating base material shown to the Example and the comparative example and the test method are as follows.
<Embossing method>
[First invention]
Embossing was performed on the sheets prepared in Examples and Comparative Examples with the total thickness of the sheet being 150 μm and the thickness of the base material layer being 25 μm using an embossing apparatus. An embossing device is generally used for embossing a PVC sheet. The embossing device can be used to heat the sheet with a heating roll from the base material layer (rear surface), and to emboss from the embossable layer, the upper layer, or the coat layer. A device for embossing with a roll.
[Second invention]
1. A method of laminating a resin sheet pre-embossed on a metal plate.
1-1 A method of transferring a pattern by pressing an embossed pattern with a roll engraved when casting molten resin during extrusion film formation.
1-2 A method in which a film formed is reheated and pressed by a roll engraved with a pattern to continuously transfer the pattern.
2. A method of embossing after laminating a metal plate and a resin.
A method of continuously transferring a pattern by extruding a molten resin onto a 2-1 metal plate and pressing it with a roll engraved with a pattern before the resin is cooled.
2-2 A method in which a coated substrate is reheated and pressed by a roll engraved with a pattern to continuously transfer the pattern.
[Third Invention to Fifth Invention]
Embossing was imparted by the embossing imparting device 30 shown in FIG.
<Embossing property>
[First invention]
The embossed part was observed with the naked eye, and it was judged as “◯” if it was firmly contained, and “x” if it was difficult to understand the shape of the embossed and poorly designed.
[Second invention]
A case where embossing could be imparted without any problem was indicated by ○, and a case where some problem occurred and embossing could not be imparted was indicated by ×.
[Third Invention to Fifth Invention]
[Embossing suitability: Tack resistance]
When embossing was imparted by the embossing device 30 shown in FIG. 3, “X” indicates that the laminated resin sheet is adhered to the heating roll, and “◯” indicates that it is not adhered. [Embossing suitability: Fusing resistance]
When embossing was imparted by the embossing device 30 shown in FIG. 3, “x” indicates that the laminated resin sheet was melted during sheet heating, and “◯” indicates that it was not adhered.
[Embossing suitability: Transferability]
The sheet embossed with the embossing device 30 shown in FIG. 3 is visually observed, “○” indicates that the embossed pattern is clearly transferred, and “△” indicates that the transfer is slightly shallower than this. “X” indicates that the embossed pattern is not good and has a shallow embossed pattern, or the surface is simply rough regardless of the embossed pattern.
[Emboss heat resistance: Emboss heat resistance during lamination to steel sheet] (fourth to fifth inventions)
When laminating the embossed sheet with the embossing device 30 shown in FIG. 3 on the metal plate 17, the extent to which the embossing is returned (embossing becomes shallower) by heat from the heated metal plate was visually observed. Compared with the sheet before laminating, `` ○ '' indicates that the shape of the emboss is almost unchanged, `` △ '' indicates that the embossed return is slightly compared to this, and embossed return is remarkable, Alternatively, “x” indicates that the embossed pattern has completely disappeared and the surface is simply rough.
[Emboss heat resistance: Boiling water resistance] (fourth to fifth inventions)
The metal plate laminated with the sheet embossed by the embossing device 30 shown in FIG. 3 was immersed in boiling water for 3 hours and then visually observed. Compared to the case before being put into boiling water, “○” indicates that the shape of the emboss is almost unchanged, “△” indicates that the embossed return has occurred slightly compared to this, and embossed return is remarkable. Or, the embossed pattern completely disappeared and the surface was simply roughed, indicated by “x”.
[Emboss heat resistance: high temperature heat resistance] (fourth to fifth inventions)
A metal plate laminated with a sheet embossed by the embossing device 30 shown in FIG. 3 was left in a hot air circulation oven at 105 ° C. for 3 hours, and then visually observed. Compared to before the oven, the shape of the emboss is almost unchanged “○”, the case where there is a little emboss return compared to this, “△”, the emboss return is remarkable, Alternatively, “x” indicates that the embossed pattern has completely disappeared and the surface is simply rough.
[Printed pattern transparency: initial stage] (fifth invention)
The sheet embossed by the embossing device 30 shown in FIG. 3 is visually observed, and “○” indicates that the printed pattern can be clearly recognized. Compared with this, the haze of the transparent layer (A layer) is somewhat large and clear. A case where the thickness is not clear is indicated by “Δ”, and a case where the haze of the transparent layer is large and the identification of the printed layer is unclear is indicated by “x”.
[Printed pattern transparency: after immersion in boiling water] (fifth invention)
(7) Printed pattern transparency:
The sheet embossed with the embossing device shown in FIG. 2 is visually observed after being immersed in boiling water for 3 hours, and there is almost no change in the clarity of the printed layer compared to the state before immersion. “◯”, a case where the haze of the transparent layer is slightly larger than this and the clarity is not clear, “Δ”, and a case where the clarity of the printed layer is remarkably lowered is indicated by “X”.
<Crystal melting peak temperature Tm>
[Second invention to third invention]
Using DSC-7 manufactured by PerkinElmer, a 10 mg sample was obtained by measuring the heating rate at 10 ° C./min in accordance with JIS-K7121 “Method for measuring plastic transition temperature—determining melting temperature”. The crystal melting peak top temperature (melting point) at the time of primary temperature rise was defined as Tm.
[Fourth to fifth inventions]
Using DSC-7 manufactured by PerkinElmer, a 10 mg sample was obtained by measuring the heating rate at 10 ° C./min according to JIS-K7121 “Method for measuring transition temperature of plastic—determining melting temperature”. The crystal melting peak top temperature at the time of primary temperature rise was defined as Tm. At the same time, the heat of crystal melting ΔHm was determined. A polyester resin constituting the A layer and a polyester resin constituting the B layer were isolated from the two-layer sheet produced by coextrusion film formation by microtome cutting, and used as specimens.
<Crystallization peak temperature Tc>
[Second invention to third invention]
Using DSC-7 manufactured by PerkinElmer, 10 mg of a sample was determined by measuring the heating rate at 10 ° C./min according to JIS-K7121 “Method for measuring plastic transition temperature—determining crystallization temperature”. The crystallization peak top temperature at the time of primary temperature rise was defined as Tc.
[Fourth to fifth inventions]
Using DSC-7 manufactured by PerkinElmer, a 10 mg sample was obtained by measuring the heating rate at 10 ° C./min in accordance with JIS-K7121 “Method for measuring the transition temperature of plastics—determining the crystallization temperature”. The crystallization peak temperature at the time of primary temperature rise was defined as Tc. At the same time, the amount of heat of crystallization ΔHc at the time of primary temperature rise was determined. The method for producing the specimen is the same as that for measuring the crystal melting peak temperature Tm.
<Weather resistance promotion test> [Third invention]
A test piece was prepared by cutting a coated base material laminated with an embossed sheet into a size of 60 mm × 50 mm. In addition, especially the sealing process of the cut part end surface of a test piece, etc. was not performed. These test pieces were put into a sunshine / weather meter acceleration tester (manufactured by Suga Test Instruments Co., Ltd.) and subjected to an exposure test at a black panel temperature of 63 ° C.
The change in color difference of the test piece after 2000 hours of exposure was measured with a color difference meter. When the change in color difference was ΔE value of 1.0 or less, “◯”, when it was 5.0 or more, “x”, and in the meantime “ △ ” Moreover, visual observation was performed also about the deterioration state other than a color difference change.
In addition, in the evaluation of embossing suitability, for a sheet showing adhesion and fusing, a sheet not provided with embossing was laminated on a metal plate to obtain a test piece. Similarly, test pieces were selected for the workability test and the evaluation of surface hardness described below.
<Workability test> [third invention]
An impact adhesion bending test was performed on the coated base material laminated with the embossed sheet, and the surface state of the sheet in the bent portion was visually determined. Those with almost no change (○), those with slight cracks that did not significantly deteriorate the appearance (△), those with a markedly deteriorated appearance due to the occurrence of cracks and those with exposed metal surfaces (×) As displayed.
The impact adhesion bending test was performed as follows. Samples of 50 mm × 150 mm were prepared from the length direction and the width direction of the coated substrate, respectively, kept at 23 ° C. for 1 hour or longer, and then bent to 180 ° (inner bending radius 2 mm) using a bending tester. A cylindrical weight having a diameter of 75 mm and a mass of 5 kg was dropped from a height of 50 cm.
<Surface hardness> [third invention]
Using a pencil of H, in accordance with JIS-S-1005 9.8 (2) pencil scratch test, a load of 0.5 kg was applied while maintaining an angle of 45 ° with respect to the resin sheet surface of the coated substrate of 80 mm × 60 mm. The surface state of the resin sheet at the drawing portion was visually determined. “◯” indicates that there was no scratch at all, “Δ” indicates that a slight trace of the line was left, and “x” indicates that the scratch was clearly scratched.
Next, the method and result of the Example and the comparative example about each of 1st invention-5th invention are shown.
<First invention>
(Example 1)
Eastman Chemical Co., which is an amorphous polyester-based resin, trade name, a composition containing a large amount of PETG6763, an embossable layer A, and a composition containing a large amount of polybutylene terephthalate, which is a crystalline polyester-based resin, as a base layer B The laminated resin sheet was obtained by film formation by T-die coextrusion method. PETG6763 is an amorphous polyester resin in which a part (about 30 to 60 mol%) of ethylene glycol of polyethylene terephthalate is substituted with 1,4-cyclohexanedimethanol.
(Example 2)
A laminated resin sheet in which printing is performed on the embossable layer of the sheet of Example 1, surface coating is performed with a urethane resin, and a printed layer and a surface coating layer are further formed on the embossable layer. Obtained.
(Example 3)
Teijin-DuPont Films, Inc., trade name, “Tefrex” sheet, printed with dry laminate adhesive and produced by the method of Example 1 (embossable layer: amorphous polyester, substrate Layer: Crystalline polyester) A laminated resin sheet obtained by laminating an embossable layer of a sheet was obtained.
(Example 4)
A laminated resin sheet was obtained in which an acrylic sheet was embossable and a biaxially stretched PET sheet was used as a base layer, and the acrylic sheet and the PET sheet were bonded together with a dry laminate adhesive.
(Comparative Example 1)
A laminated resin sheet was produced using only the material of the embossable layer (amorphous polyester) of Example 1.
(Comparative Example 2)
The material of the embossable layer of the sheet of Example 1 was changed to the material of the base material layer, and the material of the base material layer was changed to the material of the embossable layer (embossable layer: crystalline polyester, base material layer: non-material) Crystalline polyester) laminated resin sheet was obtained.
(Comparative Example 3)
Biaxially stretched PET was printed, and with a dry laminate adhesive, the printed surface and the production method of Example 1 were used (embossing possible layer: amorphous polyester, substrate layer: crystalline polyester) embossing of the sheet A laminated resin sheet bonded to the possible layer was obtained.
(Comparative Example 4)
The material of the embossable layer of Example 4 was changed to the material of the base material layer, and the material of the base material layer was changed to the material of the embossable layer (embossable layer: biaxially stretched PET, base material layer: acrylic). A laminated resin sheet was obtained.
(Comparative Example 5)
In the configuration of Example 3, an embossable layer was made of crystalline polyester (the same composition as the base material layer), and a sheet bonded with a dry laminate adhesive was obtained.
Tables 1 and 2 show the results of the above examples and comparative examples.

As is clear from Tables 1 and 2, the laminated resin sheets of Examples 1 to 4 corresponding to the present invention product in which the A layer is amorphous and the B layer is crystalline are heated rolls when embossing is applied. There was no sticking to and embossing was possible.
In contrast, Comparative Examples 1 and 2 in which the B layer was amorphous adhered to the heating roll, and the embossing was not successful. In Comparative Example 4, sticking occurred when the temperature was high.
Further, Comparative Examples 2, 4, and 5 in which the A layer was crystalline could not be embossed. The difference in embossing results between Example 3 and Comparative Example 3 is due to differences in the high temperature elastic modulus, stretch ratio, etc. of the upper layer (stretched PET).
<Second invention>
Table 3 shows the resin compositions of the sheets used in the examples and comparative examples. In addition, the raw material used by the test is as follows.
-Substantially amorphous polyester resin: Easter 6763 manufactured by Eastman Chemical Co., Ltd. (glass transition point: 81 [° C], crystal melting peak temperature; not observed)-Substantially crystalline polyester resin: NOVADUR5008 Mitsubishi Engineering Plastics (Glass transition point; 46 [° C], crystal melting peak temperature; 221 [° C])

(Examples 5-7, Comparative Examples 6-11)
For film formation, a twin screw kneading extruder equipped with a T die was used to adjust the total thickness to 150 μm. Subsequently, embossing was performed by the four types of embossing methods, and each evaluation was performed. However, in the case of the method 1-1 and 1-2, it evaluated by the sheet | seat, and in the case of the method 2-1 and 2-2, it evaluated by the coating | coated base material, respectively. In addition, the polyester-type thermosetting adhesive was used for lamination | stacking with a metal plate (steel plate). The results are shown in Table 4.

As is apparent from Table 4, all the embossing methods were applicable to the laminated sheets of Examples 5 to 7 within the scope of the present invention. In contrast, in the laminated sheets and single-layer sheets of Comparative Examples 6 to 11 outside the scope of the present invention, embossing by embossing methods 1-1, 2-1 and 2-2 was possible. Embossing by 2 could not be realized due to various problems.
A problem that has occurred will be described. In the single-layer sheet, the substantially crystalline polyester resin (Comparative Example 8) or the mixture containing the substantially crystalline polyester resin as a main component (Comparative Example 9) has no adhesion to the heating roll up to a relatively high temperature. However, when the temperature was raised above the melting point to give embossing, the sheet was blown out.
In the single-layer sheet, the substantially amorphous polyester resin (Comparative Example 10) or the mixture containing the substantially amorphous polyester resin as a main component (Comparative Example 11) adhered to the heating roll.
In the case of using the laminated sheet of Comparative Example 6, that is, a mixture mainly composed of a substantially crystalline polyester resin as the polyester resin constituting the A layer, the sheet temperature of the resin A is changed to give embossing. When the melting point is raised to the melting point or higher, the polyester resin constituting the B layer is similarly softened, so that the sheet does not serve as a base material and the sheet is blown out.
When the laminated sheet of Comparative Example 7, that is, the polyester resin constituting the B layer is a mixture containing a substantially amorphous polyester resin as a main component, the substantially amorphous polyester resin or the substantially amorphous resin is used. In the same manner as the results (Comparative Examples 10 and 11) of the single layer sheet of the mixture containing the polyester resin as the main component, it was stuck to the heating roll.
<Third invention>
(Examples 8-19, Comparative Examples 12-22)
[Production of laminated resin sheet]
The resin composition shown in Table 5 was used as the polyester-based resin constituting the A layer, the resin composition shown in Table 6 was used as the polyester-based resin constituting the B layer, and a laminated resin sheet was produced with the combinations shown in Table 10. The total thickness was 170 μm, the thickness of the embossable layer 12 was 140 μm, and the thickness of the base material layer 13 was 30 μm.
In addition, as for a part of the comparative example, a single-layer sheet having a thickness of 170 μm shown in Table 7 is used, and in Comparative Example 22, a polypropylene by a calender method having a thickness of 150 μm generally used for a coating substrate. A soft resin sheet is used.
The sheet film forming method is a feed block type co-extrusion film forming method using two twin-screw kneading extruders except for a part of the above comparative example, and is a general method of taking out the resin flowing out from the T-die with a casting roll. Depends on. The single-layer sheet shown in Table 7 was formed in the same manner with one biaxial kneading extruder.
Moreover, each raw material used by Table 5-Table 7 is as follows.
-Polycrystalline polyester resin (1): NOVADUR5008 Polybutylene terephthalate resin manufactured by Mitsubishi Engineering Plastics Co., Ltd. (glass transition point; 46 [° C], crystal melting peak temperature; 221 [° C])
-Polycrystalline polyester resin (2): NOVADUR5020S Polybutylene terephthalate resin manufactured by Mitsubishi Engineering Plastics Co., Ltd. (glass transition point; 45 [° C], crystal melting peak temperature; 223 [° C])
-Substantially amorphous polyester resin: manufactured by Easter 6763 Eastman Chemical Co., Ltd. (glass transition point: 81 [° C.], crystal melting peak temperature; not observed)

Note that “phr” in Tables 5 to 9 means the weight ratio (parts by weight) of the additive when the resin content is 100.
[Applying transparent coating layer]
The coating film shown in Table 8 or the film shown in Table 9 was provided on the embossable layer side of the laminated resin sheet. The combinations with the laminated resin sheet and the thickness of the transparent coating layer are shown in Table 10. The coating film is heated and dried after being applied by a roll coater. In Example 11 only, the embossed pattern was imparted to the laminated sheet by the embossing imparting device 30, and then a transparent coating layer was provided.
When laminating a film, apply a cyanate-crosslinked polyester adhesive on the adhesive side of the film, and after drying, overlay the layer A side surface of the laminated resin sheet and between the metal roll and rubber roll heated to 50 ° C. Was laminated by heating and pressurizing.
Moreover, each raw material used in Table 8 and Table 9 is as follows.
Acrylic polyol: A grade having a relatively low glass transition temperature (Tg) among those generally used for acrylic varnishes.
・ Udable UVG-100: HALS
・ Ultraviolet absorber copolymer crosslinkable acrylic resin. Made by Nippon Shokubai Co., Ltd.
・ Lumiflon LF-200: Fluoroethylene / vinyl ether copolymer Asahi Glass Co., Ltd.
・ Silicone graft acrylic: X22-8004 Hydroxyl group-containing Shin-Etsu Silicone Co., Ltd.
-Acrylic film semi-rigid: Film production of raw film grade acrylic resin powder using a single screw extruder. Tensile elongation at break of about 110% (23 ° C., pulling speed 200 mm / min).
-Acrylic film soft: Mixing raw film grade acrylic and flexible acrylic resin raw material powder, and using a single screw extruder to form a film. Tensile elongation at break of about 200% (23 ° C., pulling speed 200 mm / min).
Tinuvin 400: Triazine UV absorber, molecular weight = 647, manufactured by Ciba Health Chemicals Co., Ltd.
-PUVA-50M: high molecular weight (MMA copolymerization type) ultraviolet absorber, molecular weight = about 10,000, manufactured by Otsuka Chemical Co., Ltd.
LA-31: Benzotriazole-based ultraviolet absorber, molecular weight = 659, manufactured by Asahi Denka Co., Ltd. [providing embossed pattern]
An embossing pattern was imparted by an embossing imparting apparatus 30 shown in FIG. 3 by a continuous method that is generally used even for soft vinyl chloride sheets. As an outline of embossing by a continuous method, first the sheet is pre-heated by contact-type heating using a metal heating roll, then the sheet is heated to an arbitrary temperature by non-contact-type heating using an infrared heater, The embossed pattern is transferred by an embossing roll.
[Preparation of coated substrate]
Next, a thermosetting adhesive is applied by applying a polyester adhesive generally used for a polyvinyl chloride coated metal plate to a metal surface so that the adhesive film thickness after drying is about 2 to 4 μm. Form. Next, the coated surface is dried and heated by a hot-air heating furnace and an infrared heater, the surface temperature of the galvanized steel sheet (thickness 0.45 mm) is set to 235 ° C., and a laminated resin sheet (polyester resin sheet) is immediately used using a roll laminator. ) Was coated and cooled to prepare a resin-coated steel sheet.
[Evaluation of laminated resin sheet and coated substrate]
Each of the above items was evaluated. The results are summarized in Table 11.

As is apparent from Table 11, in Examples 8 to 19 within the scope of the present invention, the embossing by the embossing device used to emboss the PVC sheet does not cause adhesion or fusing of the sheet. In addition, a good embossed pattern transfer was obtained, the weather resistance was excellent, and both the workability and the surface hardness were good.
On the other hand, in the laminated sheets and single-layer sheets of Comparative Examples 12 to 22 outside the scope of the present invention, at least one of embossing suitability, weather resistance, workability, and surface hardness is evaluated as rejected (x). It was.
Comparative Example 12 and Comparative Example 13 are cases in which there is no transparent coating layer having ultraviolet absorptivity, but as a result of the weather resistance acceleration test, both have problems. That is, remarkable ejection occurred in Comparative Example 12 in which the amount of the titanium oxide pigment added to the A layer was large, and yellowing of the resin itself was conspicuous in Comparative Example 2 in which the amount of pigment addition was relatively small.
In Comparative Example 14, the transparent coating layer was thicker than the range of the present invention (25 μm), but the embossed pattern transferability was inferior. Moreover, workability was also inferior by making the thickness of the transparent coating layer thicker than the range of the present invention.
Comparative Example 15 uses a single-layer sheet having a preferable composition for the A layer without using the laminated resin sheet having the configuration of “embossable layer 12 + base material layer 13”, but the embossing device 30 was heated. Adhesion to the metal roll was generated, and embossing could not be imparted. On the other hand, Comparative Example 16 uses a single-layer sheet having a preferred composition for the B layer, and does not cause adhesion to a heated metal roll, but the embossed pattern is transferred under normal embossing conditions on the PVC sheet. Was not obtained at all.
Comparative Example 17 uses a laminated sheet, but the result was the same as Comparative Example 16 because the composition of the layer to be the A layer was a substantially crystalline composition.
Comparative Examples 18 to 21 are obtained by laminating an acrylic film having a thickness of 50 μm on the surface of the A layer of the laminated resin sheet, and the acrylic film substantially acts as an embossable layer, regardless of the composition of the A layer. It was possible to transfer the embossed pattern. However, in Comparative Example 20 and Comparative Example 21 in which no ultraviolet absorber was added, the weather resistance was not improved, and the acrylic film was partially peeled in the sample after the weather resistance evaluation.
On the other hand, in Comparative Example 18 and Comparative Example 19 to which the ultraviolet absorber was added, discoloration of the A layer and the B layer made of the polyester resin was effectively suppressed. However, in the case of Comparative Example 18, Comparative Example 20, and Comparative Example 21 in which relatively hard acrylic films are laminated, the acrylic film is completely broken at the time of bending, and the workability is inferior. In Comparative Example 19 in which a relatively soft acrylic film was laminated, there was no problem in workability, but there was a problem in surface hardness. And also in the case of the comparative example 18, comparative example 20, and the comparative example 21 which laminated | stacked the comparatively hard acrylic film, the surface hardness was inferior compared with each Example which is this invention.
Moreover, when the single layer sheet | seat of the PP-type resin film for coating base materials of the comparative example 22 was used, the surface hardness was inferior compared with soft PVC.
<Fourth Invention>
(Examples 20 to 33, Comparative Examples 23 to 34)
[Production of laminated resin sheet]
The resin composition shown in Table 12 was used as the resin for forming the A layer, the resin composition shown in Table 13 was used as the resin for forming the B layer, and laminated resin sheets were produced in the combinations shown in Table 15 and Table 17. The total thickness was 150 μm, the thickness of the A layer was 120 μm, and the thickness of the B layer was 30 μm. The resin forming the A layer contains 17 parts by weight of a titanium oxide-based beige pigment (the total amount of the resin is 100 parts by weight). Table 14 shows the DSC measurement values of the resin forming the A layer and the resin forming the B layer in the resin compositions of Tables 12 and 13.

The sheet film forming method is a feed block type co-extrusion film forming method using two twin-screw kneading extruders, and depends on a general method in which the resin flowing out from the T-die is taken up by a casting roll. A casting roll having a mirror surface was used, and the roll temperature was maintained at 65 ° C. by a hot water circulation device.
In addition, about the sheet | seat of the comparative example 30, after taking in with a casting roll, it introduce | transduced in the heating furnace which has an infrared heater, and performed the post-heating process for 160 degreeC x 40 second by non-contact heating.
Moreover, each raw material used in Table 12 and Table 13 is as follows.
NOVADURAN 5008: Homo PBT resin manufactured by Mitsubishi Engineering Plastics (glass transition point: 46 [° C.], crystal melting peak temperature: 221 [° C.]) NOVADURAN 5020S: Homo PBT resin manufactured by Mitsubishi Engineering Plastics (glass) Transition point: 45 [° C.], crystal melting peak temperature; 223 [° C.] Duranex 500 JP: Isophthalic acid copolymerized PBT resin (made by Wintech Polymer Co., Ltd. (glass transition point: 32 [° C.], crystal melting peak temperature) ; 204 [° C.])
Co-PET BK-2180: Isophthalic acid copolymerized PET resin manufactured by Mitsubishi Chemical Corporation (glass transition point; 76 [° C.], crystal melting peak temperature; 246 [° C.])
Cortera CP509200: Homo PTT resin manufactured by Shell Co., Ltd. (glass transition point: 49 [° C.], crystal melting peak temperature; 225 [° C.])
Easter 6863: Amorphous polyester resin in which about 31% of the ethylene glycol portion of polyethylene terephthalate was substituted with 1,4-cyclohexanedimethanol (Glass transition point: 81 [° C.], crystal melting Peak temperature; not observed)
PCTG5445: Amorphous polyester resin in which about 70% of the ethylene glycol portion of polyethylene terephthalate is replaced with 1,4-cyclohexanedimethanol (manufactured by Eastman Chemical Co., Ltd. (glass transition point; 88 [° C.], crystal melting peak) Temperature; not observed)
[Give embossed pattern]
An embossing pattern was imparted by a continuous method using an embossing imparting apparatus 30 shown in FIG. 3 that is generally used even for soft PVC sheets. As an outline of embossing by a continuous method, first the sheet is pre-heated by contact-type heating using a metal heating roll, then the sheet is heated to an arbitrary temperature by non-contact-type heating using an infrared heater, The embossed pattern is transferred by an embossing roll. A heating drum is set to 100 degreeC, and about Example 20-29 and Comparative Examples 23-30, the sheet | seat before contacting an embossing roll is heated to 165 degreeC with a heater. Moreover, the temperature of an embossing roll is 80 degreeC.
Regarding Examples 30 to 33 and Comparative Examples 31 to 34, the heating drum is set to 100 ° C., and the sheet temperature by heater heating is changed. Also in this case, the temperature of the embossing roll is 80 ° C.
[Preparation of coated substrate]
Next, a polyester thermosetting adhesive generally used for a polyvinyl chloride coated metal plate is applied to the metal surface so that the adhesive film thickness after drying is about 2 to 4 μm, and is thermoset. A mold adhesive layer is formed. Next, the coated surface is dried and heated with a hot air heating furnace and an infrared heater, the surface temperature of the galvanized steel sheet (thickness: 0.45 mm) is set to 235 ° C., and a laminated resin sheet (polyester resin sheet) is immediately used using a roll laminator. ) Was coated and cooled by water cooling to produce an embossed design resin-coated steel sheet.
[Evaluation of laminated resin sheet and coated substrate]
Each of the above items was evaluated. The results are summarized in Table 16 and Table 18. In Table 16, the following evaluation was not performed for those that caused sticking to the heating drum of the embossing device, and in Table 18, the evaluation of high-temperature heat resistance was performed for those in which embossing return was significant during lamination. Not done.
Comparative Example 23 is a case where only a completely non-crystalline resin is used as the resin for forming the A layer, but the embossing device is used by using a resin that meets the requirements of the present invention as the resin for forming the B layer. There is no sticking or melt fracture of the sheet. However, since the composition of the resin forming the A layer itself does not have boiling water resistance, the embossed pattern disappeared completely when immersed in boiling water.
In Comparative Example 24, the resin forming the A layer has crystallinity, but the value of ΔHm is lower than the range of the present invention. In this case as well, the embossed pattern disappeared completely by immersion in boiling water as in Comparative Example 23.
Comparative Example 25 is a case where the value of “(ΔHm (A) −ΔHc (A)) / ΔHm (A)” of the resin forming the A layer is higher than the range of the present invention, and the embossed pattern transferability deteriorates. Furthermore, in Comparative Example 26 in which “(ΔHm (A) −ΔHc (A)) / ΔHm (A)” is a large value, it was difficult to transfer the embossed pattern. If the resin forming the A layer has a relatively high crystallinity before being passed through the embossing roll, the elastic modulus of the sheet does not decrease even if the sheet is heated by the heater, and the resin is pressed with the embossing roll. This is because sufficient distortion (embossed pattern transfer) cannot be imparted.
In Comparative Example 27, the composition of the resin forming the A layer satisfies the requirements of the present invention. However, as the crystalline resin, a polyethylene terephthalate resin copolymerized with isophthalic acid having a low crystallization rate is used. A exhibits the same behavior as when A is completely non-crystalline, and the boiling water resistance is poor as in Comparative Examples 23 and 24.
Comparative Example 28 and Comparative Example 29 are cases where the value of “(ΔHm (B) −ΔHc (B)) / ΔHm (B)” of the resin forming the B layer is lower than the range of the present invention. The laminated sheet became sticky on the heating drum, and an embossed pattern could not be imparted to the sheet.
In Comparative Example 30, the sheet having the same composition and configuration as Comparative Example 29 was subjected to post-heating treatment, and the crystallization of the resin forming the B layer progressed by the heat treatment, whereby the heating drum was applied. The tack is improved. However, since the post-heat treatment was performed in the state of the laminated sheet, crystallization of the resin forming the A layer also progressed, making it difficult to transfer the embossed pattern.
In contrast to these comparative examples, in Examples 20 to 29 that satisfy the requirements of the present invention, good embossed pattern transferability is obtained without causing adhesion to the heating drum or sheet breakage during heating of the heater. Further, the resin forming the A layer has crystallinity sufficient to withstand boiling water immersion.
Example 30 to Example 33 and Comparative Example 31 to Comparative Example 34 use sheets having the same configuration and composition, and change the sheet temperature before passing through the embossing roll, but in Comparative Example 31 and Comparative Example 32, The embossing remarkably occurred during lamination. This is because the temperature at which distortion (embossed pattern transfer) was applied was low, the sheet temperature rose to near the temperature at which distortion was applied by the heat from the steel plate during lamination, and the frozen residual stress was released. to cause.
In Comparative Example 33 and Comparative Example 34, the temperature at which the strain is applied is higher than those in Comparative Example 31 and Comparative Example 32, and the embossing return at the time of lamination tends to be improved, but it is still a conventional soft PVC sheet. It doesn't reach. Moreover, the high temperature heat resistance of the embossing as a laminated steel plate is not sufficient.
On the other hand, in Examples 30 to 33, there is little emboss return at the time of lamination, which is equal to or higher than that of a conventional soft PVC sheet, and high-temperature heat resistance as a laminated steel sheet is practically sufficient. ing.
<Fifth invention>
(Creation of sheets for lamination in Examples 34 to 44 and Comparative Examples 35 to 41)
Single layer sheets were prepared using the resin composition shown in Table 19 as the A layer and the resin composition shown in Table 20 as the B layer. The A layer has a thickness of 70 μm, and no pigment is added. The B layer has a thickness of 60 μm, and 20 parts by weight of a titanium oxide pigment (with a resin weight of 100) is added. The film forming method of the sheet is a T-die film forming method using a twin-screw kneading extruder, and depends on a general method in which the resin flowing out from the T-die is drawn by a casting roll. A casting roll having a mirror surface is used and maintained at 65 ° C. by circulating hot water. Table 21 shows the combinations of the A layer and the B layer used in each example and comparative example. In addition, about the B layer of Example 44, after taking in with a casting roll, it introduce | transduced in the heating furnace which has an infrared heater, and performed the post-heating process for 160 degreeC x 40 second by non-contact heating.
Next, abstract pattern partial printing was performed on the surface of the layer B with a printing ink using a non-crosslinked polyester vehicle. The type of printing layer, coating thickness, drying conditions, etc. are the same for all examples and comparative examples.
Moreover, each raw material used in Table 19 to Table 20 is as follows.
・ Novaduran 5020S: Homo PBT resin, manufactured by Mitsubishi Engineering Plastics (glass transition point; 45 [° C.] crystal melting peak temperature; 223 [° C.])
Duranex 500 JP: isophthalic acid copolymerized PBT resin, manufactured by Wintech Polymer Co., Ltd. (glass transition point: 32 [° C.] crystal melting peak temperature; 204 [° C.])
Co-PET BK-2180: Isophthalic acid copolymerized PET resin, manufactured by Mitsubishi Chemical Corporation (glass transition point; 76 [° C.] crystal melting peak temperature; 246 [° C.])
-Cortera CP509200: Homo PTT resin manufactured by Shell (glass transition point: 49 [° C] crystal melting peak temperature: 225 [° C])
Easter 6673: Amorphous polyester resin in which about 31% of the ethylene glycol portion of polyethylene terephthalate was replaced with 1,4-cyclohexanedimethanol (Glass transition point; 81 [° C.] crystal melting peak temperature; Not observed [℃])
PCTG5445: Amorphous polyester resin in which about 70% of the ethylene glycol portion of polyethylene terephthalate is substituted with 1,4-cyclohexanedimethanol, manufactured by Eastman Chemical Co., Ltd. (glass transition point; 88 [° C.] crystal melting peak temperature ; Not observed [℃])
(Lamination and integration of sheets of Examples 34 to 44 and Comparative Examples 35 to 41 and provision of an embossed pattern)
The sheet was laminated and integrated by heat fusion and embossed pattern was imparted by an embossing apparatus 30 by a continuous method, which is generally used in the soft vinyl chloride sheet shown in FIG. As an outline of the embossing device by the continuous method, first, the sheet is pre-heated by contact-type heating using a metal heating roll, and then the sheet is heated to an arbitrary temperature by non-contact-type heating using an infrared heater. The embossed pattern is transferred by an embossing roll. A heating drum is set to 100 degreeC, and about the Examples 34-44 and Comparative Examples 35-41, the sheet | seat before contacting an embossed pattern roll is heated to 165 degreeC with a heater. Moreover, the temperature of the embossed pattern roll is 80 ° C., and it is a satin roll having a surface average roughness Ra = 10 μm.
(Creation of laminated resin sheets and application of embossed patterns in Examples 45 to 51 and Comparative Examples 42 and 43)
As the A layer, a single layer sheet having a resin composition and thickness shown in Table 23 was used. Further, the resin composition and thickness shown in Table 23 are used as the B layer, and the D layer is included in the configuration of some examples. The composition of the D layer is the same as the composition A-4 of the A layer except that it contains 20 parts by weight of the titanium oxide pigment (with the resin content being 100 parts by weight). The presence / absence and thickness of the D layer are shown in Table 23.
When the D layer is not present, the method for forming the A layer and the B layer is the same as in Examples 34 to 44 and Comparative Examples 35 to 41. When the D layer is present, two-machine biaxial kneading extrusion A co-extrusion laminated sheet of layer D and layer B was prepared by a co-extrusion T-die film forming method using a feed block method using a machine. Also in this case, the casting roll has a mirror surface and is maintained at 65 ° C. by circulating hot water.
Next, an abstract pattern was partially printed with a printing ink using an uncrosslinked polyester vehicle on the surface of the B layer or the D layer. The type of printing layer, coating thickness, drying conditions, etc. are the same for all examples and comparative examples. Further, regarding the lamination and integration of the sheets and the embossing pattern, basically the same as in the case of Examples 34 to 44 and Comparative Examples 35 to 41, but the embossed pattern roll has an average surface roughness Ra = 10 μm and Ra. Two types of satin rolls of = 20 μm were used.
(Preparation of laminated resin sheets of Examples 52 to 55 and Comparative Examples 44 to 47 and application of an embossed pattern)
The resin composition shown in Table 25 was used as the A layer, the resin composition shown in Table 25 was used as the B layer, the A layer had a thickness of 80 μm, and the B layer had a thickness of 80 μm. Printing ink application, sheet stacking integration and embossing pattern application are basically the same method as described above, but the heating drum is set to 100 ° C and the sheet arrival temperature by heater heating is changed. is there. Also in this case, the temperature of the embossed pattern roll is 80 ° C. Table 7 shows the combinations of the A layer and the B layer used in each Example and Comparative Example, and the sheet arrival temperature due to the heater heating.
[Creation of coated substrate]
Next, a polyester thermosetting adhesive generally used for a polyvinyl chloride coated metal plate is applied to the metal surface so that the adhesive film thickness after drying is about 2 to 4 μm (adhesive). Layer), followed by drying and heating of the coated surface with a hot air heating furnace and an infrared heater, setting the surface temperature of the galvanized steel sheet (metal plate: thickness 0.45 mm) to 235 ° C., and immediately using a roll laminator to make polyester The resin sheet was covered and cooled by water cooling to produce an embossed design resin-coated steel sheet.
(Evaluation of embossed sheet and coated substrate)
Each item mentioned above was evaluated. The results are shown in Table 22, Table 24 and Table 26. In Table 22, the subsequent evaluation was not performed for those that caused sticking to the heating drum of the embossing device, and the subsequent evaluation was performed for those in which the sheet was melted and fractured in the embossing device in Table 24. Absent. In Table 26, the evaluation of high-temperature heat resistance was not carried out for those with significant embossing return during lamination.

Comparative Examples 10 and 41 are cases where “(ΔHm (B) −ΔHc (B)) / ΔHm (B)” of the resin forming the B layer is lower than the claims of the present invention, and the heating drum of the embossing device Thus, the laminated sheet was sticky, so that an embossed pattern could not be given to the sheet.
Comparative Example 35 is a case where only a completely non-crystalline resin is used as the resin for forming the A layer, but embossing can be achieved by using a resin that satisfies the claims of the present invention as the resin for forming the B layer. There is no sticking or melt fracture of the sheet in the applying device. However, since the composition of the resin A itself does not have boiling water resistance, the embossed pattern disappears completely when immersed in boiling water.
In Comparative Example 36, the resin forming the A layer has crystallinity, but the value of ΔHm (A) is lower than the claims. In this case as well, as in Comparative Example 35, the embossed pattern disappears when immersed in boiling water.
In Comparative Example 39, the composition of the resin forming the A layer satisfies the requirements of the present invention. However, as the crystalline resin, a polyethylene terephthalate resin copolymerized with isophthalic acid having a low crystallization rate is used. A exhibits the same behavior as when A is completely non-crystalline, and the boiling water resistance is poor as in Comparative Examples 35 and 36.
Comparative Example 37 is a case where the value of “(ΔHm (A) −ΔHc (A)) / ΔHm (A)” of the resin forming the A layer is higher than the range of the present invention, and the embossed pattern transferability deteriorates. Furthermore, the embossed pattern transfer was difficult in Comparative Example 38 in which “(ΔHm (A) −ΔHc (A)) / ΔHm (A)” was a large value. If the resin forming the A layer has a relatively high crystallinity before being passed through the embossed pattern roll, the elastic modulus of the sheet does not decrease at a temperature below the melting point even if the sheet is heated by a heater. This is because even when pressed with an embossed pattern roll, sufficient distortion (embossed pattern transfer) cannot be imparted.
On the other hand, in Examples 34 to 44 of the present invention, good embossed pattern transferability was obtained without causing adhesion to the heating drum or sheet breakage during heating of the heater. Further, the resin forming the A layer has crystallinity sufficient to withstand boiling water immersion.
Example 44 uses the same resin that forms the A layer as Comparative Example 41, and the composition of the resin that forms the B layer is the same, but the heat treatment was performed after the film was formed on the sheet. The embossed pattern transfer is good. The boiling water resistance is also good.
ΔHm (B) of B-4 after the heat treatment was 28.9 (J / g), and “(ΔHm (B) −ΔHc (B)) / ΔHm (B)” was 0.87.
In Examples 45 to 51 and Comparative Examples 42 and 43, resins constituting the A layer having the same composition and different thicknesses are used, and the presence or absence of the D layer, the kind of the resin forming the B layer, and the thickness are changed. However, in Comparative Example 42, the emboss transferability is good because the thickness of the A layer is thick, but the haze of the A layer after embossing is large and the transparency of the printed layer is poor. Further, the transparency of the printed layer was further deteriorated after being immersed in boiling water. This is due to the fact that crystallization of the A layer progresses due to immersion in boiling water and transparency is lowered.
In Comparative Example 43, since the thickness of the B layer was thinner than the preferred range, when it was passed through an embossing device, the function required for the B layer was not sufficiently exhibited, and the sheet was melt-ruptured by heating with a heater.
In Example 45, the D layer was not used, and the thickness of the A layer was set to 30 μm. However, the emboss transferability was slightly poor because the thickness of the layer to which embossing should be applied was thin.
In Example 46, the A layer was 50 μm without the D layer, but the transfer of fine (shallow) satin embossing was good, but the transferability of the coarse (deep) embossing was not sufficient.
In Example 47, the transferability of the rough emboss was also improved by increasing the thickness of the A layer without the D layer, but the transparency of the printed layer after immersion in boiling water was slightly poor, and the A layer was Further, in Example 48 in which the thickness was increased, the transparency was slightly poor even when not immersed in boiling water.
These print layer transparency was judged to be practically acceptable depending on the print pattern and application, and it was judged to be a problem when clear transparency of the print layer was required. The reason why the transparency of the printed layer is slightly poor is the same as in Comparative Example 8.
In Example 49, the thickness of the A layer is 30 μm as in Example 45, but it has a D layer with a thickness of 50 μm, and the layer to which embossing is applied has a total of 80 μm. Accordingly, good emboss transferability can be obtained in the same manner as in Example 47, and at the same time, the thickness of the A layer related to the transparency of the printed layer is the same as in Example 45. Therefore, good printing is possible even after immersion in boiling water. The transparency of the layer is obtained. The same applies to Example 50.
In Example 51, the composition and composition of the layer to which embossing is applied are the same as in Example 49, and the thickness of the B layer is reduced. However, the basic emboss transferability and the transparency of the printed layer are good. However, when the heater was heated by the embossing apparatus, the sheet was noticeably stretched. Although melt fracture did not occur as in Comparative Example 43, the thickness of layer B was determined to be 20 μm as the lower limit of the preferred range.
In Examples 52 to 55 and Comparative Examples 44 to 47, sheets having the same configuration and composition were used, and the sheet temperature before passing through the embossed pattern roll was changed. In Comparative Examples 44 and 45, embossing was performed at the time of lamination. There was a significant return. This is because the temperature at which distortion (embossed pattern transfer) was applied was low, and the sheet surface temperature rose to near the temperature at which distortion was applied by the heat from the steel sheet during lamination, and the residual stress that had been frozen was released. caused by.
In Comparative Examples 46 and 47, the temperature at which the strain was applied was higher than those in Comparative Examples 44 and 45, and the emboss return at the time of lamination tends to be improved, but it still does not reach the conventional soft PVC sheet. Moreover, the high temperature heat resistance of the embossing as a laminated steel plate is not sufficient.
On the other hand, in Examples 52-55, there is little embossing return at the time of lamination, it is equal to or higher than that of a conventional soft PVC sheet, and high temperature heat resistance as a laminated steel sheet can be obtained at a practically sufficient level. ing.
This embodiment has the following effects.
[First invention]
(1) A sheet having a two-layer structure composed of a layer A composed of a substantially amorphous or low crystalline resin composition and a layer B composed of a substantially crystalline resin composition. Embossing was enabled from the assignable layer A. Therefore, embossing can be performed from the embossable layer A using an embossing device or the like generally used for embossing the PVC sheet. Even when the A layer is heated to a temperature at which embossing is possible, the substantially crystalline B layer has rigidity as a sheet and does not stick to the heating roll.
(2) When the glass transition temperature of the A layer is Tg (A), the melting point of the B layer is Tm (B), and the embossing temperature is T, the embossing is in the relationship of Tg (A) ≦ T ≦ Tm (B). Embossing is easy because the processing temperature can be set.
(3) The relationship between the glass transition temperature Tg (A) [° C.] of the A layer and the melting point Tm (B) [° C.] of the B layer was set to Tg (A) + 30 ≦ Tm (B). Therefore, when the embossing temperature is T, it becomes easy to set the embossing temperature in the relationship of Tg (A) ≦ T ≦ Tm (B).
(4) Even when a printed layer and a transparent upper layer are further formed on the A layer, or when a printed layer and a surface coat are further formed on the A layer, the embossing from the A layer is the same as described above. A laminated resin sheet having higher design properties can be obtained.
(5) The total thickness of all the layers of the laminated resin sheet is 50 μm to 300 μm. Therefore, the sheet is not broken at the time of bonding the laminated resin sheet to a substrate such as a metal plate or by subsequent drilling or bending, and embossing can be easily performed.
(6) When the A layer and the B layer are laminated in an unstretched state, the degree of freedom in processing temperature at the time of embossing is increased, unlike when a stretched sheet is used.
(7) When both the A layer and the B layer are made of a polyester-based resin, when both layers A and B are formed by a coextrusion method, the extrusion operation is easy and the stability of the obtained sheet is good. In addition, it is easy to obtain raw materials having necessary physical properties.
(8) Amorphous polyester resin in which a part of ethylene glycol of polyethylene terephthalate (about 30 to 60 mol%) is substituted with 1,4-cyclohexanedimethanol is used as the amorphous resin composition constituting layer A. Polybutylene terephthalate is used as the crystalline resin composition constituting the B layer. Therefore, the effect of (7) is further improved.
(9) By covering at least one surface of a base material such as a metal plate, a wooden board, or a plywood sheet with embossing applied to each of the laminated resin sheets, a door, a wall material, a floor material, etc. can be used without using PVC. It can be suitably used as a base material for household interior products such as house interior materials, furniture, furniture, elevators, AV products and the like.
The embodiment is not limited to the above, and may be embodied as follows, for example.
The material of the A layer is substantially amorphous, the material of the base material layer B is substantially crystalline, and the glass transition temperature of the embossable layer A is Tg (A), and the melting point of the B layer is Tm. When (B) and the embossing temperature is T, the embossing temperature can be set in the relationship of Tg (A) ≦ T ≦ Tm (B) and embossing can be applied from the A layer. For example, polyethylene terephthalate (PET) may be used instead of polybutylene terephthalate (PBT) as the material of the B layer.
The mixing ratio of the PBT constituting the A layer and the B layer and PETG which is an amorphous polyester resin may be other than the combination of 9/1 and 1/9.
The technical idea (invention) grasped from the embodiment will be described below.
(1) In the first invention, as the amorphous resin composition constituting the embossable layer, a part (about 30 to 60 mol%) of polyethylene glycol of polyethylene terephthalate is replaced with 1,4-cyclohexanedimethanol. Amorphous polyester resin is used, and polybutylene terephthalate is used as the crystalline resin composition constituting the substrate layer.
[Second invention]
(1) A layer made of a substantially amorphous polyester resin or a mixture containing the polyester resin as a main component, and a B layer consisting of a substantially crystalline polyester resin or a mixture containing the polyester resin as a main component A laminated resin sheet was constructed from the above. And B layer is crystallized to the state where a clear crystallization peak is not observed in the measurement by the differential scanning calorimeter (DSC) after sheet forming. Therefore, even when the A layer is heated to a temperature at which embossing can be performed, the substantially crystalline B layer has rigidity as a sheet and does not stick to the heating roll. As a result, embossing can be applied by reheating the sheet, which could not be handled with a polyester resin sheet conventionally, and various embossing methods conventionally used with soft vinyl chloride resins can be used. The embossing can be continuously given to the polyester resin sheet by the method.
(2) When the crystal melting peak temperature (melting point) of the resin forming the B layer is Tm (B) [° C.] and the glass transition point of the resin A is Tg (A) [° C.], Tm (B)> { The relationship of Tg (A) +30} is established. Accordingly, embossing can be applied to the A layer at a temperature equal to or lower than the melting point of the resin forming the B layer, and embossing is facilitated.
(3) When a transparent resin layer is laminated on the A layer, due to the presence of the transparent resin layer, the addition of deep design properties, improvement of surface physical properties, additives such as pigments added to the polyester resin, etc. It is easy to prevent the squirting.
(4) When printing is performed on the A layer to form a printed layer and a transparent resin layer is laminated thereon, various patterns can be formed on the A layer, and the design can be improved.
(5) When the substantially crystalline polyester forming the B layer is polybutylene terephthalate or a copolymer thereof, the base material layer is sufficiently crystallized at the time of forming the sheet in order to achieve good embossing. It becomes easy to perform embossing well.
(6) When the substantially amorphous polyester that forms the A layer is a cyclohexanedimethanol copolymer of polyethylene terephthalate, it is easy to obtain a resin that forms the A layer.
(7) An embossing sheet is obtained by embossing the laminated resin sheet. Therefore, in order to obtain an embossing sheet, various embossing methods conventionally used for soft vinyl chloride resins can be employed.
(8) By laminating a laminated resin sheet on a metal plate with a B layer as an adhesive surface via a thermosetting adhesive, a coated substrate that can be easily embossed by a conventional embossing method is obtained. be able to. This coated substrate can be suitably used as it is or with embossing applied, for home appliance exteriors such as AV equipment and air conditioner covers, steel furniture, elevator interiors, building interiors, and the like.
(9) By coating the embossed sheet on a metal plate with a B layer as an adhesive surface via a thermosetting adhesive, a coated substrate with high designability can be easily obtained. This coated substrate can be suitably used for home appliance exteriors such as AV equipment and air conditioner covers, steel furniture, elevator interiors, building interiors, and the like.
(10) Since the total thickness of the laminated resin sheet is 50 to 500 μm, when used as a coating substrate, the performance as a protective layer for a metal plate and the secondary workability such as punching as a coating substrate are inferior. Can be suppressed. In addition, when printing is performed, the printed pattern is hardly affected by the color of the base metal plate.
The embodiment is not limited to the above, and may be embodied as follows, for example.
The method for producing an embossing sheet having a transparent resin layer is to give embossing to the embossable layer in the state of a laminated resin sheet having a two-layer structure, or in a state where a printing layer is formed on the embossable layer, It is not restricted to the method of forming a transparent resin layer. For example, embossing may be applied from above the transparent resin layer to the laminated resin sheet on which the transparent resin layer is formed.
The laminated resin sheet and the embossed sheet are not limited to the use for laminating a metal plate via an adhesive to form a coated base material, and may be used by being laminated on a base material such as a wood board or plywood.
The invention (technical idea) grasped from the embodiment will be described below.
(1) In the second invention, the laminated resin sheet has a total thickness of 50 to 500 μm.
[Third invention]
(1) The transparent coating layer which has an ultraviolet absorptivity is provided in the surface of A layer of the sheet | seat which laminated | stacked the polyester resin layer of at least 2 layer of A layer and B layer. Therefore, the presence of the transparent coating layer having a thickness of 2 μm to 20 μm having ultraviolet absorptivity improves the light resistance, in particular, can improve the light yellowing of the polyester-based resin, impart a deep design property, It becomes easy to improve the physical properties and prevent the additives such as pigments added to the polyester resin from being ejected.
(2) The resin constituting the A layer is made of a substantially amorphous polyester resin or a mixture containing the polyester resin as a main component, and the resin constituting the B layer is a substantially crystalline polyester resin or the polyester resin It consists of the mixture which has resin as a main component. Furthermore, the B layer does not show adhesiveness to the metal roll when the sheet is heated for embossing, and the crystal melting peak temperature (melting point) of the resin component B is Tm (B) [° C.], When the glass transition point of the resin component A is Tg (A) [° C.], the relationship of Tm (B)> {Tg (A) +30} is established. Therefore, when the sheet is heated for embossing, it does not exhibit adhesiveness to the metal roll, and embossing is possible below the melting point of the base material layer relative to the embossable layer, and the base material layer is heated in the heated state. Embossing is performed well without melting and breaking. And it becomes easy to give emboss continuously with respect to a polyester-type resin sheet with the embossing provision apparatus conventionally used with soft vinyl chloride-type resin.
(3) When the transparent coating layer includes at least one coating layer of a crosslinkable resin containing an ultraviolet absorbing component, in addition to the UV absorbing property, the gloss adjustment, further improvement of scratch resistance, It becomes easy to impart secondary effects such as improvement of contamination and imparting a deep design.
(4) When the UV absorbing component is an additive type UV absorber, a general method of adding and applying the UV absorber to the coating solution can be adopted, and UV absorption is imparted to the transparent coating layer. Becomes easier.
(5) In the case where the ultraviolet absorbing component is obtained by copolymerizing a reactive ultraviolet absorber in the molecule of the crosslinkable resin, the volatilization resistance and migration resistance of the ultraviolet absorber are added to the additive type ultraviolet absorber. It becomes better compared.
(6) When the printing layer is provided between the A layer and the transparent coating layer, various patterns can be easily provided, and the design can be enhanced.
(7) After embossing is applied to the A layer of the laminated resin sheet, the embossed sheet provided with the transparent coating layer is compared with the configuration in which the transparent coating layer is provided on the laminated resin sheet and then embossed. Thus, embossing is easily performed satisfactorily.
(8) In the embossed sheet in which the embossing is performed on the layer A from above the transparent coating layer of the laminated resin sheet, the embossed sheet is completed as compared with the case where the transparent coating layer is provided after embossing the laminated resin sheet. The number of steps until the process can be reduced.
(9) The coated base material was formed by laminating the laminated resin sheet or the embossed sheet configured as described above on a metal plate through a thermosetting adhesive with the B layer side as an adhesive surface. Therefore, it is easy to be exposed to parts that are relatively easily exposed to sunlight and artificial light sources with a large amount of ultraviolet radiation in exteriors of home appliances such as AV equipment and air conditioner covers, steel furniture, elevator interiors, and interiors of buildings. It can be suitably used for the site.
(10) The total thickness of the A layer and the B layer is 100 to 240 μm, and since the thickness of the B layer is 10 to 50 μm, the embossing plate roll that has been conventionally used for embossing the PVC sheet is large. The embossed pattern can be imparted to the laminated resin sheet at the portion.
The embodiment is not limited to the above, and may be embodied as follows, for example.
It is good also as a coated base material which embossed and gave the embossing sheet | seat to the coating base material which laminated | stacked the laminated resin sheet in the state in which the embossing process was not made | formed.
The laminated resin sheet and the embossed sheet are not limited to the use for laminating a metal plate via an adhesive to form a coated base material, and may be used by being laminated on a base material such as a wood board or plywood.
The laminated resin sheet is not limited to one composed of one A layer and one B layer, it is sufficient that each of the A layer and the B layer has at least one layer, and the A layer and the B layer are plural or any one of them. May be composed of a plurality of layers.
The invention (technical idea) grasped from the embodiment will be described below.
(1) In 3rd invention, the sum total of the thickness of the said emboss provision possible layer and a base material layer is 100-240 micrometers, The thickness of a base material layer is 10-50 micrometers among them.
[Fourth Invention]
(1) The laminated resin sheet comprises a sheet obtained by laminating at least two polyester-based resin layers of the A layer and the B layer, and the A layer and the B layer have the following requirements in the sheet before embossing. . That is, the A layer has 10 ≦ ΔHm (A) ≦ 35 [J / g] and (ΔHm (A) −ΔHc (A)) / ΔHm (A) ≦ 0.5. The B layer has 180 ≦ Tm (B) ≦ 240 [° C.] and 0.5 ≦ (ΔHm (B) −ΔHc (B)) / ΔHm (B). Therefore, when continuously embossing the laminated resin sheet with an embossing machine that has been used for embossing soft PVC sheets, it prevents sticking to the heated metal roll and breakage of the sheet due to melting. An embossed pattern can be applied smoothly.
(2) If an embossed pattern is imparted to the A layer of the laminated resin sheet, an embossed pattern with good heat resistance can be obtained.
(3) After heating the laminated resin sheet to 160 ° C or higher and the crystal melting peak temperature Tm-20 ° C or lower of the B layer, the embossed pattern is given to the A layer by passing between the embossing roll and the pressure roll. The provided embossed pattern has good heat resistance. Therefore, even when used for an exterior of a household electrical appliance having an exothermic member or the like inside, it is possible to suppress the occurrence of emboss return due to the heating of the sheet.
(4) If the B layer contains a polybutylene terephthalate (PBT) resin and satisfies the requirement of 35 ≦ ΔHm ≦ 60 [J / g], a PBT resin having a high crystallization rate at the time of normal extrusion film formation However, the conditions that the base material layer 13 should have can be satisfied. Accordingly, a special process such as a heat treatment in a separate process after film formation is not necessary, and productivity can be improved and costs can be reduced.
(5) If the B layer contains a PTT resin and satisfies the requirement of 35 ≦ ΔHm ≦ 60 [J / g], the PBT resin having a high crystallization rate at the time of normal extrusion film formation is Can satisfy the conditions to be provided. Also in this case, a special process such as a heat treatment in a separate process after the film formation of the sheet is not necessary, and the productivity can be improved and the cost can be reduced.
(6) If the polyester-based resin layer of at least two layers of the A layer and the B layer is a laminated and integrated sheet by a co-extrusion method, compared to the case where the separately formed sheets are laminated and integrated in a subsequent process, Productivity can be improved and costs can be reduced. Further, since the adhesive strength between the A layer and the B layer can be strengthened, it is difficult to cause a problem of peeling with time.
(7) If a coating layer having non-adhesiveness with a heated metal is applied to the surface on the A layer side of the laminated resin sheet, when the sheet is heated with an embossing machine, it causes adhesive troubles with various auxiliary rolls. The danger of can be avoided. Also, when a heated embossing roll is used to give an embossed design with good heat resistance, the non-adhesiveness to the roll is good, that is, it is difficult to stick to the roll.
(8) If the thickness of the coating layer is 1 to 10 μm, problems such as partial adhesion to the heated metal roll due to coating unevenness because the thickness is too thin, and the thickness of the coating layer is too thick. Problems such as resin physical properties affecting important physical properties of the laminated resin sheet can be easily avoided.
(9) An embossed design that can be suitably used for various applications by laminating a B layer of an embossed sheet with an embossed pattern on the A layer of a laminated resin sheet on a metal plate with a thermosetting adhesive. It is possible to obtain a coated base material provided with the above without using a soft PVC sheet.
(10) Using the layer B of the embossed sheet as an adhesive surface, laminating using a laminating roll on a metal plate coated and baked with a thermosetting adhesive, and then immediately cooling with water will suppress embossing return during lamination. Thus, an embossed design-imparting coated base material having a deep design can be obtained.
(11) If the covering base material is used for a building interior material such as a door material, a unit bath wall material, or a unit bath interior material, a soft PVC sheet is not used and an architectural interior material excellent in design is obtained. Can do.
The embodiment is not limited to the above, and may be embodied as follows, for example.
A printed layer may be provided on the A layer of the laminated resin sheet.
The embossing sheet is not limited to the sheet having the embossed pattern on the surface of the embossing sheet. For example, if you want to obtain a design sheet that has an uneven design with an embossed pattern inside and a smooth design on the surface, or if you want to visually emphasize the recessed part with embossed grain, etc. In the case of applying a so-called wiping treatment, the transparent resin layer is laminated after embossing the laminated resin sheet.
The laminated resin sheet and the embossed sheet are not limited to the use for laminating a metal plate via an adhesive layer to form a coated base material, and may be used by being laminated on a base material such as a wood board or plywood.
The invention (technical idea) grasped from the embodiment will be described below.
(1) In the fourth invention, the coating layer has a thickness of 1 to 10 μm.
(2) Moreover, the total thickness of the said laminated resin sheet is 50-500 micrometers.
[Fifth Invention]
(1) The laminated resin sheet is composed of at least three layers in the order of the A layer, the C layer, and the B layer, and the A layer and the B layer have the following requirements in the sheet before embossing. That is, the A layer has 10 ≦ ΔHm (A) ≦ 35 and (ΔHm (A) −ΔHc (A)) / ΔHm (A) ≦ 0.5. The B layer has 180 ≦ Tm (B) ≦ 240 [° C.] and 0.5 ≦ (ΔHm (B) −ΔHc (B)) / ΔHm (B). Therefore, when continuously embossing the laminated resin sheet with an embossing machine that has been used for embossing soft PVC sheets, it prevents sticking to the heated metal roll and breakage of the sheet due to melting. An embossed pattern can be applied smoothly, and printing can be applied separately from the C layer.
(2) A pigment is added between the C layer and the B layer, and by interposing a D layer having the same characteristics as the A layer, in addition to the above effects, the obtained laminated resin sheet is colored. Can be rubbed.
(3) After heating the laminated resin sheet to 160 ° C or higher and the crystal melting peak temperature Tm-20 ° C or lower of the B layer, the embossed pattern is given to the A layer by passing between the embossing roll and the pressure roll. The provided embossed pattern has good heat resistance. Therefore, even when used for an exterior of a household electrical appliance having an exothermic member or the like inside, it is possible to suppress the occurrence of emboss return due to the heating of the sheet.
(4) If the B layer contains a polybutylene terephthalate (PBT) resin and satisfies the requirement of 35 ≦ ΔHm ≦ 60 [J / g], a PBT resin having a high crystallization rate at the time of normal extrusion film formation However, the conditions that the base material layer 13 should have can be satisfied. Accordingly, a special process such as a heat treatment in a separate process after film formation is not necessary, and productivity can be improved and costs can be reduced.
(5) If the B layer contains a PTT resin and satisfies the requirement of 35 ≦ ΔHm ≦ 60 [J / g], the PBT resin having a high crystallization rate at the time of normal extrusion film formation is Can satisfy the conditions to be provided. Also in this case, a special process such as a heat treatment in a separate process after the film formation of the sheet is not necessary, and the productivity can be improved and the cost can be reduced.
(6) If a coating layer having non-adhesiveness with a heated metal is applied to the surface of the A layer side of the laminated resin sheet, when the sheet is heated with an embossing machine, adhesion troubles with various auxiliary rolls, etc. The danger of can be avoided. Also, when a heated embossing roll is used to give an embossed design with good heat resistance, the non-adhesiveness to the roll is good, that is, it is difficult to stick to the roll.
(7) If the thickness of the coating layer is 1 to 10 μm, problems such as partial adhesion to the heated metal roll due to coating unevenness due to the thickness being too thin, and the thickness of the coating layer being too thick. Problems such as resin physical properties affecting important physical properties of the laminated resin sheet can be easily avoided.
(8) An embossed design that can be suitably used for various applications by laminating a B layer of an embossed sheet with an embossed pattern on the A layer of a laminated resin sheet on a metal plate with a thermosetting adhesive. It is possible to obtain a coated base material provided with the above without using a soft PVC sheet.
(9) Using the B layer of the embossed sheet as an adhesive surface, laminating a metal plate coated with a thermosetting adhesive and baking using a laminating roll, and then immediately cooling with water suppresses embossing return during lamination. Thus, an embossed design-imparting coated base material having a deep design can be obtained.
(10) If the covering base material is used for a building interior material such as a door material, a unit bath wall material, or a unit bath interior material, a soft PVC sheet is not used and an architectural interior material excellent in design is obtained. Can do.
The embodiment is not limited to the above, and may be embodied as follows, for example.
The embossing sheet is not limited to the sheet having the embossed pattern on the surface of the embossing sheet. For example, if you want to obtain a design sheet that has an uneven design with an embossed pattern inside and a smooth design on the surface, or if you want to visually emphasize the recessed part with embossed grain, etc. In the case of applying a so-called wiping treatment, the transparent resin layer is laminated after embossing the laminated resin sheet.
The laminated resin sheet and the embossed sheet are not limited to the use for laminating a metal plate via an adhesive layer to form a coated base material, and may be used by being laminated on a base material such as a wood board or plywood.
The invention (technical idea) grasped from the embodiment will be described below.
(1) In the fifth invention, the coating layer has a thickness of 1 to 10 μm. The laminated resin sheet has a total thickness of 50 to 500 μm.
The invention's effect
The resin laminated sheet according to the present invention does not use PVC, and in the embossing process to the sheet, even if it is brought into contact with a heating roll for heating the sheet, it does not stick and stick, and embossing can be performed. It can be implemented, and can cope with various embossing methods that have been generally used for soft vinyl chloride resin sheets.
In addition, by using this resin laminated sheet or an embossed sheet obtained by embossing this resin laminated sheet, the interior of buildings such as a house interior, the exterior of home appliances such as AV equipment and an air conditioner cover, steel furniture, A coated substrate using a coated sheet that is suitable as a substrate for an elevator interior or the like and does not use PVC is obtained.
Furthermore, in the third invention, the light resistance of the resulting embossed sheet is good.
[Brief description of the drawings]
FIGS. 1A and 1C are side views showing examples of laminated resin sheets according to the first to fifth inventions, and FIG. 1B is a first invention to the second invention. It is a side view which shows the example of an emboss provision sheet | seat.
FIGS. 2A to 2D are side views showing examples of coated substrates according to the second to fifth inventions.
FIG. 3 is a schematic diagram showing an example of the structure of the embossing device.

Claims (38)

A substantially non-crystalline or low-crystalline resin composition or an embossable layer (A layer) containing a large amount of the substantially non-crystalline or low-crystalline resin composition, and substantially crystalline And a base material layer (B layer) containing a large amount of the resin composition that is substantially crystalline, and the A layer can be embossed. When the glass transition temperature of the A layer is Tg (A), the melting point of the B layer is Tm (B), and the embossing temperature is T, the embossing is in the relationship of Tg (A) ≦ T ≦ Tm (B). The laminated resin sheet according to claim 1, wherein the temperature can be set. The laminated resin sheet according to claim 1, wherein a printed layer and a transparent upper layer are further formed on the A layer. The laminated resin sheet according to claim 1, wherein a printed layer and a surface coat layer are further formed on the A layer. The laminated resin sheet according to any one of claims 1 to 4, wherein the total thickness of all layers is 50 µm to 300 µm. The laminated resin sheet according to any one of claims 1 to 5, wherein the A layer and the B layer are laminated in an unstretched state. The layered resin according to claim 1, wherein the A layer and the B layer are two types of polyester resins having different compositions, and each of the A layer and the B layer can be embossed by satisfying the following conditions. Sheet.
Layer A: From a substantially amorphous polyester-based resin or a mixture containing 50% or more by weight of the polyester-based resin in which no clear crystal melting peak is observed at the time of temperature rise in measurement with a differential scanning calorimeter (DSC) Become.
B layer: from a substantially crystalline polyester resin or a mixture containing 50% or more by weight of the polyester resin, in which a clear crystal melting peak is observed when the temperature is raised in the measurement with a differential scanning calorimeter (DSC). Furthermore, the resin layer after film formation is crystallized to a state where no clear crystallization peak is observed in the measurement with a differential scanning calorimeter (DSC). When the crystal melting peak temperature (melting point) of the polyester resin constituting the B layer is Tm (B) [° C.] and the glass transition point of the polyester resin constituting the A layer is Tg (A) [° C.] The laminated resin sheet according to claim 7, wherein a relationship of Tm (B)> {Tg (A) +30} is established. The laminated resin sheet according to claim 7 or 8, wherein a transparent resin layer is laminated on the A layer. The laminated resin sheet according to claim 7 or 8, wherein printing is performed on the A layer, and a transparent resin layer is laminated thereon. The laminated resin sheet according to any one of claims 7 to 10, wherein the substantially crystalline polyester used for the B layer is polybutylene terephthalate or a copolymer thereof. The laminated resin sheet according to any one of claims 7 to 11, wherein the substantially amorphous polyester used for the polyester-based resin constituting the A layer is a cyclohexanedimethanol copolymer of polyethylene terephthalate. The transparent coating layer of the thickness range of 2 micrometers-20 micrometers which has ultraviolet absorptivity was provided in the surface of the said A layer of the sheet | seat which laminated | stacked the polyester resin layer of the said A layer and B layer at least 2 layers. The laminated resin sheet described. The laminated resin sheet according to claim 13, wherein the A layer and the B layer satisfy the following conditions.
Layer A: The polyester resin constituting the layer A is a substantially amorphous polyester resin or a polyester resin in which no clear crystal melting peak is observed at the time of temperature rise in the measurement with a differential scanning calorimeter (DSC). It consists of a mixture containing 50% or more by weight.
Substrate layer: Polyester resin constituting the B layer is a substantially crystalline polyester resin or a polyester resin in which a clear crystal melting peak is observed at the time of temperature rise in the measurement with a differential scanning calorimeter (DSC). Is a mixture containing 50% or more by weight, and when the sheet is heated for embossing, it does not exhibit adhesiveness to the metal roll.
When the crystal melting peak temperature (melting point) of the polyester resin constituting the B layer is Tm (B) [° C.] and the glass transition point of the resin component is Tg (A) [° C.], Tm (B) > {Tg (A) +30} is established. The laminated resin sheet according to claim 13 or 14, wherein the transparent coating layer includes at least one coating layer of a crosslinkable resin containing an ultraviolet absorbing component. The laminated resin sheet according to claim 15, wherein the ultraviolet absorbing component is an additive type ultraviolet absorber. The laminated resin sheet according to claim 15, wherein the ultraviolet absorbing component is obtained by copolymerizing a reactive ultraviolet absorber in the molecule of the crosslinkable resin. The laminated resin sheet according to any one of claims 13 to 17, wherein a printed layer is provided between the A layer and the transparent coating layer. The laminated resin sheet according to claim 1, comprising a sheet obtained by laminating at least two polyester resin layers of the A layer and the B layer, wherein the A layer and the B layer have the following requirements.
A layer: In the sheet before embossing, at the time of temperature rise as measured by a differential scanning calorimeter (DSC), a clear crystallization peak temperature Tc (A) [° C.] and a crystal melting peak temperature Tm (A) [° C. ] Is observed, and the following relational expression holds when the heat of crystallization is ΔHc (A) [J / g] and the heat of crystal fusion is ΔHm (A) [J / g].
10 ≦ ΔHm (A) ≦ 35
(ΔHm (A) −ΔHc (A)) / ΔHm (A) ≦ 0.5
B layer: In the sheet before embossing, a clear crystal melting peak temperature Tm (B) [° C.] was observed at the time of temperature rise as measured by a differential scanning calorimeter (DSC), and the heat of crystallization was ΔHc (B) When [J / g] and the amount of heat of crystal melting is ΔHm (B) [J / g], the following relational expression is established.
180 ≦ Tm (B) ≦ 240
0.5 ≦ (ΔHm (B) −ΔHc (B)) / ΔHm The laminated resin sheet according to claim 19, wherein the B layer includes a polybutylene terephthalate (PBT) resin or a polytrimethylene terephthalate (PTT) resin, and the following relational expression is satisfied.
35 ≦ ΔHm (B) ≦ 60 The laminated resin sheet according to claim 19 or 20, which is a sheet in which at least two polyester resin layers of the A layer and the B layer are laminated and integrated by a coextrusion method. The laminated resin sheet according to any one of claims 19 to 21, wherein a coating layer having non-adhesiveness with a heated metal is provided on the surface of the layer A. The laminated resin sheet according to claim 1, comprising at least three layers in the order of the A layer, the C layer, and the B layer, wherein the A layer and the B layer have the following characteristics.
Layer A: An unstretched polyester resin layer having a thickness of 15 μm or more and 120 μm or less, and a clear crystallization peak temperature Tc (A) when heated by a differential scanning calorimeter (DSC) in a sheet before embossing. (° C.) and a crystal melting peak temperature Tm (A) (° C.) are observed, the crystallization heat quantity is ΔHc (A) (J / g), and the crystal fusion heat quantity is ΔHm (A) (J / g) Both of the following relational expressions hold.
10 ≦ ΔHm (A) ≦ 35
(ΔHm (A) −ΔHc (A)) / ΔHm (A) ≦ 0.5
B layer: In the sheet before embossing, a clear crystal melting peak Tm (B) (° C.) is observed at the time of temperature rise by a differential scanning calorimeter (DSC), and the amount of crystallization is ΔHc (B) (J / g) When the amount of heat of crystal fusion is ΔHm (B) (J / g), both of the following relational expressions hold.
180 ≦ Tm (B) ≦ 240
0.5 ≦ (ΔHm (B) −ΔHc (B)) / ΔHm (B) The laminated resin sheet according to claim 23, wherein a polyester-based resin layer (D layer) having the following characteristics is interposed between the C layer and the B layer.
D layer: colored by pigment addition, and on the sheet before embossing, a clear crystallization peak temperature Tc (D) (° C.) and a crystal melting peak temperature when heated by a differential scanning calorimeter (DSC) When Tm (D) (° C.) is observed, the crystallization heat quantity is ΔHc (J / g), and the crystal melting heat quantity is ΔHm (J / g), the following relational expression is established.
10 ≦ ΔHm (D) ≦ 35
(ΔHm (D) −ΔHc (D)) / ΔHm (D) ≦ 0.5 The laminated resin sheet according to claim 23 or 24, wherein the B layer includes a polybutylene terephthalate (PBT) resin or a polytrimethylene terephthalate (PTT) resin, and the following relational expression is satisfied.
30 ≦ ΔHm (B) ≦ 65 The laminated resin sheet according to any one of claims 23 to 25, wherein a coating layer having non-adhesiveness with a heated metal having a thickness of 1 to 10 µm is provided on the surface of the A layer side. The embossing sheet | seat which provided the embossing to the said A layer of the laminated resin sheet in any one of Claims 1-6. The embossing sheet | seat which provided the embossing to the laminated resin sheet in any one of Claims 7-12. The embossing provision sheet | seat in which the said transparent coating layer was formed after embossing was given to the said A layer of the laminated resin sheet in any one of Claims 13-18. The embossing sheet | seat with which the embossing with respect to the said A layer is given from the said transparent coating layer of the laminated resin sheet in any one of Claims 13-18. The embossing provision sheet | seat which gave the embossing pattern to the said A layer of the laminated resin sheet in any one of Claims 19-26. The embossed pattern is heated to 160 ° C. or higher and {B layer crystal melting peak temperature (Tm (B)) − 20} ° C. or lower, and then passes between an embossed plate roll engraved with an embossed pattern and a pressure-bonding roll. The embossing provision sheet | seat of Claim 31 provided by making it. After the laminated resin sheet according to any one of claims 19 to 26 is heated to 160 ° C or higher and the {B layer crystal melting peak temperature (Tm (B)) -20} ° C or lower, an embossed pattern is formed. The manufacturing method of the embossing sheet | seat which provides an embossing pattern to the said A layer by passing between the engraved embossing roll and nip roll. A coated base material obtained by coating the embossed sheet obtained by embossing the laminated resin sheet according to any one of claims 1 to 6 on at least one surface of a base material selected from a metal plate, a wooden board, or a plywood. The laminated resin sheet according to any one of claims 7 to 12, the embossed sheet according to claim 28, the laminated resin sheet according to any one of claims 13 to 18, or the claim 29 or 30. A coated substrate obtained by laminating the embossed sheet according to 1 above on a metal plate through a thermosetting adhesive with the B layer as an adhesive surface. A coated substrate obtained by laminating the embossed sheet according to claim 31 or 32 on a metal plate with a thermosetting adhesive with the B layer as an adhesive surface. The covering base material according to claim 36 used as a building interior material selected from a door material, a unit bath wall material, or a unit bath interior material. The embossed sheet according to claim 31 or 32 is laminated on a metal plate coated with a thermosetting adhesive using a laminating roll with the B layer as an adhesive surface, and immediately cooled by water cooling. Production method.

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