JP2004090507A - Decorative sheet and water-based coating liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet in which a weather resistance and adhesive properties are improved and to provide a water-based coating liquid which can be suitably used for such a decorative sheet, etc. <P>SOLUTION: In the decorative sheet 1 in which a substrate 2, a coloring layer 11, an adhesive layer 5, a transparent resin layer 6 and a protective layer 9 are sequentially laminated in this order, at least one or more layers of the layers 11, 5 and 9 are each formed of the water coating liquid which contains a water soluble or water dispersive ultraviolet absorber and/or a water soluble or water dispersive light stabilizer, and at least one or more layers of the layer 11, the layer 5 and the layer 9 are each formed of a hydrophobic ultraviolet absorber and/or a non-hydrophilic light stabilizer. The layer 11, the layer 5 and the layer 9 are preferred to be formed of the water coating liquid. As an embodiment of the decorative sheet 1, a rugged pattern 7 can be formed on a surface side of the layer 6 (to the layer 9), a partially coloring layer 8 can be formed on a recess part 17 of the pattern 7 or a primer layer 10 can be formed on a rear surface of the substrate. <P>COPYRIGHT: (C)2004,JPO

Description

【００５３】
上記以外の水溶性または水分散性の紫外線吸収剤として、水溶性および／または水分散性の樹脂の分子内に紫外線吸収剤成分を導入したものを用いることもできる。例えば、下記化学式２の化合物（モノマー分子量：３２３、ＣＡＳ−Ｎｏ．９６４７８−０９−０）からなる紫外線吸収剤成分と、親水性成分と、メタクリル酸メチル、スチレン等とをラジカル重合により共重合体にした水性樹脂を挙げることができる。
【化２】

ここで、こうした水性樹脂が、水分散性となるか、または水溶性となるかは、個々の樹脂に対しての親水性成分の水和力及び親水性成分（親水性基）の含有量で決まる。水性樹脂における親水性基の量が増加することにより、紫外線吸収剤は水分散性から水溶性となる。親水性成分としては、中和により親水性となりうるものと、成分そのもので親水性を有するものがある。中和により親水性となりうるものとしては、例えば、カルボキシル基、スルホン酸基、りん酸基、第三級アミノ基、第四級アミノ基等が挙げられる。また、その場合の中和剤としては、中和あるいはイオン化できるものであれば特に制限はないが、例えば、水酸化ナトリウム、水酸化カリウム等の不揮発性塩基；トリメチルアミン、トリエチルアミン、トリエタノールアミン等の第三級アミン類；アンモニア等の揮発性塩基；塩酸、硝酸等の無機酸；蟻酸、酢酸、乳酸、クエン酸、酒石酸等の有機酸等が挙げられる。成分そのもので親水性を有するものとしては、水酸基、エーテル結合が挙げられる。このうち、耐候性を向上させる観点から、水酸基を導入した化合物が好ましく用いられる。なお、紫外線吸収剤成分である化合物の含有割合は、共重合化合物１００重量％に対し、０．０１〜５０重量％の範囲で調整される。
【００５４】
水溶性および／または水分散性の樹脂の分子内に紫外線吸収剤成分を導入した紫外線吸収剤の他の例としては、例えば、上記水溶性及び水分散性の紫外線吸収剤共重合物をプレポリマーとしたポリウレタン樹脂、ポリエステル樹脂、アクリル樹脂、ビニル樹脂等が挙げられる。なお、紫外線吸収剤を分子内に導入した水性樹脂は、後述する主剤としての役割を果たすこともできる。
【００５５】
水分散性の光安定剤（ラジカル捕集剤）としては、例えば、下記化学式３の化合物（分子量：約９００、比重：０．９８、粘度：７０００ｍＰａ・ｓ（ｃｐｓ）、ＣＡＳ−Ｎｏ．１０１５４４−９８−３，８４６９６−７２−０，１０７１１９−９１−５）を乳化剤等により水分散性処理したもの（比重０．９９９、粘度：４５ｍＰａ・ｓ（ｃｐｓ））を挙げることができる。
【００５６】
【化３】

水溶性または水分散性である紫外線吸収剤および／または光安定剤は、主剤、架橋剤および溶媒（水系）からなる塗工液を１００としたときに、０．００１〜１０の割合で配合される。紫外線吸収剤と光安定剤とを両方配合させる場合には、紫外線吸収剤：光安定剤の配合割合は特に限定されない。
【００５７】
▲２▼主剤および架橋剤；
主剤としては、例えば、ポリウレタン樹脂、ポリエステル樹脂、アクリル樹脂、ビニル樹脂、エポキシ樹脂等及びこれらの共重合物、これらの混合物等が挙げられる。こうした主剤は、架橋剤成分と反応する官能基を有することが必要とされる。
【００５８】
架橋剤としては、例えば、イソシアネート化合物、エポキシ化合物、オキサゾリン化合物、カルボジイミド化合物、シラノール基含有化合物等が挙げられる。このうち、イソシアネート化合物を用いることが好ましい。
【００５９】
主剤：架橋剤の配合割合は、１００：０．５〜１００：１００、好ましくは１００：５〜１００：２０である。
【００６０】
▲３▼溶媒である水は、従来より水系塗工液に使用されているグレードの工業用水が使用される。また、水とアルコール等とからなる混合溶媒を、水系塗工液の溶媒として使用することもできる。そうした混合溶媒を構成するアルコール等としては、エタノール、イソプロピルアルコール、ｎ−プロピルアルコール等の低級アルコール、グリコール類およびそのエステル類等を挙げることができる。なお、これら低級アルコール、グリコール類およびそのエステル類等の溶媒は、水系塗工液の流動性改良、被塗工体である着色層への濡れの向上、乾燥性の調整等の目的で使用されるものであり、その目的に応じてその種類、使用量等が決定される。本発明で使用される水系塗工液は、ベンゼン、トルエン、キシレン等の危険性の高い芳香族炭化水素系の有機性揮発物質が用いられておらず、また、その他の有機溶剤の使用も抑えているので、ＶＯＣの発生を減少させることができる。
【００６１】
水とアルコール等とからなる混合溶媒においては、それらの配合割合を、水：アルコール等（例えば、イソプロピルアルコール、メタノール、エタノール、ｎ−プロピルアルコール等が挙げられる。）＝２０：８０〜１００：０の範囲で調整できる。また、水系塗工液中の溶媒の配合割合は、主剤と架橋剤を１００とした場合に、５０〜４００の割合で配合させることが好ましい。
【００６２】
水系塗工液には、上記紫外線吸収剤と光安定剤の他に、着色剤、分散剤、消泡剤、レベリング剤、安定剤、充填剤、潤滑剤、滑剤等の添加剤を任意に添加してもよい。
【００６３】
接着層用の水系塗工液は、▲１▼紫外線吸収剤および／または光安定剤、▲２▼主剤および架橋剤、▲３▼水系の溶媒を、上記の割合で配合し、ミキサー等で十分に混合することにより調製される。
【００６４】
着色層１１および／または保護層９が、本発明の水系塗工液により形成された場合においては、接着層５を、紫外線吸収剤や光安定剤が含有されていない水系塗工液や、溶剤系塗工液、無溶剤系塗工剤により形成することもできるが、本発明の水系塗工液を用いて形成することが最も好ましい。
【００６５】
なお、溶剤系塗工液としては、２液性の油性ウレタン樹脂、油性アクリル樹脂と油性ウレタン樹脂との混合物等を挙げることができる。２液性の油性ウレタン樹脂は、油性ウレタン樹脂と架橋剤であるイソシアネートとを、樹脂成分：架橋剤成分＝１０：１〜１０：６０の範囲で含有する。また、油性アクリル樹脂と油性ウレタン樹脂との混合物は、例えば、油性ウレタン樹脂と、メタクリル酸メチル（ＭＭＡ）、メタクリル酸ヒドロキシエチル（ＨＥＭＡ）、ジメチルアミノエチルメタクリレート等との混合物が挙げられる。この場合において、溶剤系の塗工剤を塗布・乾燥して得られた接着剤層中のウレタン樹脂が１０〜１００重量％含有するように、油性アクリル樹脂と油性ウレタン樹脂とを混合しておくことが好ましい。
【００６６】
また、無溶剤系（ノンソル系）の塗工剤としては、ポリオール化合物とポリイソシアネート化合物からなるものが挙げられる。ポリオール化合物としては、例えば、ポリエステルポリオール、ポリエーテルポリオール等が挙げられる。ポリイソシアネート化合物としては、例えば、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート等のポリイソシアネート単量体から誘導されたイソシアヌレート、ビューレット、アロファネート等の多官能ポリイソシアネート化合物、あるいはトリメチロールプロパン、グリセリン等の３官能以上のポリオール化合物との反応により得られる末端イソシアネート基含有の多官能ポリイソシアネート化合物等を挙げられる。
【００６７】
溶剤系塗工液や無溶剤系塗工剤に添加する紫外線吸収剤としては、ベンゾトリアゾール、ベンゾフェノン、トリアジン、サリチル酸エステル等の有機物、または、酸化亜鉛、酸化セシウム、酸化チタン等の無機物を０．２μｍ径以下の微粒子状としたものを用いることができる。同様の光安定剤としては、ビス−（２，２，６，６−テトラメチル−４−ビペリジニル）セバケート、ビス−（Ｎ−メチル−２，２，６，６−テトラメチル−４−ビペリジニル）セバケートや、その他特公平４−８２６２５号公報に開示されている化合物等のヒンダード系ラジカル捕集剤、ビペリジニル系ラジカル補足剤等を用いることができる。
【００６８】
なお、本発明においては、着色層１１、接着層５、保護層９のいずれの層も、非親水性の紫外線吸収剤、および／または、非親水性の光安定剤を含有する水系塗工液では形成されない。そのため、この接着層５においてもそうした水系塗工液では形成されない。ここで、非親水性の紫外線吸収剤、非親水性の光安定剤とは、その化合物自身が水に溶解せず、かつ、安定して水に分散しない物質をいい、乳化剤等を用いて強制的に水に分散しても水中で安定化しない物質を含む。従って、上記した溶剤系塗工液や無溶剤系塗工液に添加する紫外線吸収剤および光安定剤のうち、非親水性の性質を有するものは、上述した接着層用の水系塗工液には添加されない。水系塗工液に非親水性の紫外線吸収剤および／または光安定剤を添加した場合には、その水系塗工液で形成した接着層を有する化粧シートの層間密着性や耐候性、耐擦傷性、接着特性等が悪くなる場合がある。
【００６９】
接着層５は、上述した接着層用塗工液を、着色層１１上に塗工または印刷等によって設けた後、乾燥させて形成される。塗工方法としては、公知の各種方法、例えばロールコート、カーテンフローコート、ワイヤーバーコート、リバースコート、グラビアコート、グラビアリバースコート、エアーナイフコート、キスコート、ブレードコート、スムーズコート、コンマコート、スプレーコート、かけ流しコート、刷毛塗り等の方法を用いることができ、乾燥後の膜厚が１〜１０μｍ程度になるように塗工される。
【００７０】
（透明樹脂層）
透明樹脂層６は、トップ樹脂層ともいわれ、着色層１１を擦り傷等から保護したり、化粧シート１の表面強度を向上させたり、塗装感を付与すること等を目的として、接着層５を介して着色層１１上に積層される。
【００７１】
透明樹脂層６を構成する樹脂としては、上述した接着層５を介して着色層１１上に密着よく形成される透明な樹脂であれば特に限定されるものではないが、例えば、透明ポリプロピレン等のオレフィン系樹脂が好ましく挙げられる。透明樹脂層用の樹脂として使用できるオレフィン樹脂以外の樹脂としては、上述の基材２に使用される樹脂材料と同じものを使用することができる。こうした透明樹脂層６を形成する樹脂には、必要に応じて、着色剤、充填剤、紫外線吸収剤、光安定剤、マット剤等の公知の添加剤が添加される。
【００７２】
透明樹脂層６は、接着層５上に、別個に形成された透明樹脂シートを積層して形成されたり、溶融押出し塗工法により成膜されたり、その他公知の方法で積層される。
【００７３】
また、図２に示すように、透明樹脂層６を２層以上の複層構造にしてもよい。２層以上積層させてなる透明樹脂層１６は、基材２側の透明樹脂層６’と保護層側の透明樹脂層６”とに異なる作用効果を持たせることができる点で有利である。一の具体例として、保護層側の透明樹脂層６”については、フッ化ビニリデン等のフッ素系樹脂を主成分とした樹脂で形成して優れた耐汚染性等の表面機能を付与し、基材側の透明樹脂層６’については、熱可塑性（メタ）アクリル樹脂等で形成し、接着層５との間の密着性等を向上させることができる。また、他の具体例として、保護層側の透明樹脂層６”については、耐候剤を添加したポリプロピレン系樹脂で形成して優れた耐候性を付与し、基材側の透明樹脂層６’については、エラストマーを含有したポリプロピレン系樹脂で形成して耐候性と密着性を向上させることができる。
【００７４】
２層以上の透明樹脂層１６は、複数の樹脂組成物を溶融共押出しして形成されたり、ドライラミネーションや熱ラミネーション等の各種のラミネート法で形成される。このとき、図３に示すように、プライマー層またはアンカー層として作用する接着層１２を介して２以上の層からなる透明樹脂層１６を形成することもできる。なお、この場合における接着層１２は、透明樹脂層６’、６”と共に溶融共押出しして形成されたり、水性ウレタン樹脂を含有する水系塗工液で塗布されて形成される。その場合には、ＶＯＣの発生をより一層抑制することができる。
【００７５】
透明樹脂層６の厚さは、２０〜３００μｍ程度であり、塗工液で形成される場合には、１５〜４００ｇ／ｍ^２　程度の塗布量で塗工する。
【００７６】
（凹凸模様）
凹凸模様７は、エンボス模様ともいわれ、図１に示すように、必要に応じて上述の透明樹脂層６の表面に形成される。また、図２および図３に示すように２層以上の透明樹脂層１６を形成した場合には、凹凸模様７を最表面の透明樹脂層に形成したり、最表面以外の透明樹脂層に形成したりすることができる。
【００７７】
凹凸模様７は、特に限定されず、化粧シート１の用途に応じた模様であればよい。例えば、木目導管溝、木目年輪凹凸、浮造年輪凹凸、木肌凹凸、砂目、梨地、ヘアライン、万線状溝、花崗岩の劈開面等の石材表面凹凸、布目の表面テクスチュア、皮絞、文字、幾何学模様等の模様が挙げられる。
【００７８】
凹凸模様７を形成する手段としては、例えば、加熱加圧によるエンボス加工法やＴダイ溶融押出し法が挙げられる。加熱加圧によるエンボス加工法は、透明樹脂層６の表面を加熱軟化させ、その表面をエンボス版で加圧してエンボス版の凹凸模様７を賦形し、冷却して固定化する方法であり、公知の枚葉式または輪転式のエンボス機が用いられる。エンボス加工法で凹凸模様を形成する場合には、ラミネート加工により積層する前の透明樹脂層用シートに予めエンボス加工したり、透明樹脂層用シートを積層すると同時に（いわゆるダブリングエンボス法）エンボス加工をする。また、Ｔダイ溶融押出し法で透明樹脂層６を積層する場合には、賦形ローラを兼用させた冷却ローラを使用し、透明樹脂層６の成膜・積層と同時に凹凸模様７を形成する。また、ヘアライン加工、サンドブラスト加工等によってもエンボス模様を形成することができる。
【００７９】
（部分着色層）
部分着色層８は、凹凸模様７の凹陥部１７にワイピング法により形成される。ワイピング法は、ドクターブレードコート法またはナイフコート法で凹陥部１７を含む表面全面に部分着色層用の塗工液を塗布した後、凹陥部１７以外の表面から部分着色層用の塗工液を除去することにより、凹陥部１７のみに部分着色層８を形成する方法である。部分着色層用の塗工液としては、有機顔料、無機顔料、光輝性顔料等の着色顔料と、熱可塑性樹脂、熱硬化性樹脂、電離性放射線硬化型樹脂等のバインダー樹脂とからなる塗工液や、エマルジョン型の水系塗工液等を使用できる。
【００８０】
また、上述のベタ着色層３および／または絵柄着色層４を形成する水系塗工液を好ましく用いることもでき、そうした場合には、環境安全性の点でより好ましい。
【００８１】
（保護層）
保護層９は、トップコート層またはオーバープリント層（ＯＰ層）ともいわれ、凹凸模様７を形成する凹陥部１７やその凹陥部１７に形成された部分着色層８の表面を被って、化粧シート１を保護することを目的として設けられるものである。具体的には、耐擦傷性や耐汚染性、耐候性等の表面物性を向上させることにより、化粧シート１を保護する。
【００８２】
保護層９は、上述の接着層の段落にて詳述した本発明の水系塗工液を適用して形成することが好ましく、特に耐候性および耐光性に優れた保護層を有する化粧シート１を提供することができると共に、ＶＯＣの発生を抑制して環境安全性を向上した化粧シート１を提供することができる。
【００８３】
保護層用の水系塗工液は、紫外線吸収剤および／または光安定剤、主剤、架橋剤および溶媒を基本構成とするものであり、紫外線吸収剤、光安定剤、溶媒は、接着層のところで説明したものと同じものを用いることができる。なお、主剤としては、例えば、ポリウレタン樹脂、ポリエステル樹脂、アクリル樹脂、ビニル樹脂、エポキシ樹脂等及びこれらの共重合物、及び混合物等が挙げられる。こうした主剤は、架橋剤成分と反応する官能基を有することが必要とされる。架橋剤としては、例えば、イソシアネート化合物、エポキシ化合物、オキサゾリン化合物、カルボジイミド化合物、シラノール基含有化合物等が挙げられる。このうち、イソシアネート化合物を用いることが好ましい。なお、この水系塗工液には、電離性放射線硬化型樹脂を用いてもよい。主剤：架橋剤の配合割合は、１００：０．５〜１００：１００、好ましくは１００：５〜１００：２０である。
【００８４】
紫外線吸収剤および／または光安定剤は、主剤、架橋剤および溶媒（水系）からなる塗工液を１００としたときに、０．００１〜１０の割合で配合される。紫外線吸収剤と光安定剤とを両方配合させる場合には、紫外線吸収剤：光安定剤の配合割合は特に限定されない。主剤：架橋剤の配合割合は、１００：０．５〜１００：１００、好ましくは１００：５〜１００：２０である。また、溶媒の配合割合は、主剤と架橋剤との和を１００とした場合に、５０〜４００の割合で配合させる。
【００８５】
なお、着色層１１および／または接着層５が、本発明の水系塗工液により形成された場合においては、保護層９を、紫外線吸収剤や光安定剤が含有されていない水系塗工液や、溶剤系塗工液、無溶剤系塗工液により形成することもできるが、本発明の水系塗工液を用いて形成することが最も好ましい。特に、着色層１１、接着層５、保護層９の全てを本発明の水系塗工液により形成することが最も好ましい。
【００８６】
溶剤系塗工液としては、アクリル樹脂、ポリウレタン樹脂、エポキシ樹脂等、これらの共重合物、またはこれらの混合物を主剤とし、イソシアネート化合物、エポキシ化合物等の架橋剤成分を用いたもの、または、電離性放射線硬化型樹脂を塗工した後、電離性放射線を照射して硬化させるもの等を用いることができる。無溶剤系塗工液としては、電離性放射線硬化型樹脂を用いた塗工液が好ましい。こうした溶剤系塗工液や無溶剤系塗工液には、保護層９により良好な耐候性や耐光性を付与するために、紫外線吸収剤および／または光安定剤を添加することが好ましい。
【００８７】
なお、本発明においては、着色層１１、接着層５、保護層９のいずれの層も、非親水性の紫外線吸収剤、および／または、非親水性の光安定剤を含有する水系塗工液では形成されない。そのため、この保護層９においてもそうした水系塗工液では形成されない。その結果、形成された化粧シートの耐候性、接着特性が低下することがない。
【００８８】
保護層９は、シリカ等の公知の艶消し剤を塗工液に添加することにより艶調整したものとしたり、塗装感等の意匠性を付与させたものとすることができる。その他の添加剤としては、着色剤、分散剤、消泡剤、レベリング剤、安定剤、充填剤、潤滑剤、滑剤、帯電防止剤、難燃剤等が用いられる。
【００８９】
保護層９は、上述した各種の塗工液を、グラビアコート法、リバースロールコート法、ナイフコート法、キスコート法、その他塗工法等の公知の塗工法で塗工形成して形成される。また、グラビア印刷、シルクスクリーン印刷等の公知の印刷法で形成される。形成された保護層９の厚みは３〜４０μｍ程度が好ましく、１０〜３０μｍがより好ましい。
【００９０】
（プライマー層）
プライマー層１０は、本発明の化粧シート１を各種の被着体１５に接着させ易くすることを目的として、基材２の裏面側に形成される。プライマー層１０の形成には、（メタ）アクリル系樹脂、塩化ビニル−酢酸ビニル共重合体、ポリエステル、ポリウレタン、塩素化ポリプロピレン、塩素化ポリエチレン等が使用されるが、上述した着色層１１や接着層５を形成するのに好ましく採用される水系塗工液を用いることが環境安全性の観点から好ましい。
【００９１】
（化粧シート）
以上説明したように、本発明に係る水系塗工液を用いて各々の層（着色層、接着層、保護層）を形成して得られた化粧シート１は、従来の水系塗工液で各々の層を形成して得られた化粧シートに比べて、耐候性を向上させることができる。
【００９２】
上述の構成を有する本発明の化粧シート１は、他の被着体１５（裏打材）に積層して用いられる。
【００９３】
被着体１５としては、図４に示すような立体形状物品４１や、図５に示すような平板状、曲面状等の板材５１、シート（或いはフィルム）等の各種形状の物品が対象となる。こうした被着体１５としては、木材単板、木材合板、パーティクルボード、中密度繊維板（ＭＤＦ）等の木材板、木質繊維板等の木質板、鉄、アルミニウム等の金属、（メタ）アクリル、ポリエステル、ポリスチレン、ポリオレフィン、ＡＢＳ樹脂、フェノール樹脂、ポリ塩化ビニル樹脂、セルロース系樹脂、ゴム等の樹脂、硝子、陶磁器等のセラミックス、石膏等の非セメント窯業系材料、上質紙、和紙等の紙、炭素、石綿、チタン酸カリウム、硝子、合成樹脂等の繊維からなる不織布または織布、等々が挙げられる。
【００９４】
化粧シート１と被着体１５との関係において、化粧シート１の基材２またはプライマー層１０の種類により、被着体１５にそのまま熱融着等で接着できる場合には、化粧シート１と被着体１５とを接着剤を用いずに積層させることができるが、化粧シート１の基材２またはプライマー層１０の種類により、被着体１５にそのまま熱融着等で接着できない場合には、適当な接着剤を用いて積層させる。なお、接着剤としては、酢ビ系、尿素系等の接着剤が挙げられる。
【００９５】
また、一般的な積層方法としては、例えば、（ａ）接着剤を介して被着体１５に加圧ローラーで加圧して積層する方法、（ｂ）特公昭５０−１９１３２号公報、特公昭４３−２７４８８号公報等に記載のように、化粧シート１を射出成形の雌雄両金型間に挿入して、両金型を閉じ、雄型のゲートから溶融樹脂を射出充填した後、冷却して樹脂成型品の成形と同時にその表面に化粧シート１を接着積層する射出成形同時ラミネート方法、（ｃ）特公昭５６−４５７６８号公報、特公昭６０−５８０１４号公報等に記載のように、接着剤を介して成形品の表面に化粧シート１を対向させ、成形品側からの真空吸引による圧力差により化粧シート１を成形品表面に積層する真空プレス積層方法、（ｄ）特公昭６１−５８９５号公報、特公平３−２６６６号公報等に記載のように、円柱、多角柱等の柱状被着体の長軸方向に、接着剤を介して化粧シート１を供給しつつ、複数の向きの異なるローラーにより、柱状被着体を構成する複数の側面に順次化粧シート１を加圧接着して積層してゆくラッピング加工方法等が挙げられる。
【００９６】
本発明の化粧シート１を積層した各種の被着体１５は、所定の成形加工等を施して、各種装飾用素材等として用いられる。例えば、壁、天井、床等建築物の内装、窓枠、扉、手摺等の建具の表面化粧、家具または弱電・ＯＡ機器のキャビネットの表面化粧、自動車、電車等の車輌内装、航空機内装、窓硝子の化粧用等の用途が挙げられる。
【００９７】
【実施例】
以下に、実施例と比較例を挙げて、本発明を更に詳しく説明する。なお、以下において、部とは重量部のことである。
【００９８】
（実施例１）
基材２として三菱化学ＭＫＶ株式会社製のポリプロピレン系エラストマー着色シートＰＢ０１３（厚さ６０μｍ）を用い、その上にコロナ放電処理を施した後、線数５４線／インチ、版深４０μｍのグラビア版を用いて下記配合のベタ着色層用水系塗工液Ａ、絵柄着色層用水系塗工液Ｂを順次グラビア印刷法で塗布・乾燥し、約３μｍのベタ着色層３および約１μｍの絵柄着色層４を順次形成した。さらにその上に、線数５４線／インチ、版深４０μｍのグラビア版を用いて下記配合の接着層用水系塗工液ａをグラビア印刷法で、約３ｇ／ｍ^２　となるように塗布・乾燥し、乾燥後厚さ３μｍの接着層５を形成した。
さらにその接着層５上に、三菱化学ＭＫＶ株式会社製の透明ポリプロピレンフィルム「ＰＥ００２Ｃ」（厚さ８０μｍ）をドライラミネート方式で積層して透明樹脂層６を形成した。次に、その積層シートの表面に、エンボス加工により凹凸模様７を形成し、さらにその上に、線数５４線／インチ、版深４０μｍのグラビア版を用いて、下記配合の保護層用水系塗工液Ｃをグラビア印刷法にて塗布・乾燥し、約３μｍの保護層９を形成した。その後、温度２５℃で７日間養生することにより、実施例１の化粧シートを得た。
【００９９】
ベタ着色層用水系塗工液Ａ；
水性ウレタン系白色インキ（紫外線吸収剤等未添加；ザ・インクテック製、オーデＷＫＥ白ベタ）：１００部、水分散性イソシアネート架橋剤（日華化学株式会社製、Ｘ９００３）：５部、水分散性紫外線吸収剤（旭電化工業株式会社製、ＬＸ−３０１）：１部、水分散性光安定剤（旭電化工業株式会社製、ＬＸ−３３２）：１部、水：２０部、イソプロピルアルコール：２０部
絵柄着色層用水系塗工液Ｂ；
水性ウレタン系黄色インキ（紫外線吸収剤等未添加；ザ・インクテック製、オーデＷＫＥ黄）：１００部、水分散性紫外線吸収剤（旭電化工業株式会社製、ＬＸ−３０１）：１部、水分散性光安定剤（旭電化工業株式会社製、ＬＸ−３３２）：１部、水：２０部、イソプロピルアルコール：２０部
接着層用水系塗工液ａ；
水性ウレタン樹脂（紫外線吸収剤等未添加；日華化学株式会社製、ＨＯ１４）：１００部、水分散性イソシアネート架橋剤（日華化学株式会社製、Ｘ９００３）：５部、水分散性紫外線吸収剤（旭電化工業株式会社製、ＬＸ−３０１）：１部、水分散性光安定剤（旭電化工業株式会社製、ＬＸ−３３２）：１部、水：２０部、イソプロピルアルコール：２０部
保護層用水系塗工液ｂ；
水性ウレタン樹脂（紫外線吸収剤等未添加；株式会社昭和インク工業所製、１３５）：１００部、水分散性イソシアネート架橋剤（日華化学株式会社製、Ｘ９００３）：５部、水分散性紫外線吸収剤（旭電化工業株式会社製、ＬＸ−３０１）：１部、水分散性光安定剤（旭電化工業株式会社製、ＬＸ−３３２）：１部、水：２０部、イソプロピルアルコール：２０部
【０１００】
（実施例２）
実施例１の接着層用溶剤系塗工液ａに代えて、下記配合の接着層用溶剤系塗工液ｃを用いた。その他は実施例１と同様にして実施例２の化粧シートを得た。
接着層用溶剤系塗工液ｃ；
ポリエステル樹脂系接着剤（紫外線吸収剤、光安定剤含有；大日精化工業株式会社製、Ｅ２９５Ｌ−ＮＴ）１００部、イソシアネート架橋剤（大日精化工業株式会社製、Ｃ５５）：１０部、酢酸エチル：８０部
【０１０１】
（実施例３）
実施例１の接着層用水系塗工液ａに代えて、下記配合の接着層用水系塗工液ｄを用いた。その他は実施例１と同様にして実施例３の化粧シートを得た。
接着層用水系塗工液ｄ；
水性ウレタン樹脂（紫外線吸収剤等未添加；日華化学株式会社製、ＨＯ１４）：１００部、水分散性イソシアネート架橋剤（日華化学株式会社製、Ｘ９００３）：５部、紫外線吸収剤を分子内に含有する水性樹脂（大塚化学株式会社製、ＰＵＶＡ−３０Ｗ）：１部、水分散性光安定剤（旭電化工業株式会社製、ＬＸ３３２）：１部、水：２０部、イソプロピルアルコール：２０部
【０１０２】
（実施例４）
実施例１の保護層用水系塗工液ｂに代えて、下記配合の保護層用水系塗工液ｅを用いた。その他は実施例１と同様にして実施例４の化粧シートを得た。
保護層用水系塗工液ｅ；
水性ウレタン樹脂（紫外線吸収剤等未添加；株式会社昭和インク工業所製、１３５）：１００部、水分散性イソシアネート架橋剤（日華化学株式会社製、Ｘ９００３）：５部、紫外線吸収剤を分子内に含有する水性樹脂（大塚化学株式会社製、ＰＵＶＡ−３０Ｗ）：１部、水分散性光安定剤（旭電化工業株式会社製、ＬＸ３３２）：１部、水：２０部、イソプロピルアルコール：２０部
【０１０３】
（実施例５）
実施例１の透明樹脂層６の形成方法に代えて、溶融押出方式による形成方法を用いた。具体的には、接着層５上に、ランダム重合ポリプロピレンに、フェノール系酸化防止剤０．２重量％、ヒンダードアミン系光安定剤０．３重量％、ブロッキング防止剤０．２重量％をそれぞれ添加した樹脂を、Ｔダイにより溶融状態で押出し、１８０℃の熱で厚さ８０μｍの透明樹脂層６を積層した。その他は実施例１と同様にして実施例５の化粧シートを得た。
【０１０４】
（比較例１）
実施例１のベタ着色層用水系塗工液Ａ、絵柄着色層用水系塗工液Ｂに代えて、下記配合のベタ着色層用水系塗工液Ｃ、絵柄着色層用水系塗工液Ｄを用いた。その他は実施例１と同様にして比較例１の化粧シートを得た。
ベタ着色層用水系塗工液Ｃ；
水性ウレタン系白色インキ（紫外線吸収剤等未添加；ザ・インクテック製、オーデＷＫＥ白ベタ）：１００部、水分散性イソシアネート架橋剤（日華化学株式会社製、Ｘ９００３）：５部、紫外線吸収剤（旭電化工業株式会社製、ＬＡ−３６）：０．３部、光安定剤（旭電化工業株式会社製、ＬＡ−６２）：０．３部、水：２０部、イソプロピルアルコール：２０部
絵柄着色層用水系塗工液Ｄ；
水性ウレタン系黄色インキ（紫外線吸収剤等未添加；ザ・インクテック製、オーデＷＫＥ黄）：１００部、紫外線吸収剤（旭電化工業株式会社製、ＬＡ−３６）：０．３部、光安定剤（旭電化工業株式会社製、ＬＡ−６２）：０．３部、水：２０部、イソプロピルアルコール：２０部
【０１０５】
（比較例２）
実施例１の接着層用水系塗工液ａに代えて、接着層用水系塗工液ｆを用いた。その他は実施例１と同様にして比較例２の化粧シートを得た。
接着層用水系塗工液ｆ；
水性ウレタン樹脂（紫外線吸収剤等未添加；日華化学株式会社製、ＨＯ１４）：１００部、水分散性イソシアネート架橋剤（日華化学株式会社製、Ｘ９００３）：５部、紫外線吸収剤（旭電化工業株式会社製、ＬＡ−３６）：０．３部、光安定剤（旭電化工業株式会社製、ＬＡ−６２）：０．３部、水：２０部、イソプロピルアルコール：２０部
【０１０６】
（比較例３）
実施例１の保護層用水系塗工液ｂに代えて、下記配合の保護層用水系塗工液ｇを用いた。その他は実施例１と同様にして比較例３の化粧シートを得た。
保護層用水系塗工液ｇ；
水性ウレタン樹脂（紫外線吸収剤等未添加；株式会社昭和インク工業所製、１３５）：１００部、水分散性イソシアネート架橋剤（日華化学株式会社製、Ｘ９００３）：５部、紫外線吸収剤（旭電化工業株式会社製、ＬＡ−３６）：０．３部、光安定剤（旭電化工業株式会社製、ＬＡ−６２）：０．３部、水：２０部、イソプロピルアルコール：２０部
【０１０７】
（各特性の評価方法）
実施例１〜４および比較例１〜３で得られた各化粧シートの層間密着性、耐候性試験後の層間密着性、および耐スクラッチ性の評価を下記の方法により行った。得られた結果を表１に示した。
【０１０８】
（層間密着性の評価方法）
幅１インチにカットした化粧シート１を試験片とし、この試験片の基材２と透明樹脂層６とをＩＮＳＴＲＯＮ５５００引張試験機を用い、２５℃の雰囲気中において引張速度１００ｍｍ／分、基材２と透明樹脂層６との間の開き角１８０°の条件にて引張り、剥離強度で評価した。剥離強度が１９．６Ｎ以上のものを合格として○で表し、１９．６Ｎ未満のものを不合格として×で表した。
【０１０９】
（耐候性試験後の層間密着性の評価方法）
耐候性試験後の層間密着性は、耐候性試験後に上述した層間密着性を評価し、剥離強度が１０Ｎ以上のものを合格として○で表し、１０Ｎ未満のものを不合格とした。不合格の中でも１０Ｎ未満５Ｎ以上のものを△で表し、５Ｎ未満のものを×で表した。なお、耐候性試験は、化粧シート１の試験片を、スガ試験機製サンシャイン・ウエザ・オ・メーター「ＷＥＬ−３００」にセットし、ブラックパネル温度６３℃、１２０分間中１８分間の雨ありサイクルの条件下で、１０００時間紫外線を照射して行った。１２０分間中１８分間の雨ありサイクルとは、１２０分間の内１８分間に、試験片に雨を擬した水を噴射することをいう。
【０１１０】
（耐スクラッチ性の評価方法）
耐スクラッチ性は、得られた化粧シートをウレタン系接着剤（日本ＮＳＣ製、ＲＬ９６）を用いて、化粧板用の木質系基材に貼り合わせ、その化粧板について、コインスクラッチ試験を行うことにより評価した。コインスクラッチ試験は、化粧板の化粧シート塗膜面（最表面の保護層９）に対し、１０円硬貨の平面が４５度の角度となるよう硬貨のエッジをあて、５００ｇの荷重をかけながら押しつけるように１０円硬貨の平面と垂直な方向に引っ張り、化粧板表面の外観を観察評価することにより行った。コインスクラッチ性評価基準は、Ａ；傷つきなしかつ絵柄界面剥離なし、Ｂ；傷つき軽微かつ絵柄界面剥離なし、Ｃ；傷つきありかつ絵柄界面剥離なし、Ｄ；絵柄界面剥離あり、とし、Ａ，Ｂを合格として○で表し、Ｃ，Ｄを不合格として×で表した。
【０１１１】
【表１】

【０１１２】
【発明の効果】
以上説明したように、本発明によれば、水溶性または水分散性の紫外線吸収剤、および／または、水溶性または水分散性の光安定剤を含有する水系塗工液を、着色層、接着層、保護層のうち、少なくとも１以上の層に使用するので、耐候性に優れた化粧シートを提供することができる。本発明の化粧シートによれば、接着特性を有する着色層および／または接着層を、基材と透明樹脂層との間に形成したものとすることができる。さらに、その水系塗工液は、水系の塗工液であるので、作業環境中のＶＯＣの揮発量および化粧シート中のＶＯＣ残存量を極力減少させることができる。その結果、環境安全性をより向上させることができる。さらに、本発明によれば、着色層、接着層、保護層のいずれも層も、従来の溶剤系塗工液に含有されていたような非親水性の紫外線吸収剤および／または非親水性の光安定剤を含有した水系塗工液では形成されないので、化粧シートの耐候性や接着特性が悪くなるという問題が生じない。
【０１１３】
また、本発明の水系塗工液によれば、耐候性および接着特性を有する着色層、接着層および保護層を形成することができる。
【図面の簡単な説明】
【図１】本発明の化粧シートの層構成の一例を示す断面図である。
【図２】本発明の化粧シートの層構成の他の一例を示す断面図である。
【図３】本発明の化粧シートの層構成の更に他の一例を示す断面図である。
【図４】本発明の化粧シートの実施形態の一例を示す断面図である。
【図５】本発明の化粧シートの実施形態の他の一例を示す断面図である。
【符号の説明】
１　化粧シート
２　基材
３　ベタ着色層
４　絵柄着色層
５　接着層
６、６’、６”　透明樹脂層
７　凹凸模様
８　部分着色層
９　保護層
１０　プライマー層
１１　着色層
１２　接着層
１５　被着体
１６　多層からなる透明樹脂層
１７　凹陥部
４１　立体形状物品
５１　板材[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a decorative sheet and a water-based coating liquid used for interior decoration of buildings, surface decoration of fittings, interior decoration of vehicles, and the like, and more particularly to a decorative sheet having improved adhesive properties and weather resistance, and a decorative sheet and the like. The present invention relates to a water-based coating liquid which can be suitably used for a liquid.
[0002]
[Prior art]
As a decorative sheet used for interiors of buildings, surface decoration of fittings, interiors of vehicles, etc., a base material, a coloring layer composed of a solid coloring layer and / or a pattern coloring layer, an adhesive layer, and a transparent resin layer are sequentially laminated. Things are generally known.
[0003]
In such a conventional decorative sheet, as described in Patent Document 1, a coloring layer (also referred to as an ink layer) and an adhesive layer are formed of an aromatic solvent such as toluene or xylene, or an aliphatic solvent such as methyl ethyl ketone or ethyl acetate. And a solvent-based coating solution containing Conventionally, an ultraviolet absorber and a light stabilizer (radical scavenger) have been added to the solvent-based coating liquid for forming the colored layer, the adhesive layer and the like of such a decorative sheet for the purpose of improving weather resistance. .
[0004]
Incidentally, such aromatic solvents such as toluene and xylene, and aliphatic solvents such as methyl ethyl ketone and ethyl acetate are organic volatile substances (hereinafter referred to as VOCs), and their use has recently been demanded to be reduced. In particular, aromatic solvents such as toluene and xylene are listed as chemical substances designated by the PRTR Law and guideline values for chemical substances in indoor air. "Aromatic solvents are not used. Other solvents are also used. Let's reduce it. "
[0005]
In particular, in the production of decorative sheets, there is a problem in the working environment due to the volatilization of VOCs contained in the solvent-based coating liquid, and the environmental safety due to the supply of VOCs remaining in the decorative sheets to ordinary living spaces. There are problems. To address these problems, various means have been proposed to reduce the use of VOCs. For example, Patent Literature 2 discloses a decorative sheet in which a coloring layer and an adhesive layer are formed with an aqueous coating liquid in which the VOC content is reduced as much as possible. Such a decorative sheet can further reduce the volatilization amount and the residual amount of VOC, and thus is effective in solving the above-mentioned environmental problems.
[Patent Document 1]
JP-A-11-198309
[Patent Document 2]
JP 2001-62970 A
[0006]
[Problems to be solved by the invention]
Conventionally, UV absorbers and light stabilizers (radical scavengers) that have been added to solvent-based coating liquids are blended into aqueous coating liquids, and the resulting colored coatings and adhesive layers formed with the aqueous coating liquids are However, as compared with the case where a conventional solvent-based coating liquid was used, the weather resistance could not be improved.
[0007]
The present inventors have attempted to form a colored layer and an adhesive layer using an aqueous coating solution to which another type of ultraviolet absorber or the like has been added. However, the weather resistance of the decorative sheet cannot be improved, and moreover, there has been a problem that the adhesiveness between the substrate and the transparent resin layer or between the substrate / colored layer and the transparent resin layer is deteriorated. . It was considered that such a problem was largely caused by the uneven distribution of the added ultraviolet absorber and the like in the aqueous coating solution.
[0008]
Under such circumstances, there has been a demand for improving the weather resistance of the colored layer and the adhesive layer formed with the aqueous coating liquid and improving the adhesive properties.
[0009]
The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a decorative sheet having improved weather resistance and adhesive properties, and a water-based coating liquid which can be suitably used for such decorative sheets. Things.
[0010]
[Means for Solving the Problems]
The decorative sheet of the present invention for solving the above problems is a decorative sheet in which a base material, a colored layer, an adhesive layer, a transparent resin layer, and a protective layer are laminated in this order, and the colored layer, the adhesive layer, and the protective layer At least one of the layers is formed of an aqueous coating solution containing a water-soluble or water-dispersible ultraviolet absorber and / or a water-soluble or water-dispersible light stabilizer, and the colored layer Neither the adhesive layer nor the protective layer is formed by a water-based coating solution containing a non-hydrophilic ultraviolet absorber and / or a non-hydrophilic light stabilizer.
[0011]
According to the present invention, the water-soluble or water-dispersible ultraviolet absorber and / or the water-soluble or water-dispersible light stabilizer are uniformly dissolved and dispersed in the aqueous coating solution without being unevenly distributed. Therefore, the colored layer, adhesive layer or protective layer formed with such an aqueous coating liquid has excellent weather resistance and excellent adhesive properties. Furthermore, this aqueous coating liquid can reduce the volatile amount of VOC in the working environment and the residual amount of VOC in the decorative sheet as much as possible, and as a result, the environmental safety can be further improved. In addition, any of the colored layer, the adhesive layer, and the protective layer is a water-based coating containing a non-hydrophilic ultraviolet absorber and a non-hydrophilic light stabilizer, such as those contained in conventional solvent-based coating solutions. Since the decorative sheet is not formed by the working liquid, there is no problem that the weather resistance and the adhesive property of the decorative sheet are deteriorated.
[0012]
In addition, as a specific configuration of the decorative sheet of the present invention described above, an uneven pattern is formed on the surface side (between the protective layer) of the transparent resin layer and a partially colored layer is formed in a concave portion of the uneven pattern. Or a primer layer can be formed on the back surface of the substrate.
[0013]
The water-based coating liquid of the present invention that solves the above-mentioned problems is characterized in that it contains a water-soluble or water-dispersible ultraviolet absorber and / or a water-soluble or water-dispersible light stabilizer.
[0014]
According to the present invention, a layer having excellent weather resistance and having adhesive properties can be formed.
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the decorative sheet of the present invention will be described with reference to the drawings.
[0016]
FIG. 1 is a cross-sectional view illustrating an example of the layer configuration of the decorative sheet 1 of the present invention. In the decorative sheet 1 of the present invention shown in FIG. 1, a base material 2, a solid colored layer 3, a picture colored layer 4, an adhesive layer 5, a transparent resin layer 6, an uneven pattern 7, a partially colored layer 8, and a protective layer 9 are sequentially laminated. It is the form which was done. A primer layer 10 is formed on the back surface of the substrate 2.
[0017]
(Base material)
The base material 2 is an essential component of the decorative sheet 1, and various olefin resins shown below can be preferably applied. For example, (a) a mixture having high-density polyethylene or polypropylene as a hard segment and an elastomer or an inorganic filler as a soft segment, (b) JP-A-9-111055, JP-A-5-77371, Ethylene-propylene-butene copolymer described in JP-A-7-316358 and the like; (c) Isotactic polypropylene as a hard segment and attack as a soft segment described in JP-B-6-23278 A mixture with tic polypropylene can be used.
[0018]
The high-density polyethylene as the hard segment (a) is preferably a polyethylene having a specific gravity of 0.94 to 0.96, a high degree of crystallinity obtained by a low-pressure method, and a small number of branched structures in the molecule. High-density polyethylene, which is a polymer, is used. As the polypropylene as the hard segment, preferably, isotactic polypropylene is used.
[0019]
As the elastomer as the soft segment of (a), a diene rubber, a hydrogenated diene rubber, an olefin elastomer or the like is used. The hydrogenated diene-based rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene-based rubber molecule, and suppresses the crystallization of the polyolefin-based resin to improve its flexibility. . Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene butadiene rubber. The olefin elastomer is an elastic copolymer obtained by adding at least one kind of polyene copolymerizable with two or more kinds of olefins. As the olefin, ethylene, propylene, α-olefin or the like is used. , 1,4 hexadiene, cyclic dienes, norbornene and the like are used. Preferred olefin elastomers include, for example, elastic copolymers containing an olefin as a main component, such as ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene rubber, and ethylene-butadiene copolymer rubber. In addition, these elastomers may be excessively cross-linked by using a cross-linking agent such as an organic peroxide or sulfur, if necessary.
[0020]
The addition amount of these elastomers is 10 to 60% by weight, preferably about 30% by weight. If the amount of the elastomer is less than 10% by weight, the change in elongation at a constant load becomes too steep, and the elongation at break, impact resistance, and easy adhesion decrease. When the amount of the elastomer is higher than 60% by weight, transparency, weather resistance and creep resistance are reduced.
[0021]
As the inorganic filler (a), powder having an average particle size of about 0.1 to 10 μm such as calcium carbonate, barium sulfate, clay, and talc is used. The amount of addition is 1 to 60% by weight, preferably 5 to 30% by weight. If the amount of the inorganic filler is less than 1% by weight, the creep deformation resistance and the easy adhesion are reduced. If the amount of the inorganic filler exceeds 60% by weight, elongation at break and impact resistance are reduced.
[0022]
As the olefin resin (b), a thermoplastic elastomer composed of an ethylene / propylene / butene copolymer resin is used. Here, as butene, any one of the three structural isomers of 1-butene, 2-butene and isobutylene can be used. The copolymer is a random copolymer and partially includes an amorphous portion.
[0023]
Preferred specific examples of the ethylene-propylene-butene copolymer resin include the following (a) to (c).
[0024]
(A) A random copolymer based on a terpolymer of ethylene, propylene and butene described in JP-A-9-111055. In this random copolymer, the weight ratio of the propylene component is preferably 90% by weight or more, and the melt flow rate is preferably 1 to 50 g / 10 minutes under the conditions of 230 ° C and 2.16 kg. preferable. Such a random copolymer contains 0.01 to 50 parts by weight of a transparent nucleating agent containing a phosphoric acid aryl ester compound as a main component and a fatty acid amide having 12 to 22 carbon atoms based on 100 parts by weight of the random copolymer. 0.003 to 0.3 parts by weight are melt-kneaded.
[0025]
(B) Terpolymers of ethylene, propylene and butene described in JP-A-5-77371. This copolymer is obtained by adding 80 to 0% by weight of crystalline polypropylene to 20 to 100% by weight of an amorphous polymer having a weight ratio of a propylene component of 50% by weight or more.
[0026]
(C) Terpolymers of ethylene, propylene and 1-butene described in JP-A-7-316358. This copolymer was prepared by mixing 80 to 0% by weight of a crystalline polyolefin such as isotactic polypropylene with 20 to 100% by weight of a low crystalline polymer having a propylene and / or 1-butene content of 50% by weight or more. An oil gelling agent such as an N-acylamino acid amine salt or an N-acylamino acid ester is added to the composition in an amount of 0.5% by weight.
[0027]
The ethylene-propylene-butene copolymer resins (a) to (c) may be used alone or, if necessary, may be mixed with other polyolefin resins.
[0028]
As the olefin resin (C), as described in Japanese Patent Publication No. 23278/1994, (A) the soft segment has a number average molecular weight Mn of 25,000 or more, and a weight average molecular weight Mw and a number average molecular weight Mn. 10 to 90% by weight of atactic polypropylene soluble in boiling heptane having a ratio Mw / Mn ≦ 7, and (B) a hard segment having a melt index of 0.1 to 4 g / 10 min. Soft polypropylene consisting of a mixture with 90 to 10% by weight of a tic polypropylene.
[0029]
Among the olefinic thermoplastic elastomers of the above (c), those comprising a mixture of isotactic polypropylene and atactic polypropylene and having a weight ratio of atactic polypropylene of 5 to 50% by weight are preferably used. Those having a weight ratio of 20 to 40% by weight are particularly preferably used. If the weight ratio of the atactic polypropylene is less than 5% by weight, unevenness of the sheet-like base material due to necking may occur when embossing or when forming into a three-dimensional or uneven article. As a result, wrinkles, distortion of a picture, and the like occur. On the other hand, when the weight ratio of the atactic polypropylene exceeds 50% by weight, the sheet-like substrate itself is easily deformed, and when the substrate is passed through a printing machine, the substrate is deformed, and the pattern of the colored layer 11 is distorted. In the case of multicolor printing, defects such as misregistration are likely to occur, and the sheet is easily broken during molding.
[0030]
A coloring agent, a heat stabilizer, a flame retardant, an ultraviolet absorber, a radical scavenger, and the like are added to the olefin resin forming the base material 2 as needed.
[0031]
Examples of coloring agents include inorganic pigments such as titanium white, zinc white, red iron, vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue and the like. Organic pigments or dyes, metal pigments made of foil powder such as aluminum and brass, pearlescent pigments made of foil powder such as titanium dioxide-coated mica, and basic zinc carbonate. If necessary, an inorganic filler may be added at a ratio of 5 to 60% by weight. Examples of the inorganic filler include powders such as calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), and alumina (aluminum oxide). The coloring agent is added to give the base material 2 a necessary color as the decorative sheet 1, and may be either transparent coloring or opaque (concealing) coloring, but is generally for covering the adherend 15. Opaque coloring is preferred.
[0032]
As the heat stabilizer, a known heat stabilizer such as a phenol type, a sulfite type, a phenylalkane type, a physphite type, and an amine type can be used, and the prevention of deterioration such as thermal discoloration during thermal processing can be improved. The flame retardant is added when imparting flame retardancy, and powder such as aluminum hydroxide and magnesium hydroxide is used. The ultraviolet absorber is for imparting good weather resistance (light resistance) to the resin, and is an organic substance such as benzotriazole, benzophenone, or salicylate, or fine-particle zinc oxide having a diameter of 0.2 μm or less; Inorganic substances such as cerium oxide and titanium oxide are used. In addition, a reactive ultraviolet absorber having an acryloyl group or a methacryloyl group introduced into a benzotriazole skeleton is also used. In addition, the addition amount of these ultraviolet absorbers is usually about 0.5 to 10% by weight. The radical scavenger is for further preventing deterioration due to ultraviolet rays and improving weather resistance, and includes bis- (2,2,6,6-tetramethyl-4-biperidinyl) sebacate and bis- (N-methyl). -2,2,6,6-tetramethyl-4-biperidinyl) sebacate, and other hindered radical scavengers such as the compounds disclosed in Japanese Patent Publication No. 4-82625 and biperidinyl radical scavengers are used. Is done.
[0033]
The substrate 2 can be obtained by arbitrarily selecting and blending the above-described materials and forming a film by a common method such as calendering. The thickness of the substrate 2 is 50 to 200 μm, preferably about 100 μm.
[0034]
It is preferable that the surface of the base material 2 on the surface side (the transparent resin layer 6 side) of the decorative sheet 1 is subjected to an easy-adhesion treatment such as application of an easy-adhesion layer, corona discharge treatment, plasma treatment, and ozone treatment. Examples of the resin constituting the easy-adhesion layer (also referred to as a primer layer or an anchor layer) include (meth) acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, urethane resin, chlorinated polypropylene, and polyethylene chloride. .
[0035]
In addition to the base material 2 made of the above-mentioned polyolefin-based resin, a woven or non-woven fabric using an organic resin such as polyester or vinylon, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer , Vinyl resins such as ethylene-vinyl alcohol copolymer, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, (meth) acrylic resins such as polymethyl methacrylate, polymethyl acrylate and polyethyl methacrylate, polystyrene, acrylonitrile A sheet or film made of a resin such as butadiene-styrene copolymer (ABS), cellulose triacetate, cellophane, or polycarbonate can be used as the base material 2. In addition, paper such as tissue paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, woodfree paper, coated paper, art paper, parchment paper, glassine paper, parchment paper, paraffin paper, or polychlorinated paper A so-called vinyl wallpaper raw material obtained by sol coating or dry laminating vinyl can also be used. Further, a sheet or film made of inorganic fibers such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, and carbon fiber can be used as the base material 2. Further, metal foil of aluminum, iron, stainless steel, copper, or the like can be used. Furthermore, it is also possible to use a material obtained by laminating a plurality of such base materials as the base material 2.
[0036]
(Colored layer)
The coloring layer 11 is an essential layer in the decorative sheet 1 and includes the solid coloring layer 3 and / or the picture coloring layer 4.
[0037]
As shown in FIG. 1, the solid colored layer 3 is provided for the purpose of concealing the background of the base material 2 and the like, and is usually formed as a completely solid colored layer without a pattern. On the other hand, the pattern coloring layer 4 has a pattern or color composed of a wood pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric pattern, and the like by using figures, characters, symbols, colors, combinations thereof, and the like. On the coloring layer 3, it is formed as a flat, uneven, or convex layer (see FIG. 1). The pattern coloring layer 4 may also serve as the solid coloring layer 3. In this case, the pattern coloring layer 4 becomes the solid coloring layer 3. The solid colored layer 3 and / or picture colored layer 4 thus formed may be provided on the entire surface of the substrate 2 or may be provided partially. As shown in FIG. 1, the coloring layer 11 includes a solid coloring layer 3 provided on the entire surface of the base material 2 and a picture coloring layer 4 partially provided on the surface of the solid coloring layer 3. You can also.
[0038]
In the decorative sheet 1 of the present invention, at least one of the coloring layer 11, the adhesive layer 5, and the protective layer 9 has a water-soluble or water-dispersible ultraviolet absorber and / or a water-soluble or water-dispersible. It is formed of an aqueous coating solution containing a light stabilizer (hereinafter, this coating solution is referred to as “aqueous coating solution” unless otherwise specified). Therefore, it is preferable that the coating liquid for the colored layer for forming the colored layer is also such an aqueous coating liquid. The water-based coating liquid will be described in detail in the description of the adhesive layer 5.
[0039]
The decorative sheet 1 provided with the coloring layer 11 formed with the coloring layer aqueous coating liquid can further improve the adhesive properties, weather resistance, and environmental safety. When the adhesive layer 5 or the protective layer 9 is formed with the water-based coating liquid according to the present invention, the colored layer is formed with a water-based coating liquid or a solvent-based coating liquid not containing an ultraviolet absorber or a light stabilizer. 11 can be formed, but it is most preferable to form all of the colored layer 11, the adhesive layer 5, and the protective layer 9 with an aqueous coating solution.
[0040]
The aqueous coating liquid for a colored layer has an ultraviolet absorber and / or a light stabilizer, a main agent, a crosslinking agent, and a solvent as a basic configuration. The ultraviolet absorber and / or the light stabilizer are blended at a ratio of 0.001 to 10 when the coating liquid comprising the main agent, the crosslinking agent and the solvent (aqueous) is taken as 100. When both the ultraviolet absorber and the light stabilizer are mixed, the mixing ratio of the ultraviolet absorber and the light stabilizer is not particularly limited. The mixing ratio of the main agent and the crosslinking agent is 100: 0.5 to 100: 100, preferably 100: 5 to 100: 20. Further, the mixing ratio of the solvent is 50 to 400 when the sum of the main agent and the crosslinking agent is 100.
[0041]
Examples of the aqueous coating liquid for a colored layer that does not contain an ultraviolet absorber or a light stabilizer include, for example, an aqueous urethane resin-based coloring coating liquid, an aqueous polyester resin-based coloring coating liquid, and an aqueous acrylic resin-based coloring liquid. A coating liquid, an aqueous epoxy resin-based colored coating liquid, an aqueous urethane acrylic resin-based colored coating liquid, an aqueous casein resin-based colored coating liquid, and a colored coating liquid composed of a mixture of these resins are used. .
[0042]
As the solvent-based coating liquid for the colored layer, a colored coating liquid containing, as a resin component contained in the solvent-based coating liquid, a mixture of an oil-based (meth) acrylic resin and an oil-based urethane resin which can be mixed with each other. Is used. For example, the (meth) acrylic resin includes a mixture of methyl methacrylate (MMA), hydroxyethyl methacrylate (HEMA), and dimethylaminoethyl methacrylate. Examples of the urethane resin include those produced using butanediol as a polyhydric alcohol, isophorone diisocyanate (IPDI) as an isocyanate, and adipic acid as raw materials. In the case where the colored layer 11 is formed of a mixed resin of an oil-based urethane resin and an oil-based (meth) acrylic resin, the urethane resin in the layer obtained by applying and drying the solvent-based coating liquid contains the urethane resin in the binder component. The (meth) acrylic resin and the urethane resin are preferably mixed so as to contain 10 to 100% by weight, and more preferably 20 to 80% by weight. When the content of the urethane resin in the layer is less than 10% by weight, the adhesion between the base material 2 and the transparent resin layer 6 may not be improved in some cases. As the solvent, an ester organic solvent such as methyl acetate and butyl acetate, and a ketone organic solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone are usually used. Such a solvent-based coating liquid may contain a conventionally used ultraviolet absorber or light stabilizer.
[0043]
In the present invention, each of the colored layer 11, the adhesive layer 5, and the protective layer 9 is a water-based coating solution containing a non-hydrophilic ultraviolet absorber and / or a non-hydrophilic light stabilizer. Is not formed. Therefore, the colored layer 11 is not formed by such an aqueous coating liquid. As a result, the weather resistance and the adhesive properties of the formed decorative sheet are not reduced.
[0044]
Organic or inorganic pigments can be used as the color pigments to be contained in the above-mentioned various color layer coating liquids. For example, as the yellow pigment, azo pigments such as monoazo, disazo and polyazo, organic pigments such as isoindolinone, and inorganic pigments such as graphite, yellow iron oxide, cadmium yellow, titanium yellow, and antimony yellow can be used. it can. As the red pigment, azo pigments such as monoazo, disazo and polyazo, organic pigments such as quinacridone, and inorganic pigments such as red iron oxide, vermilion, cadmium red, and chromium vermilion can be used. In addition, as the blue pigment, an organic pigment such as phthalocyanine blue and indaslen blue, and an inorganic pigment such as navy blue, ultramarine blue and cobalt blue can be used. Further, as the black pigment, an organic pigment such as aniline black or an inorganic pigment such as carbon black can be used. As the white pigment, inorganic pigments such as titanium dioxide, zinc white, and antimony trioxide can be used. Further, a filler such as silica, a volume pigment such as organic beads, a neutralizing agent, a surfactant and the like can be optionally contained.
[0045]
Depending on the type of the coating liquid used for the solid coloring layer 3 and the pattern coloring layer 4, depending on the type of the coating liquid, besides the above-mentioned ultraviolet absorber and light stabilizer, waxes, dispersants, defoamers It is prepared by arbitrarily adding an agent, a leveling agent, a stabilizer, a filler, a lubricant, a lubricant, and other additives, and thoroughly mixing with a mixer or the like.
[0046]
The solid coloring layer 3 and the picture coloring layer 4 are formed by applying the above-mentioned various coloring layer coating liquids by coating or printing, and then drying. More specifically, the solid color layer 3 is usually formed by applying or printing a solid color layer coating liquid, followed by drying and curing. The pattern coloring layer 4 is also formed by applying or printing a coating liquid for a pattern coloring layer, followed by drying and curing. As the coating method, various known methods, for example, roll coat, curtain flow coat, wire bar coat, reverse coat, gravure coat, gravure reverse coat, air knife coat, kiss coat, blade coat, smooth coat, comma coat, spray coat , Pouring coating, brush coating, or the like. In addition, as a printing method, various known methods such as gravure, letterpress, relief printing such as flexo, lithographic offset, lithographic printing such as dilitho printing, stencil printing such as silk screen, electrostatic printing, and ink jet printing may be used. Can be. The solid coloring layer 3 is coated or printed so that the film thickness after drying is about 0.5 to 10 μm, and the pattern coloring layer 4 is coated so that the film thickness after drying is about 0.1 to 10 μm. Coated or printed.
[0047]
(Adhesive layer)
As shown in FIG. 1, the adhesive layer 5 is provided between the colored layer 11 and the transparent resin layer 6 to improve the adhesion between the substrate 2 or the substrate 2 / the colored layer 11 and the transparent resin layer 6. It has a role as a primer layer or an anchor layer to be improved, and has an effect of improving durability and long-term appearance maintenance. Such an action can maintain the formed picture for a long time, and is extremely effective.
[0048]
The adhesive layer 5 is preferably formed of an aqueous coating liquid for an adhesive layer containing a water-soluble or water-dispersible ultraviolet absorber and / or a water-soluble or water-dispersible light stabilizer. Since the UV absorber and light stabilizer contained in this aqueous coating solution for an adhesive layer are water-soluble or water-dispersible, these UV absorbers and light stabilizers are uniformly dissolved or dispersed in the coating solution. Spread. In the adhesive layer formed by such a coating solution, since the ultraviolet absorber and the light stabilizer are present in a state of being uniformly dispersed, the decorative sheet obtained by forming the adhesive layer with the conventional aqueous coating solution is used. In comparison, the weather resistance can be improved.
[0049]
The adhesive layer 5 formed with the aqueous coating liquid for an adhesive layer is excellent because it is provided between the base material 2 and the transparent resin layer 6 or between the base material 2 / the colored layer 11 and the transparent resin layer 6. Shows the adhesive properties. Further, since the water-based coating liquid for the adhesive layer is a water-based coating liquid, the volatile amount of VOC in the working environment and the residual amount of VOC in the decorative sheet can be reduced as much as possible, and the environmental safety can be further improved. Can be improved.
[0050]
The aqueous coating liquid for the adhesive layer comprises (1) a water-soluble or water-dispersible ultraviolet absorber and / or a water-soluble or water-dispersible light stabilizer, (2) a main agent and a crosslinking agent, and (3) water. Or a mixed solvent composed of water and alcohol.
[0051]
(1) Water-soluble or water-dispersible ultraviolet absorber, water-soluble or water-dispersible light stabilizer;
Examples of the water-dispersible ultraviolet absorber include those obtained by subjecting a compound represented by the following chemical formula 1 (molecular weight: 315, melting point: 139 ° C., CAS-No. 3896-11-5) to hydrophilic treatment with an emulsifier or the like (specific gravity: 1). 0.094, viscosity: 225 mPa · s (cps)).
[0052]
Embedded image

[0053]
As a water-soluble or water-dispersible ultraviolet absorber other than the above, a water-soluble and / or water-dispersible resin in which an ultraviolet absorber component is introduced in the molecule can also be used. For example, a copolymer obtained by radical polymerization of an ultraviolet absorber component composed of a compound represented by the following chemical formula 2 (monomer molecular weight: 323, CAS-No. 96478-09-0), a hydrophilic component, methyl methacrylate, styrene, etc. Aqueous resin.
Embedded image

Here, whether such an aqueous resin becomes water-dispersible or water-soluble depends on the hydration power of the hydrophilic component and the content of the hydrophilic component (hydrophilic group) with respect to each resin. Decided. As the amount of the hydrophilic group in the aqueous resin increases, the ultraviolet absorber becomes water-soluble from water-dispersible. As the hydrophilic component, there are a component that can be made hydrophilic by neutralization and a component that has hydrophilicity by itself. Examples of those which can be made hydrophilic by neutralization include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a tertiary amino group, and a quaternary amino group. The neutralizing agent in this case is not particularly limited as long as it can neutralize or ionize. For example, non-volatile bases such as sodium hydroxide and potassium hydroxide; trimethylamine, triethylamine, triethanolamine and the like; Tertiary amines; volatile bases such as ammonia; inorganic acids such as hydrochloric acid and nitric acid; organic acids such as formic acid, acetic acid, lactic acid, citric acid and tartaric acid. Examples of the component itself having a hydrophilic property include a hydroxyl group and an ether bond. Among these, a compound having a hydroxyl group introduced is preferably used from the viewpoint of improving weather resistance. In addition, the content ratio of the compound which is an ultraviolet absorber component is adjusted in the range of 0.01 to 50% by weight based on 100% by weight of the copolymer compound.
[0054]
Other examples of the UV absorber in which the UV absorber component is introduced in the molecule of the water-soluble and / or water-dispersible resin include, for example, the above-mentioned water-soluble and water-dispersible UV-absorber copolymer prepolymer. Polyurethane resin, polyester resin, acrylic resin, vinyl resin and the like. In addition, the aqueous resin in which the ultraviolet absorbent is introduced into the molecule can also play a role as a main agent described later.
[0055]
As the water-dispersible light stabilizer (radical scavenger), for example, a compound represented by the following chemical formula 3 (molecular weight: about 900, specific gravity: 0.98, viscosity: 7000 mPa · s (cps), CAS-No. 101544) 98-3, 84696-72-0, 107119-91-5) treated with an emulsifier or the like in water dispersibility (specific gravity 0.999, viscosity: 45 mPa · s (cps)).
[0056]
Embedded image

The water-soluble or water-dispersible ultraviolet absorber and / or light stabilizer is compounded in a ratio of 0.001 to 10 when the coating liquid comprising the main agent, the crosslinking agent and the solvent (aqueous) is taken as 100. You. When both an ultraviolet absorber and a light stabilizer are blended, the blending ratio of the ultraviolet absorber and the light stabilizer is not particularly limited.
[0057]
(2) main agent and crosslinking agent;
Examples of the main agent include a polyurethane resin, a polyester resin, an acrylic resin, a vinyl resin, an epoxy resin, a copolymer thereof, a mixture thereof, and the like. Such a base material is required to have a functional group that reacts with a crosslinking agent component.
[0058]
Examples of the crosslinking agent include an isocyanate compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a compound having a silanol group. Among these, it is preferable to use an isocyanate compound.
[0059]
The mixing ratio of the main agent and the crosslinking agent is 100: 0.5 to 100: 100, preferably 100: 5 to 100: 20.
[0060]
{Circle around (3)} As the solvent water, industrial grade water conventionally used for aqueous coating liquids is used. Further, a mixed solvent composed of water, alcohol, and the like can be used as a solvent for the aqueous coating liquid. Examples of the alcohol constituting the mixed solvent include lower alcohols such as ethanol, isopropyl alcohol and n-propyl alcohol, glycols and esters thereof. Solvents such as lower alcohols, glycols and esters thereof are used for the purpose of improving the fluidity of the aqueous coating solution, improving the wetting of the colored layer which is the object to be coated, and adjusting the drying property. The type, amount used, etc. are determined according to the purpose. The water-based coating liquid used in the present invention does not use high-risk aromatic hydrocarbon-based organic volatile substances such as benzene, toluene, and xylene, and also suppresses the use of other organic solvents. Therefore, generation of VOC can be reduced.
[0061]
In a mixed solvent composed of water, alcohol, and the like, the mixing ratio of water: alcohol or the like (for example, isopropyl alcohol, methanol, ethanol, n-propyl alcohol, etc.) = 20:80 to 100: 0. Can be adjusted in the range of Moreover, it is preferable that the mixing ratio of the solvent in the aqueous coating liquid is 50 to 400 when the main agent and the crosslinking agent are 100.
[0062]
In addition to the above-mentioned ultraviolet absorber and light stabilizer, additives such as a coloring agent, a dispersant, an antifoaming agent, a leveling agent, a stabilizer, a filler, a lubricant, and a lubricant are optionally added to the aqueous coating liquid. May be.
[0063]
The aqueous coating liquid for the adhesive layer is prepared by mixing (1) an ultraviolet absorber and / or a light stabilizer, (2) a main agent and a crosslinking agent, and (3) an aqueous solvent in the above ratio, and using a mixer or the like. It is prepared by mixing.
[0064]
When the coloring layer 11 and / or the protective layer 9 are formed by the aqueous coating liquid of the present invention, the adhesive layer 5 may be coated with an aqueous coating liquid containing no ultraviolet absorber or light stabilizer, or a solvent. Although it can be formed with a system-based coating solution and a non-solvent-based coating agent, it is most preferable to form with a water-based coating solution of the present invention.
[0065]
Examples of the solvent-based coating liquid include a two-component oil-based urethane resin and a mixture of an oil-based acrylic resin and an oil-based urethane resin. The two-component oil-based urethane resin contains the oil-based urethane resin and an isocyanate as a crosslinking agent in a range of resin component: crosslinking agent component = 10: 1 to 10:60. Examples of the mixture of the oil-based acrylic resin and the oil-based urethane resin include a mixture of the oil-based urethane resin and methyl methacrylate (MMA), hydroxyethyl methacrylate (HEMA), dimethylaminoethyl methacrylate, or the like. In this case, the oil-based acrylic resin and the oil-based urethane resin are mixed so that the urethane resin in the adhesive layer obtained by applying and drying the solvent-based coating agent is contained at 10 to 100% by weight. Is preferred.
[0066]
Examples of the solvent-free (non-sol-based) coating agent include those comprising a polyol compound and a polyisocyanate compound. Examples of the polyol compound include a polyester polyol and a polyether polyol. As the polyisocyanate compound, for example, a polyfunctional polyisocyanate compound such as 2,4-tolylene diisocyanate, isocyanurate derived from a polyisocyanate monomer such as 2,6-tolylene diisocyanate, buret, allophanate, or Examples include a polyfunctional polyisocyanate compound having a terminal isocyanate group, which is obtained by a reaction with a trifunctional or higher functional polyol compound such as trimethylolpropane or glycerin.
[0067]
As the ultraviolet absorber to be added to the solvent-based coating liquid or the solventless coating agent, an organic substance such as benzotriazole, benzophenone, triazine, salicylate, or an inorganic substance such as zinc oxide, cesium oxide, or titanium oxide may be used. Fine particles having a diameter of 2 μm or less can be used. Similar light stabilizers include bis- (2,2,6,6-tetramethyl-4-biperidinyl) sebacate and bis- (N-methyl-2,2,6,6-tetramethyl-4-biperidinyl) Hindered radical scavengers and biperidinyl radical scavengers such as sebacate and other compounds disclosed in Japanese Patent Publication No. 4-82625 can be used.
[0068]
In the present invention, each of the colored layer 11, the adhesive layer 5, and the protective layer 9 is a water-based coating solution containing a non-hydrophilic ultraviolet absorber and / or a non-hydrophilic light stabilizer. Is not formed. Therefore, the adhesive layer 5 is not formed with such an aqueous coating liquid. Here, the non-hydrophilic ultraviolet absorber and the non-hydrophilic light stabilizer refer to a substance in which the compound itself does not dissolve in water and does not stably disperse in water. Includes substances that do not stabilize in water even when dispersed in water. Therefore, among the ultraviolet absorbers and light stabilizers to be added to the above-mentioned solvent-based coating liquid or non-solvent-based coating liquid, those having non-hydrophilic properties are used in the above-mentioned aqueous coating liquid for the adhesive layer. Is not added. When a non-hydrophilic UV absorber and / or light stabilizer is added to the aqueous coating solution, the interlayer adhesion, weather resistance, and scratch resistance of the decorative sheet having the adhesive layer formed with the aqueous coating solution can be improved. In some cases, the adhesive properties may be deteriorated.
[0069]
The adhesive layer 5 is formed by applying the above-mentioned coating liquid for an adhesive layer on the colored layer 11 by coating or printing, and then drying. Examples of the coating method include various known methods such as roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, comma coating, and spray coating. A method such as pouring coating or brush coating can be used, and coating is performed so that the film thickness after drying is about 1 to 10 μm.
[0070]
(Transparent resin layer)
The transparent resin layer 6 is also referred to as a top resin layer. The transparent resin layer 6 is provided with an adhesive layer 5 interposed therebetween for the purpose of protecting the colored layer 11 from abrasion, improving the surface strength of the decorative sheet 1, giving a feeling of painting, and the like. And is laminated on the colored layer 11.
[0071]
The resin constituting the transparent resin layer 6 is not particularly limited as long as it is a transparent resin which is formed on the colored layer 11 with good adhesion via the above-mentioned adhesive layer 5, and for example, transparent polypropylene or the like Olefin resins are preferred. As the resin other than the olefin resin that can be used as the resin for the transparent resin layer, the same resin material as that used for the base material 2 can be used. Known additives such as a coloring agent, a filler, an ultraviolet absorber, a light stabilizer, and a matting agent are added to the resin forming the transparent resin layer 6 as necessary.
[0072]
The transparent resin layer 6 is formed by laminating a separately formed transparent resin sheet on the adhesive layer 5, formed by a melt extrusion coating method, or laminated by other known methods.
[0073]
Further, as shown in FIG. 2, the transparent resin layer 6 may have a multilayer structure of two or more layers. The transparent resin layer 16 formed by laminating two or more layers is advantageous in that the transparent resin layer 6 ′ on the base material 2 side and the transparent resin layer 6 ″ on the protective layer side can have different functions and effects. As one specific example, the transparent resin layer 6 ″ on the protective layer side is formed of a resin containing a fluorine-based resin such as vinylidene fluoride as a main component to impart excellent surface functions such as excellent stain resistance. The transparent resin layer 6 ′ on the material side is formed of a thermoplastic (meth) acrylic resin or the like, so that the adhesion between the adhesive layer 5 and the like can be improved. Further, as another specific example, the transparent resin layer 6 ″ on the protective layer side is formed of a polypropylene resin to which a weathering agent is added to impart excellent weather resistance, and the transparent resin layer 6 ′ on the substrate side is provided. Can be formed of a polypropylene resin containing an elastomer to improve weather resistance and adhesion.
[0074]
The two or more transparent resin layers 16 are formed by melt co-extrusion of a plurality of resin compositions, or by various lamination methods such as dry lamination and heat lamination. At this time, as shown in FIG. 3, a transparent resin layer 16 composed of two or more layers can be formed via an adhesive layer 12 acting as a primer layer or an anchor layer. In this case, the adhesive layer 12 is formed by melt co-extrusion with the transparent resin layers 6 ′ and 6 ″, or is formed by applying a water-based coating solution containing an aqueous urethane resin. , VOC can be further suppressed.
[0075]
The thickness of the transparent resin layer 6 is about 20 to 300 μm, and when formed with a coating solution, 15 to 400 g / m ² Coat with a small amount of coating.
[0076]
(Uneven pattern)
The concavo-convex pattern 7 is also called an embossed pattern, and is formed on the surface of the above-described transparent resin layer 6 as necessary, as shown in FIG. When two or more transparent resin layers 16 are formed as shown in FIGS. 2 and 3, the concavo-convex pattern 7 is formed on the outermost transparent resin layer or on the other transparent resin layer. Or you can.
[0077]
The concavo-convex pattern 7 is not particularly limited, and may be a pattern according to the use of the decorative sheet 1. For example, wood-grain conduit grooves, wood-grain annual ring unevenness, floating ring-shaped unevenness, wood-grain unevenness, sand grain, satin finish, hairline, line-shaped groove, stone surface unevenness such as granite cleavage surface, cloth grain surface texture, leather squeezing, characters, geometry A pattern such as a study pattern is given.
[0078]
Means for forming the concavo-convex pattern 7 include, for example, an embossing method by heating and pressing and a T-die melt extrusion method. The embossing method by heating and pressurizing is a method in which the surface of the transparent resin layer 6 is heated and softened, the surface is pressurized with an embossing plate to shape the embossed plate uneven pattern 7, and then cooled and fixed. A known single-wafer or rotary embossing machine is used. In the case of forming an uneven pattern by the embossing method, embossing is performed in advance on the transparent resin layer sheet before lamination by laminating, or simultaneously with laminating the transparent resin layer sheet (so-called doubling embossing method). I do. When the transparent resin layer 6 is laminated by the T-die melt extrusion method, a concave / convex pattern 7 is formed simultaneously with the formation and lamination of the transparent resin layer 6 by using a cooling roller also serving as a shaping roller. The embossed pattern can also be formed by hairline processing, sandblasting, or the like.
[0079]
(Partial colored layer)
The partial coloring layer 8 is formed in the concave portion 17 of the uneven pattern 7 by a wiping method. In the wiping method, a coating solution for the partial coloring layer is applied to the entire surface including the recess 17 by a doctor blade coating method or a knife coating method, and then the coating solution for the partial coloring layer is applied from the surface other than the recess 17. This is a method in which the partial coloring layer 8 is formed only in the concave portion 17 by removing. As a coating liquid for the partially colored layer, a coating liquid composed of a coloring pigment such as an organic pigment, an inorganic pigment, and a bright pigment, and a binder resin such as a thermoplastic resin, a thermosetting resin, and an ionizing radiation-curable resin. A liquid or an emulsion-type aqueous coating liquid can be used.
[0080]
Further, an aqueous coating liquid for forming the solid color layer 3 and / or the pattern color layer 4 described above can be preferably used, and in such a case, it is more preferable from the viewpoint of environmental safety.
[0081]
(Protective layer)
The protective layer 9 is also called a top coat layer or an overprint layer (OP layer), and covers the surface of the concave portion 17 forming the concave-convex pattern 7 and the partial coloring layer 8 formed in the concave portion 17 to cover the decorative sheet 1. It is provided for the purpose of protecting. Specifically, the decorative sheet 1 is protected by improving surface properties such as scratch resistance, stain resistance, and weather resistance.
[0082]
The protective layer 9 is preferably formed by applying the aqueous coating liquid of the present invention described in detail in the paragraph of the above-mentioned adhesive layer. Particularly, the decorative sheet 1 having the protective layer excellent in weather resistance and light resistance is used. It is possible to provide the decorative sheet 1 which can be provided and which suppresses generation of VOCs and improves environmental safety.
[0083]
The water-based coating liquid for the protective layer is basically composed of an ultraviolet absorber and / or a light stabilizer, a main agent, a cross-linking agent and a solvent, and the ultraviolet absorber, the light stabilizer and the solvent are located in the adhesive layer. The same ones as described can be used. In addition, as a main agent, polyurethane resin, polyester resin, acrylic resin, vinyl resin, epoxy resin, etc., a copolymer thereof, a mixture thereof, and the like are exemplified. Such a base material is required to have a functional group that reacts with a crosslinking agent component. Examples of the crosslinking agent include an isocyanate compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a compound having a silanol group. Among these, it is preferable to use an isocyanate compound. Note that an ionizing radiation-curable resin may be used for the aqueous coating liquid. The mixing ratio of the main agent and the crosslinking agent is 100: 0.5 to 100: 100, preferably 100: 5 to 100: 20.
[0084]
The ultraviolet absorber and / or the light stabilizer are blended at a ratio of 0.001 to 10 when the coating liquid comprising the main agent, the crosslinking agent and the solvent (aqueous) is taken as 100. When both an ultraviolet absorber and a light stabilizer are blended, the blending ratio of the ultraviolet absorber and the light stabilizer is not particularly limited. The mixing ratio of the main agent and the crosslinking agent is 100: 0.5 to 100: 100, preferably 100: 5 to 100: 20. Further, the mixing ratio of the solvent is 50 to 400 when the sum of the main agent and the crosslinking agent is 100.
[0085]
When the coloring layer 11 and / or the adhesive layer 5 is formed of the aqueous coating liquid of the present invention, the protective layer 9 may be formed of an aqueous coating liquid containing no ultraviolet absorber or light stabilizer. Although it can be formed by a solvent-based coating solution or a non-solvent-based coating solution, it is most preferable to use the water-based coating solution of the present invention. In particular, it is most preferable that all of the colored layer 11, the adhesive layer 5, and the protective layer 9 are formed by the aqueous coating solution of the present invention.
[0086]
As the solvent-based coating liquid, an acrylic resin, a polyurethane resin, an epoxy resin, or the like, or a copolymer thereof, or a mixture thereof, using a crosslinking agent component such as an isocyanate compound, an epoxy compound, or ionization, After applying the ionic radiation-curable resin, a resin cured by irradiation with ionizing radiation can be used. As the solvent-free coating liquid, a coating liquid using an ionizing radiation-curable resin is preferable. It is preferable to add an ultraviolet absorber and / or a light stabilizer to such a solvent-based coating liquid or a non-solvent-based coating liquid in order to provide the protective layer 9 with better weather resistance and light resistance.
[0087]
In the present invention, each of the colored layer 11, the adhesive layer 5, and the protective layer 9 is a water-based coating solution containing a non-hydrophilic ultraviolet absorber and / or a non-hydrophilic light stabilizer. Is not formed. Therefore, the protective layer 9 is not formed by such an aqueous coating liquid. As a result, the weather resistance and the adhesive properties of the formed decorative sheet are not reduced.
[0088]
The protective layer 9 may be a layer whose gloss has been adjusted by adding a known matting agent such as silica to the coating liquid, or a layer having a design such as a feeling of painting. As other additives, colorants, dispersants, defoamers, leveling agents, stabilizers, fillers, lubricants, lubricants, antistatic agents, flame retardants and the like are used.
[0089]
The protective layer 9 is formed by applying the above-described various coating solutions by a known coating method such as a gravure coating method, a reverse roll coating method, a knife coating method, a kiss coating method, or another coating method. Further, it is formed by a known printing method such as gravure printing and silk screen printing. The thickness of the formed protective layer 9 is preferably about 3 to 40 μm, more preferably 10 to 30 μm.
[0090]
(Primer layer)
The primer layer 10 is formed on the back surface side of the base material 2 for the purpose of making the decorative sheet 1 of the present invention easily adhere to various adherends 15. For forming the primer layer 10, a (meth) acrylic resin, a vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, or the like is used. It is preferable from the viewpoint of environmental safety to use a water-based coating liquid that is preferably employed to form the composition No. 5.
[0091]
(Decorative sheet)
As described above, the decorative sheet 1 obtained by forming each layer (coloring layer, adhesive layer, and protective layer) using the aqueous coating liquid according to the present invention was prepared using a conventional aqueous coating liquid. The weather resistance can be improved as compared with a decorative sheet obtained by forming a layer of.
[0092]
The decorative sheet 1 of the present invention having the above-described configuration is used by being laminated on another adherend 15 (backing material).
[0093]
The object to be adhered 15 is a three-dimensional article 41 as shown in FIG. 4, a flat or curved plate 51 as shown in FIG. 5, or an article of various shapes such as a sheet (or film). . Examples of the adherend 15 include wood veneer, wood plywood, particle board, wood board such as medium density fiber board (MDF), wood board such as wood fiber board, metal such as iron and aluminum, (meth) acrylic, Polyester, polystyrene, polyolefin, ABS resin, phenolic resin, polyvinyl chloride resin, cellulose resin, rubber and other resins, glass, ceramics such as ceramics, non-cement ceramics materials such as plaster, high quality paper, paper such as Japanese paper, Non-woven fabrics or woven fabrics made of fibers such as carbon, asbestos, potassium titanate, glass, and synthetic resins, and the like.
[0094]
Regarding the relationship between the decorative sheet 1 and the adherend 15, if the decorative sheet 1 can be directly adhered to the adherend 15 by heat fusion or the like depending on the type of the base material 2 or the primer layer 10, The adherend 15 can be laminated without using an adhesive. However, depending on the type of the base material 2 or the primer layer 10 of the decorative sheet 1, when the adherend 15 cannot be directly adhered to the adherend 15 by heat fusion or the like, Laminate using a suitable adhesive. Note that examples of the adhesive include a vinyl acetate-based adhesive and a urea-based adhesive.
[0095]
Examples of the general laminating method include (a) a method of laminating the adherend 15 with a pressure roller via an adhesive, (b) Japanese Patent Publication No. 50-19132, and Japanese Patent Publication No. As described in Japanese Patent No. 27488, etc., the decorative sheet 1 is inserted between the male and female molds for injection molding, the molds are closed, the molten resin is injected and filled from the male mold gate, and then cooled. Injection molding simultaneous laminating method in which a decorative sheet 1 is adhered and laminated on the surface of a resin molded product at the same time as molding, and (c) as described in JP-B-56-45768 and JP-B-60-58014, etc. A vacuum press laminating method in which the decorative sheet 1 is opposed to the surface of the molded article through the surface of the molded article, and the decorative sheet 1 is laminated on the surface of the molded article by a pressure difference caused by vacuum suction from the molded article side, (d) JP-B-61-5895. Gazette, Tokuhei 3-26 As described in Japanese Patent Publication No. 6 (1994), etc., while supplying the decorative sheet 1 via an adhesive in the longitudinal direction of a columnar adherend such as a cylinder or a polygonal column, the columnar adherend is applied by rollers having different directions. A lapping method or the like in which the decorative sheet 1 is sequentially pressure-adhered and laminated on a plurality of side surfaces constituting the body is exemplified.
[0096]
The various adherends 15 on which the decorative sheets 1 of the present invention are laminated are subjected to a predetermined molding process and the like, and used as various decorative materials and the like. For example, interior decoration of buildings such as walls, ceilings and floors, surface decoration of fittings such as window frames, doors, handrails, surface decoration of cabinets of furniture or light electric / OA equipment, vehicle interiors of automobiles and trains, aircraft interiors, windows Uses such as glass cosmetics can be mentioned.
[0097]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following, parts are parts by weight.
[0098]
(Example 1)
As a base material 2, a polypropylene elastomer colored sheet PB013 (thickness: 60 μm) manufactured by Mitsubishi Chemical MKV Co., Ltd. was subjected to corona discharge treatment, and then a gravure plate having 54 lines / inch and a plate depth of 40 μm was prepared. Aqueous coating liquid A for solid coloring layer and aqueous coating liquid B for picture coloring layer having the following composition are sequentially applied by a gravure printing method and dried, and about 3 μm solid coloring layer 3 and about 1 μm picture coloring layer 4 Were sequentially formed. Further, a gravure plate having a line number of 54 lines / inch and a plate depth of 40 μm was further coated thereon with an aqueous coating liquid a for an adhesive layer having the following composition by gravure printing at about 3 g / m ² And dried to form an adhesive layer 5 having a thickness of 3 μm.
Further, a transparent polypropylene film “PE002C” (thickness: 80 μm) manufactured by Mitsubishi Chemical MKV Co., Ltd. was laminated on the adhesive layer 5 by a dry lamination method to form a transparent resin layer 6. Next, a concavo-convex pattern 7 is formed on the surface of the laminated sheet by embossing, and a gravure plate having a number of lines of 54 lines / inch and a plate depth of 40 μm is further formed thereon using a gravure plate having the following composition. The working liquid C was applied by a gravure printing method and dried to form a protective layer 9 of about 3 μm. Thereafter, the decorative sheet of Example 1 was obtained by curing at 25 ° C. for 7 days.
[0099]
Aqueous coating liquid A for solid colored layer ;
Aqueous urethane-based white ink (no added ultraviolet absorber, etc .; manufactured by The Inktec, Ode WKE white solid): 100 parts, water-dispersible isocyanate cross-linking agent (Nika Chemical Co., Ltd., X9003): 5 parts, water dispersion UV absorber (Asahi Denka Kogyo KK, LX-301): 1 part, water dispersible light stabilizer (Asahi Denka Kogyo KK, LX-332): 1 part, water: 20 parts, isopropyl alcohol: 20 copies
Aqueous coating liquid B for pattern coloring layer ;
Aqueous urethane-based yellow ink (no added UV absorber, etc .; manufactured by The Inktec, Ode WKE Yellow): 100 parts, water-dispersible UV absorber (LX-301, manufactured by Asahi Denka Kogyo Co., Ltd.): 1 part, water Dispersible light stabilizer (LX-332, manufactured by Asahi Denka Kogyo Co., Ltd.): 1 part, water: 20 parts, isopropyl alcohol: 20 parts
Aqueous coating liquid for adhesive layer a ;
Aqueous urethane resin (no UV absorber or the like added; HO14, manufactured by Nika Chemical Co., Ltd.): 100 parts, water-dispersible isocyanate crosslinking agent (X9003, manufactured by Nika Chemical Co., Ltd.): 5 parts, water-dispersible ultraviolet absorber (Asahi Denka Kogyo KK, LX-301): 1 part, water dispersible light stabilizer (Asahi Denka Kogyo KK, LX-332): 1 part, water: 20 parts, isopropyl alcohol: 20 parts
Water-based coating solution for protective layer b ;
Aqueous urethane resin (not added with ultraviolet absorber, etc .; 135 manufactured by Showa Ink Industries Co., Ltd.): 100 parts, water-dispersible isocyanate crosslinking agent (X9003 manufactured by Nika Chemical Co., Ltd.): 5 parts, water-dispersible ultraviolet absorption 1 part, water-dispersible light stabilizer (LX-332, manufactured by Asahi Denka Kogyo KK): 1 part, water: 20 parts, isopropyl alcohol: 20 parts
[0100]
(Example 2)
Instead of the solvent-based coating liquid for adhesive layer a of Example 1, a solvent-based coating liquid for adhesive layer c having the following composition was used. Otherwise, the decorative sheet of Example 2 was obtained in the same manner as in Example 1.
Solvent-based coating liquid for adhesive layer c ;
100 parts of a polyester resin adhesive (containing an ultraviolet absorber and a light stabilizer; E295L-NT, manufactured by Dainichi Seika Kogyo Co., Ltd.), 10 parts of an isocyanate crosslinking agent (C55, manufactured by Dainichi Seika Kogyo Co., Ltd.), ethyl acetate : 80 copies
[0101]
(Example 3)
Instead of the aqueous coating liquid a for an adhesive layer in Example 1, an aqueous coating liquid d for an adhesive layer having the following composition was used. Otherwise, the decorative sheet of Example 3 was obtained in the same manner as in Example 1.
Water-based coating liquid for adhesive layer d ;
Aqueous urethane resin (no UV absorber or the like added; HO14, manufactured by Nika Chemical Co., Ltd.): 100 parts, water-dispersible isocyanate crosslinking agent (X9003, manufactured by Nika Chemical Co., Ltd.): 5 parts, ultraviolet absorber in the molecule : 1 part of aqueous resin (PUVA-30W, manufactured by Otsuka Chemical Co., Ltd.), 1 part of water-dispersible light stabilizer (LX332, manufactured by Asahi Denka Kogyo KK), 20 parts of water, 20 parts of isopropyl alcohol
[0102]
(Example 4)
Instead of the aqueous coating solution b for a protective layer in Example 1, an aqueous coating solution e for a protective layer having the following composition was used. Except for this, the decorative sheet of Example 4 was obtained in the same manner as in Example 1.
Water-based coating liquid e for protective layer ;
Aqueous urethane resin (not added with UV absorber, etc .; 135 manufactured by Showa Ink Industries Co., Ltd.): 100 parts, water-dispersible isocyanate crosslinking agent (X9003 manufactured by Nika Chemical Co., Ltd.): 5 parts, UV absorber is a molecule Aqueous resin (PUVA-30W, manufactured by Otsuka Chemical Co., Ltd.) contained therein: 1 part, water-dispersible light stabilizer (LX332, manufactured by Asahi Denka Kogyo Co., Ltd.): 1 part, water: 20 parts, isopropyl alcohol: 20 Department
[0103]
(Example 5)
Instead of the method of forming the transparent resin layer 6 of Example 1, a forming method by a melt extrusion method was used. Specifically, on the adhesive layer 5, 0.2% by weight of a phenolic antioxidant, 0.3% by weight of a hindered amine light stabilizer, and 0.2% by weight of an antiblocking agent were added to the randomly polymerized polypropylene. The resin was extruded in a molten state using a T-die, and a transparent resin layer 6 having a thickness of 80 μm was laminated by heating at 180 ° C. Except for this, the decorative sheet of Example 5 was obtained in the same manner as in Example 1.
[0104]
(Comparative Example 1)
Instead of the aqueous coating liquid A for solid color layers and the aqueous coating liquid B for picture colored layers in Example 1, an aqueous coating liquid C for solid colored layers and an aqueous coating liquid D for picture colored layers having the following composition were used. Using. Except for this, the decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1.
Aqueous coating liquid C for solid colored layer ;
Aqueous urethane-based white ink (no added UV absorber, etc .; manufactured by The Inktec, Ode WKE white solid): 100 parts, water-dispersible isocyanate cross-linking agent (X9003, manufactured by Nikka Chemical Co., Ltd.): 5 parts, ultraviolet absorption Agent (Asahi Denka Kogyo KK, LA-36): 0.3 part, light stabilizer (Asahi Denka Kogyo KK, LA-62): 0.3 part, water: 20 parts, isopropyl alcohol: 20 parts
Aqueous coating liquid D for colored pattern layer ;
Aqueous urethane yellow ink (no added UV absorber, etc .; manufactured by The Inktec, Ode WKE yellow): 100 parts, UV absorber (LA-36, manufactured by Asahi Denka Kogyo Co., Ltd.): 0.3 parts, light stable Agent (Asahi Denka Kogyo Co., Ltd., LA-62): 0.3 part, water: 20 parts, isopropyl alcohol: 20 parts
[0105]
(Comparative Example 2)
Instead of the aqueous coating liquid a for the adhesive layer in Example 1, the aqueous coating liquid f for the adhesive layer was used. Except for this, the decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1.
Aqueous coating liquid for adhesive layer f ;
Aqueous urethane resin (no added UV absorber, etc .; HO14, manufactured by Nika Chemical Co., Ltd.): 100 parts, water-dispersible isocyanate crosslinking agent (X9003, manufactured by Nika Chemical Co., Ltd.): 5 parts, ultraviolet absorber (Asahi Denka) Industrial Co., Ltd., LA-36): 0.3 part, light stabilizer (Asahi Denka Kogyo Co., Ltd., LA-62): 0.3 part, water: 20 parts, isopropyl alcohol: 20 parts
[0106]
(Comparative Example 3)
Instead of the aqueous coating solution b for a protective layer in Example 1, an aqueous coating solution g for a protective layer having the following composition was used. Except for this, the decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1.
Water-based coating liquid for protective layer g ;
Aqueous urethane resin (not added with UV absorber, etc .; 135 manufactured by Showa Ink Industries Co., Ltd.): 100 parts, water-dispersible isocyanate crosslinking agent (X9003 manufactured by Nika Chemical Co., Ltd.): 5 parts, ultraviolet absorber (Asahi) Denka Kogyo Co., Ltd., LA-36): 0.3 part, light stabilizer (Asahi Denka Kogyo Co., Ltd., LA-62): 0.3 part, water: 20 parts, isopropyl alcohol: 20 parts
[0107]
(Evaluation method for each characteristic)
The interlayer adhesion, the interlayer adhesion after the weather resistance test, and the scratch resistance of each decorative sheet obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated by the following methods. Table 1 shows the obtained results.
[0108]
(Method of evaluating interlayer adhesion)
The decorative sheet 1 cut to a width of 1 inch was used as a test piece, and the base material 2 and the transparent resin layer 6 of the test piece were subjected to a tensile speed of 100 mm / min in an atmosphere of 25 ° C. and 100 mm / min using an INSTRON 5500 tensile tester. The film was pulled under the condition of an opening angle of 180 ° between the resin and the transparent resin layer 6, and evaluated by peel strength. Those having a peel strength of 19.6 N or more were evaluated as "good", and those having a peel strength of less than 19.6 N were evaluated as unacceptable, and evaluated as "x".
[0109]
(Evaluation method of interlayer adhesion after weather resistance test)
Regarding the interlayer adhesion after the weather resistance test, the above-described interlayer adhesion was evaluated after the weather resistance test. Those having a peel strength of 10 N or more were evaluated as ○, and those with a peel strength of less than 10 N were rejected. Among the rejects, those with less than 10N and 5N or more were represented by Δ, and those with less than 5N were represented by x. In the weather resistance test, the test piece of the decorative sheet 1 was set on a sunshine weather-o-meter “WEL-300” manufactured by Suga Test Instruments, and a black panel temperature of 63 ° C. and a cycle with a rain of 18 minutes for 120 minutes were used. Irradiation was performed for 1,000 hours under the conditions. The rainy cycle of 18 minutes out of 120 minutes refers to spraying water simulating rain on a test piece for 18 minutes out of 120 minutes.
[0110]
(Evaluation method for scratch resistance)
The scratch resistance is determined by bonding the obtained decorative sheet to a wooden base material for decorative board using a urethane-based adhesive (RL96, manufactured by NSC Japan), and performing a coin scratch test on the decorative board. evaluated. In the coin scratch test, the edge of the coin is placed so that the plane of the 10-yen coin is at an angle of 45 degrees with respect to the decorative sheet coating surface of the decorative board (the outermost protective layer 9), and pressed while applying a load of 500 g. The coin was pulled in a direction perpendicular to the plane of the 10-yen coin, and the appearance of the decorative plate surface was observed and evaluated. Coinscratch evaluation criteria were as follows: A: no damage and no pattern interface peeling, B: slight damage and no pattern interface peeling, C: scratched and no pattern interface peeling, D: pattern interface peeling, and A, B Pass was represented by ○, and C and D were rejected by ×.
[0111]
[Table 1]

[0112]
【The invention's effect】
As described above, according to the present invention, a water-based coating solution containing a water-soluble or water-dispersible ultraviolet absorber and / or a water-soluble or water-dispersible light stabilizer is coated with a colored layer, Since it is used for at least one of the layers and the protective layer, a decorative sheet having excellent weather resistance can be provided. According to the decorative sheet of the present invention, the colored layer and / or the adhesive layer having the adhesive property can be formed between the base material and the transparent resin layer. Further, since the water-based coating liquid is a water-based coating liquid, the amount of volatile VOCs in the working environment and the amount of VOCs remaining in the decorative sheet can be reduced as much as possible. As a result, environmental safety can be further improved. Further, according to the present invention, any of the colored layer, the adhesive layer, and the protective layer may have a non-hydrophilic ultraviolet absorbent and / or a non-hydrophilic property as contained in a conventional solvent-based coating solution. Since a water-based coating liquid containing a light stabilizer is not formed, there is no problem that the weather resistance and adhesive properties of the decorative sheet are deteriorated.
[0113]
Further, according to the aqueous coating liquid of the present invention, a colored layer, an adhesive layer, and a protective layer having weather resistance and adhesive properties can be formed.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view illustrating an example of a layer configuration of a decorative sheet of the present invention.
FIG. 2 is a cross-sectional view showing another example of the layer configuration of the decorative sheet of the present invention.
FIG. 3 is a cross-sectional view showing still another example of the layer configuration of the decorative sheet of the present invention.
FIG. 4 is a sectional view showing an example of an embodiment of the decorative sheet of the present invention.
FIG. 5 is a sectional view showing another example of the embodiment of the decorative sheet of the present invention.
[Explanation of symbols]
1 Makeup sheet
2 Base material
3 Solid colored layer
4 Pattern coloring layer
5 Adhesive layer
6, 6 ', 6 "transparent resin layer
7 Uneven pattern
8 Partially colored layer
9 Protective layer
10 Primer layer
11 Colored layer
12 Adhesive layer
15 adherend
16 Transparent resin layer consisting of multiple layers
17 Recess
41 Three-dimensional articles
51 board

Claims (2)

A decorative sheet in which a base material, a colored layer, an adhesive layer, a transparent resin layer, and a protective layer are laminated in this order,
Water-based coating in which at least one of the coloring layer, the adhesive layer and the protective layer contains a water-soluble or water-dispersible ultraviolet absorber and / or a water-soluble or water-dispersible light stabilizer. Formed of liquid, and
None of the above-mentioned colored layer, adhesive layer, and protective layer are formed of an aqueous coating solution containing a non-hydrophilic ultraviolet absorber and / or a non-hydrophilic light stabilizer. Makeup sheet. A water-based coating liquid containing a water-soluble or water-dispersible ultraviolet absorber and / or a water-soluble or water-dispersible light stabilizer.

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