JP4397572B2 - Cosmetic sheet and water-based coating solution - Google Patents

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／ｍ² 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／ｍ² 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]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative sheet and a water-based coating liquid used for interiors of buildings, surface decorations of fittings, interiors of vehicles, and the like, and more particularly, decorative sheets having improved adhesive properties and weather resistance, such decorative sheets, and the like It is related with the water-system coating liquid which can be used conveniently for.
[0002]
[Prior art]
As a decorative sheet used for the interior of a building, the surface decoration of a fitting, the interior of a vehicle, etc., a base layer, a colored layer composed of a solid colored layer and / or a pattern colored 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 colored layer (also referred to as an ink layer) and an adhesive layer are composed of an aromatic solvent such as toluene or xylene, or an aliphatic solvent such as methyl ethyl ketone or ethyl acetate. It was formed with the solvent-type coating liquid containing. Conventionally, an ultraviolet absorber or a light stabilizer (radical scavenger) has been added to the solvent-based coating liquid for forming a colored layer, an adhesive layer, and the like of such a decorative sheet for the purpose of improving weather resistance. .
[0004]
By the way, 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 VOC), and their use has been demanded to be reduced in recent years. In particular, aromatic solvents such as toluene and xylene are listed as PRTR-designated chemical substances and substances for formulating guideline values for indoor air chemical substances. “Do not use aromatic solvents, use other solvents. There is a strong demand to “decrease.”
[0005]
In particular, in the production of decorative sheets, there are problems in the working environment due to volatilization of VOC contained in the solvent-based coating liquid, and environmental safety due to the supply of VOC remaining in the decorative sheet to the general living space. There are problems. In response to these problems, various means have been proposed to reduce the use of VOCs. For example, Patent Document 2 discloses a decorative sheet in which a colored layer or an adhesive layer is formed with an aqueous coating liquid in which the VOC content is reduced as much as possible. Since such a decorative sheet can further reduce the volatilization amount and residual amount of VOC, it is effective in solving the environmental problems described above.
[Patent Document 1]
JP-A-11-198309
[Patent Document 2]
JP 2001-62970 A
[0006]
[Problems to be solved by the invention]
Conventionally, a colored layer or an adhesive layer formed with an aqueous coating solution obtained by blending an ultraviolet absorber or a light stabilizer (radical scavenger) that has been added to a solvent-based coating solution into an aqueous coating solution. The weather resistance could not be improved as compared with the case of using a conventional solvent-based coating solution.
[0007]
The present inventor tried to form a colored layer or an adhesive layer using an aqueous coating solution to which another type of ultraviolet absorber or the like was added. However, the weather resistance of the decorative sheet cannot be improved, and there is a problem that the adhesion between the base material and the transparent resin layer or between the base material / colored layer and the transparent resin layer is deteriorated. . Such a problem is considered to be largely attributable to the uneven distribution of the added ultraviolet absorber or the like in the aqueous coating solution.
[0008]
Under such circumstances, there has been a demand for improved weather resistance and improved adhesive properties of the colored layer and adhesive layer formed with the aqueous coating solution.
[0009]
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a decorative sheet having improved weather resistance and adhesive properties, and an aqueous coating solution that can be suitably used for such a decorative sheet. Is.
[0010]
[Means for Solving the Problems]
The decorative sheet of the present invention that solves 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 includes the colored layer, the adhesive layer, and the protective layer. Of these, at least one or more layers are formed of a water-based 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 described above The adhesive layer and the protective layer are characterized in that they are not formed with a water-based coating solution containing a non-hydrophilic ultraviolet absorber and / or a non-hydrophilic light stabilizer.
[0011]
According to this invention, the water-soluble or water-dispersible UV absorber and / or the water-soluble or water-dispersible light stabilizer is uniformly dissolved and dispersed without being unevenly distributed in the aqueous coating solution. Therefore, a colored layer, an adhesive layer or a protective layer formed with such an aqueous coating solution has excellent weather resistance and excellent adhesive properties. Furthermore, this aqueous coating liquid can reduce the volatilization amount of VOC in the working environment and the remaining amount of VOC in the decorative sheet as much as possible, and as a result, the environmental safety can be further improved. In addition, the colored layer, the adhesive layer, and the protective layer are all water-based coatings that contain a non-hydrophilic UV absorber and a non-hydrophilic light stabilizer that are contained in conventional solvent-based coating solutions. Since it is not formed with a working liquid, the problem that the weather resistance and adhesive characteristic of a decorative sheet worsen does not arise.
[0012]
In addition, as a specific structure of the decorative sheet of the present invention described above, a concavo-convex pattern is formed on the surface side (between the protective layer) of the transparent resin layer, or a partially colored layer is formed in the concave portion of the concavo-convex pattern Or a primer layer can be formed on the back surface of the substrate.
[0013]
The aqueous coating solution of the present invention that solves the above problems is characterized in that it contains a water-soluble or water-dispersible UV absorber and / or a water-soluble or water-dispersible light stabilizer.
[0014]
According to the present invention, a layer having excellent weather resistance and adhesive properties can be formed.
[0015]
DETAILED DESCRIPTION OF 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 showing an example of the layer structure of the decorative sheet 1 of the present invention. The decorative sheet 1 of the present invention shown in FIG. 1 has a base material 2, a solid colored layer 3, a pattern 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 laminated in order. It is a form made. A primer layer 10 is formed on the back surface of the substrate 2.
[0017]
(Base material)
The base material 2 is an indispensable structure in 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-9-1111055, JP-A-5-77371, Ethylene-propylene-butene copolymer described in Kaihei 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, which has a high degree of crystallinity obtained by the low-pressure method and has few branched structures in the molecule. High-density polyethylene, which is a polymer, is used. As the polypropylene as the hard segment, isotactic polypropylene is preferably used.
[0019]
Diene rubber, hydrogenated diene rubber, olefin elastomer, and the like are used as the elastomer (i) as the soft segment. The hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene rubber molecule, and suppresses the crystallization of the polyolefin 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 to which at least one polyene copolymerizable with two or more olefins is added. Ethylene, propylene, α-olefin, etc. are used as the olefin, 1,4 hexadiene, cyclic diene, norbornene and the like are used. Preferred examples of the olefin elastomer include elastic copolymers containing olefin as a main component such as ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene rubber, and ethylene-butadiene copolymer rubber. Note that these elastomers may be overcrosslinked using a crosslinking agent such as an organic peroxide or sulfur as necessary.
[0020]
The amount of these elastomers added is 10 to 60% by weight, preferably about 30% by weight. If the amount of elastomer added is less than 10% by weight, the change in the constant load elongation becomes too steep, and the elongation at break, impact resistance, and easy adhesion are reduced. When the added amount of the elastomer is higher than 60% by weight, transparency, weather resistance and creep resistance are deteriorated.
[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. As addition amount, it is 1 to 60 weight%, Preferably it is 5 to 30 weight%. When the added amount of the inorganic filler is less than 1% by weight, the creep deformation resistance and the easy adhesion property are lowered. Moreover, when the addition amount of an inorganic filler exceeds 60 weight%, the elongation at break and impact resistance will fall.
[0022]
As the (olefin) olefin resin, a thermoplastic elastomer made of an ethylene / propylene / butene copolymer resin is used. Here, as butene, any of the three structural isomers of 1 butene, 2 butene, and isobutylene can be used. The copolymer is a random copolymer and includes a part of an amorphous part.
[0023]
Preferable specific examples of the ethylene / propylene / butene copolymer resin include the following (a) to (c).
[0024]
(A) A random copolymer made of a terpolymer of ethylene, propylene and butene described in JP-A-9-1111055. In this random copolymer, the weight ratio of the propylene component is preferably 90% by weight or more, and the melt flow rate is 1 to 50 g / 10 min under the conditions of 230 ° C. and 2.16 kg. preferable. Such a random copolymer comprises 0.01 to 50 parts by weight of a transparent nucleating agent mainly composed of a phosphoric acid aryl ester compound and a fatty acid amide having 12 to 22 carbon atoms with respect to 100 parts by weight of the random copolymer. 0.003 to 0.3 parts by weight is melt kneaded.
[0025]
(B) A terpolymer 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 propylene component weight ratio of 50% by weight or more.
[0026]
(C) A terpolymer of ethylene, propylene and 1-butene described in JP-A-7-316358. In this copolymer, propylene and / or 1 butene content was mixed with 20 to 100% by weight of a low crystalline polymer having a content of 50% by weight or more and 80 to 0% by weight of a crystalline polyolefin such as isotactic polypropylene. An oil gelling agent such as N acylamino acid amine salt and N acylamino acid ester is added in an amount of 0.5% by weight to the composition.
[0027]
The ethylene / propylene / butene copolymer resins of the above (a) to (c) may be used alone, or may be further mixed with other polyolefin resins as necessary.
[0028]
As the olefin-based resin (c), as described in Japanese Patent Publication No. 6-23278, the (A) soft segment has a number average molecular weight Mn of 25000 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 with a ratio Mw / Mn ≦ 7, and (B) as a hard segment, an isotactic insoluble in boiling heptane having a melt index of 0.1 to 4 g / 10 min. Examples thereof include soft polypropylene composed of a mixture of 90 to 10% by weight of tic polypropylene.
[0029]
Among the olefinic thermoplastic elastomers (c) above, those composed of a mixture of isotactic polypropylene and atactic polypropylene and having a weight ratio of 5 to 50% by weight of atactic polypropylene are preferably used. Those having a weight ratio of 20 to 40% by weight are particularly preferably used. When the weight ratio of the atactic polypropylene is less than 5% by weight, when embossing or forming into an article having a three-dimensional shape or a concavo-convex shape, deformation of the non-uniform sheet-like substrate due to necking may occur. As a result, wrinkles, pattern distortion, etc. occur. On the other hand, when the weight ratio of the atactic polypropylene exceeds 50% by weight, the sheet-like base material itself is easily deformed, and the base material is deformed when the base material is passed through a printing machine, and the pattern of the colored layer 11 is distorted. In addition, defects such as misregistration are likely to occur in the case of multicolor printing, and the sheet is easily torn during molding.
[0030]
A colorant, a heat stabilizer, a flame retardant, an ultraviolet absorber, a radical scavenger, and the like are added to the above-described olefin resin forming the substrate 2 as necessary.
[0031]
Coloring agents include titanium white, zinc white, red bean, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, etc. Organic pigments or dyes, metallic 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, and the like are used. Moreover, you may add an inorganic filler in the ratio of 5 to 60 weight% as needed. Examples of the inorganic filler include powders of calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), alumina (aluminum oxide), and the like. The colorant is added to give the base material 2 a color necessary for the decorative sheet 1, and may be either transparent coloring or opaque (concealing) coloring, but generally the concealment of the adherend 15. Opaque coloring is preferred.
[0032]
As the heat stabilizer, known ones such as phenol, sulfite, phenylalkane, phosphite, and amine can be used, and the prevention of deterioration such as thermal discoloration during heat processing can be improved. A flame retardant is added when imparting flame retardancy, and powders such as aluminum hydroxide and magnesium hydroxide are used. The ultraviolet absorber is for imparting better weather resistance (light resistance) to the resin, and is an organic substance such as benzotriazole, benzophenone, salicylic acid ester, or particulate 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 in which an acryloyl group or a methacryloyl group is introduced into the benzotriazole skeleton is also used. In addition, the addition amount of these ultraviolet absorbers is about 0.5 to 10 weight% normally. 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 compounds disclosed in JP-B-4-82625, biperidinyl radical scavengers, etc. Is done.
[0033]
The base material 2 can be obtained by forming a film obtained by arbitrarily selecting and blending the above materials by a conventional method such as calendering. The thickness of the base material 2 is 50-200 micrometers, Preferably it is about 100 micrometers.
[0034]
The surface of the substrate 2 on the surface side (transparent resin layer 6 side) of the decorative sheet 1 is preferably subjected to easy adhesion treatment such as application of an easy adhesion layer, corona discharge treatment, plasma treatment, ozone treatment and the like. 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 composed of the above-described polyolefin 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 substrate 2. In addition, thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, fine paper, coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, etc. A so-called vinyl wallpaper original fabric obtained by sol coating or dry laminating vinyl can also be used. Further, a sheet or film made of inorganic fibers such as glass fibers, asbestos, potassium titanate fibers, alumina fibers, silica fibers, and carbon fibers can be used as the substrate 2. Moreover, metal foils, such as aluminum, iron, stainless steel, copper, etc. can also be used. Further, a material obtained by laminating a plurality of such base material materials can be used as the base material 2.
[0036]
(Colored layer)
The colored layer 11 is an essential layer in the decorative sheet 1 and is composed of the solid colored layer 3 and / or the pattern colored layer 4.
[0037]
As shown in FIG. 1, the solid colored layer 3 is provided for the purpose of concealing the background of the substrate 2, and is usually formed as a solid solid colored layer without a pattern. On the other hand, the pattern coloring layer 4 has a pattern or color composed of a wood grain pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, etc., depending on figures, characters, symbols, colors, combinations thereof, etc. On the colored layer 3, it is formed as a layer having a planar shape, an uneven shape, or a convex shape (see FIG. 1). Note that the pattern coloring layer 4 may also function as the solid coloring layer 3, and in this case, the pattern coloring layer 4 becomes the solid coloring layer 3. The solid colored layer 3 and / or the pattern colored layer 4 thus formed may be provided on the entire surface of the substrate 2 or may be partially provided. Further, as shown in FIG. 1, the colored layer 11 is composed of a solid colored layer 3 provided on the entire surface of the substrate 2 and a pattern colored layer 4 partially provided on the surface of the solid colored layer 3. You can also
[0038]
In the decorative sheet 1 of the present invention, at least one of the colored layer 11, the adhesive layer 5 and the protective layer 9 is a water-soluble or water-dispersible UV absorber and / or a water-soluble or water-dispersible layer. It is formed with an aqueous coating solution containing a light stabilizer (hereinafter, unless otherwise specified, “this coating solution is referred to as an“ aqueous coating solution ”). Therefore, the colored layer coating solution for forming the colored layer is also preferably such an aqueous coating solution. The aqueous coating solution will be described in detail in the description of the adhesive layer 5.
[0039]
The decorative sheet 1 provided with the colored layer 11 formed with the aqueous coating liquid for the colored layer can further improve the adhesive properties, weather resistance, and environmental safety. In addition, when the adhesive layer 5 or the protective layer 9 is formed with the aqueous coating solution according to the present invention, the colored layer is formed with an aqueous coating solution or a solvent-based coating solution that does not contain an ultraviolet absorber or a light stabilizer. 11 may 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 the colored layer is basically composed of an ultraviolet absorber and / or a light stabilizer, a main agent, a crosslinking agent, and a solvent. The ultraviolet absorber and / or the light stabilizer are blended at a ratio of 0.001 to 10 when the coating liquid composed of the main agent, the crosslinking agent and the solvent (aqueous system) is taken as 100. When both the ultraviolet absorber and the light stabilizer are blended, the blending ratio of the ultraviolet absorber: the light stabilizer is not particularly limited. The mixing ratio of the main agent: crosslinking agent is 100: 0.5 to 100: 100, preferably 100: 5 to 100: 20. Moreover, the mixing | blending ratio of a solvent is mix | blended in the ratio of 50-400 when the sum of a main ingredient and a crosslinking agent is set to 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 colored coating liquid, an aqueous polyester resin-based colored coating liquid, and an aqueous acrylic resin-based coloring. Coating liquids, water-based epoxy resin-based color coating liquids, water-based urethane acrylic resin-based color coating liquids, water-based casein resin-based color coating liquids, and color coating liquids composed of mixtures of these resins are used. .
[0042]
As the solvent-based coating liquid for the colored layer, as a resin component contained in the solvent-based coating liquid, a colored coating liquid containing a mixture of an oil-based (meth) acrylic resin and an oil-based urethane resin that can be mixed with each other Is used. For example, examples of the (meth) acrylic resin include 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 a raw material. When 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 is contained 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 substrate 2 and the transparent resin layer 6 may not be improved. As the solvent, ester organic solvents such as methyl acetate and butyl acetate, and ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone are usually used. Such solvent-based coating liquids can contain conventionally used ultraviolet absorbers and light stabilizers.
[0043]
In the present invention, any of the colored layer 11, the adhesive layer 5, and the protective layer 9 is an aqueous coating solution containing a non-hydrophilic UV absorber and / or a non-hydrophilic light stabilizer. Is not formed. Therefore, even this colored layer 11 is not formed with such an aqueous coating solution. As a result, the weather resistance and adhesive properties of the formed decorative sheet do not deteriorate.
[0044]
Organic or inorganic pigments can be used as the color pigments contained in the various colored layer coating liquids described above. For example, as yellow pigments, azo pigments such as monoazo, disazo and polyazo, organic pigments such as isoindolinone, inorganic pigments such as yellow lead, 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 petals, vermilion, cadmium red and chrome vermilion can be used. As the blue pigment, organic pigments such as phthalocyanine blue and indanthrene blue, and inorganic pigments such as bitumen, ultramarine blue, and cobalt blue can be used. Moreover, as a black pigment, organic pigments, such as aniline black, and inorganic pigments, 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. Moreover, fillers, such as a silica, volume pigments, such as an organic bead, a neutralizing agent, surfactant, etc. can be contained arbitrarily.
[0045]
The colored layer coating liquid used for the solid colored layer 3 and the pattern colored layer 4 is a wax, a dispersant, an antifoam, in addition to the above-described ultraviolet absorber and light stabilizer, depending on the type of the coating liquid. An agent, a leveling agent, a stabilizer, a filler, a lubricant, a lubricant, and other additives are optionally added, and the mixture is sufficiently mixed with a mixer or the like.
[0046]
The solid colored layer 3 and the pattern colored layer 4 are formed by applying the above-described various colored layer coating liquids by coating or printing, and then drying. More specifically, the solid colored layer 3 is usually formed by applying or printing a solid colored layer coating solution, followed by drying and curing. The pattern coloring layer 4 is also formed by applying or printing a pattern coloring layer coating solution, followed by drying and curing. As coating methods, 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, spray coating. It is possible to use a method such as flow coating or brush coating. As printing methods, various known methods such as letterpress printing such as gravure, letterpress and flexo, planographic printing such as planographic offset and dilitho printing, stencil printing such as silk screen, electrostatic printing, and ink jet printing are used. Can do. The solid colored layer 3 is coated or printed so that the film thickness after drying is about 0.5 to 10 μm, and the pattern colored layer 4 is about 0.1 to 10 μm after drying. 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, and provides adhesion between the base material 2 or the base material 2 / colored layer 11 and the transparent resin layer 6. It has a role as an improved primer layer or anchor layer, and has the effect of improving durability and long-term appearance maintenance. Such an action can hold the formed pattern for a long time and is extremely effective.
[0048]
The adhesive layer 5 is preferably formed of an aqueous coating solution for an adhesive layer containing a water-soluble or water-dispersible ultraviolet absorber and / or a water-soluble or water-dispersible light stabilizer. In this adhesive layer aqueous coating solution, since the ultraviolet absorber and the light stabilizer contained therein are water-soluble or water-dispersible, these ultraviolet absorber and light stabilizer can be dissolved or uniformly dissolved in the coating solution. scatter. In the adhesive layer formed with such a coating liquid, since the ultraviolet absorber and the light stabilizer are present in a uniformly dispersed state, the decorative sheet obtained by forming the adhesive layer with a conventional aqueous coating liquid is used. Compared to the weather resistance, the weather resistance can be improved.
[0049]
The adhesive layer 5 formed with the aqueous coating liquid for adhesive layer is excellent by being provided between the substrate 2 and the transparent resin layer 6 or between the substrate 2 / colored layer 11 and the transparent resin layer 6. Show adhesive properties. Furthermore, since the aqueous coating liquid for the adhesive layer is an aqueous coating liquid, it is possible to reduce the amount of VOC volatilized in the working environment and the remaining amount of VOC in the decorative sheet as much as possible, thereby further improving environmental safety. Can be improved.
[0050]
The water-based coating liquid for the adhesive layer is: (1) water-soluble or water-dispersible UV absorber and / or water-soluble or water-dispersible light stabilizer, (2) main agent and crosslinking agent, (3) water Or the mixed solvent which consists of water, alcohol, etc. is contained.
[0051]
(1) Water-soluble or water-dispersible UV absorbers / water-soluble or water-dispersible light stabilizers; Examples of water-dispersible UV absorbers include compounds of the following chemical formula 1 (molecular weight: 315, melting point: 139 ° C., CAS-No. 3896-11-5) treated with a hydrophilic agent with an emulsifier or the like (specific gravity 1.094, viscosity: 225 mPa · s (cps)).
[0052]
[Chemical 1]

[0053]
As other water-soluble or water-dispersible ultraviolet absorbers, those obtained by introducing an ultraviolet absorber component into the water-soluble and / or water-dispersible resin molecules can also be used. For example, an ultraviolet absorber component composed of a compound of the following chemical formula 2 (monomer molecular weight: 323, CAS-No. 96478-09-0), a hydrophilic component, methyl methacrylate, styrene, etc. are copolymerized by radical polymerization. The water-based resin made into can be mentioned.
[Chemical formula 2]

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) for each resin. Determined. 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 rendered hydrophilic by neutralization and a component that is hydrophilic in itself. Examples of those that can be rendered hydrophilic by neutralization include carboxyl groups, sulfonic acid groups, phosphoric acid groups, tertiary amino groups, and quaternary amino groups. In this case, the neutralizing agent is not particularly limited as long as it can be neutralized or ionized. 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 hydrophilicity include a hydroxyl group and an ether bond. Among these, from the viewpoint of improving the weather resistance, a compound having a hydroxyl group introduced is preferably used. In addition, the content rate of the compound which is an ultraviolet absorber component is adjusted in 0.01-50 weight% with respect to 100 weight% of copolymer compounds.
[0054]
As another example of the ultraviolet absorber in which the ultraviolet absorber component is introduced into the molecule of the water-soluble and / or water-dispersible resin, for example, the water-soluble and water-dispersible ultraviolet absorber copolymer is a prepolymer. And polyurethane resins, polyester resins, acrylic resins, vinyl resins, and the like. In addition, the aqueous resin which introduce | transduced the ultraviolet absorber into the molecule | numerator can also play the role of the main ingredient mentioned later.
[0055]
As a water dispersible light stabilizer (radical scavenger), for example, a compound of the following chemical formula 3 (molecular weight: about 900, specific gravity: 0.98, viscosity: 7000 mPa · s (cps), CAS-No. 98-3,84696-72-0,107119-91-5) treated with water dispersibility with an emulsifier or the like (specific gravity 0.999, viscosity: 45 mPa · s (cps)).
[0056]
[Chemical 3]

The water-soluble or water-dispersible UV absorber and / or light stabilizer is blended at a ratio of 0.001 to 10 when the coating liquid composed of the main agent, crosslinking agent and solvent (aqueous) is taken as 100. The When both the ultraviolet absorber and the light stabilizer are blended, the blending ratio of the ultraviolet absorber: the light stabilizer is not particularly limited.
[0057]
(2) Main agent and crosslinking agent;
Examples of the main agent include polyurethane resin, polyester resin, acrylic resin, vinyl resin, epoxy resin and the like, copolymers thereof, and mixtures thereof. Such a main agent is required to have a functional group that reacts with the crosslinking agent component.
[0058]
Examples of the crosslinking agent include isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, silanol group-containing compounds, and the like. Among these, it is preferable to use an isocyanate compound.
[0059]
The mixing ratio of the main agent: crosslinking agent is 100: 0.5 to 100: 100, preferably 100: 5 to 100: 20.
[0060]
{Circle around (3)} The water used as the solvent is industrial water of the grade conventionally used for aqueous coating solutions. A mixed solvent composed of water and alcohol can also be used as a solvent for the aqueous coating solution. Examples of alcohols constituting such a mixed solvent include lower alcohols such as ethanol, isopropyl alcohol and n-propyl alcohol, glycols and esters thereof. These solvents such as lower alcohols, glycols and esters thereof are used for the purpose of improving the fluidity of the aqueous coating liquid, improving the wetness of the colored layer as the coated body, and adjusting the drying property. The type, amount used, etc. are determined according to the purpose. The aqueous coating liquid used in the present invention does not use high-risk aromatic hydrocarbon organic volatile substances such as benzene, toluene, xylene, etc., and also suppresses the use of other organic solvents. Therefore, the occurrence of VOC can be reduced.
[0061]
In a mixed solvent composed of water and alcohol, the blending ratio of water: alcohol and the like (for example, isopropyl alcohol, methanol, ethanol, n-propyl alcohol, etc.) = 20:80 to 100: 0. It can be adjusted within the range. Moreover, it is preferable to mix | blend the mixture ratio of the solvent in an aqueous coating liquid in the ratio of 50-400, when a main ingredient and a crosslinking agent are set to 100.
[0062]
In addition to the above UV absorbers and light stabilizers, additives such as colorants, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, lubricants, etc., are optionally added to the aqueous coating solution. May be.
[0063]
The aqueous coating solution for the adhesive layer is composed of (1) ultraviolet absorber and / or light stabilizer, (2) main agent and cross-linking agent, and (3) aqueous solvent in the above proportions, and is sufficient with a mixer or the like. It is prepared by mixing.
[0064]
In the case where the colored layer 11 and / or the protective layer 9 is formed of the aqueous coating solution of the present invention, the adhesive layer 5 is made of an aqueous coating solution containing no ultraviolet absorber or light stabilizer, or a solvent. Although it can be formed by a system coating solution or a solventless coating agent, it is most preferably formed by using the aqueous coating solution of the present invention.
[0065]
Examples of the solvent-based coating solution include a two-component oily urethane resin, a mixture of an oily acrylic resin and an oily urethane resin, and the like. The two-component oil-based urethane resin contains an oil-based urethane resin and an isocyanate that is 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, and 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 contains 10 to 100% by weight. It is preferable.
[0066]
Examples of the solventless (non-sol) coating agent include those composed of a polyol compound and a polyisocyanate compound. Examples of the polyol compound include polyester polyol and polyether polyol. Examples of the polyisocyanate compound include polyfunctional polyisocyanate compounds such as isocyanurates, burettes, and allophanates derived from polyisocyanate monomers such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, or Examples thereof include polyfunctional polyisocyanate compounds containing terminal isocyanate groups obtained by reaction with trifunctional or higher functional polyol compounds such as trimethylolpropane and glycerin.
[0067]
Examples of the ultraviolet absorber added to the solvent-based coating solution and the solvent-free coating agent include organic substances such as benzotriazole, benzophenone, triazine, and salicylic acid ester, and inorganic substances such as zinc oxide, cesium oxide, and titanium oxide. 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, bis- (N-methyl-2,2,6,6-tetramethyl-4-biperidinyl). Hindered radical scavengers, biperidinyl radical scavengers and the like such as sebacate and other compounds disclosed in JP-B-4-82625 can be used.
[0068]
In the present invention, any of the colored layer 11, the adhesive layer 5, and the protective layer 9 is an aqueous coating solution containing a non-hydrophilic UV absorber and / or a non-hydrophilic light stabilizer. Is not formed. Therefore, even this adhesive layer 5 is not formed with such an aqueous coating solution. Here, non-hydrophilic ultraviolet absorbers and non-hydrophilic light stabilizers are substances whose compounds themselves do not dissolve in water and do not stably disperse in water. In other words, it contains substances that are not stabilized in water even when dispersed in water. Therefore, among the ultraviolet absorbers and light stabilizers added to the solvent-based coating liquid and the solvent-free 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 an adhesive layer formed with the aqueous coating solution In some cases, the adhesive properties and the like are deteriorated.
[0069]
The adhesive layer 5 is formed by providing the above-described adhesive layer coating solution on the colored layer 11 by coating or printing, and then drying. As coating methods, 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, spray coating. A method such as flow coating or brush coating can be used, and the 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, and is provided through the adhesive layer 5 for the purpose of protecting the colored layer 11 from scratches, improving the surface strength of the decorative sheet 1, and imparting a feeling of painting. And 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 that is formed in close contact with the colored layer 11 via the adhesive layer 5 described above. Preferred are olefin resins. 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 substrate 2 can be used. Known resins such as a colorant, 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 separately formed transparent resin sheets 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 different effects can be imparted to the transparent resin layer 6 ′ on the substrate 2 side and the transparent resin layer 6 ″ on the protective layer side. As one specific example, the transparent resin layer 6 ″ on the protective layer side is formed of a resin mainly composed of a fluorine-based resin such as vinylidene fluoride to give excellent surface functions such as stain resistance. The material-side transparent resin layer 6 ′ can be formed of a thermoplastic (meth) acrylic resin or the like to improve the adhesion between the adhesive layer 5 and the like. 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 give excellent weather resistance, and the transparent resin layer 6 ′ on the substrate side is given. Can be formed of a polypropylene-based resin containing an elastomer to improve weather resistance and adhesion.
[0074]
The two or more transparent resin layers 16 are formed by melt coextrusion of a plurality of resin compositions, or by various lamination methods such as dry lamination and thermal lamination. At this time, as shown in FIG. 3, a transparent resin layer 16 composed of two or more layers can be formed through an adhesive layer 12 acting as a primer layer or an anchor layer. In this case, the adhesive layer 12 is formed by melt coextrusion with the transparent resin layers 6 ′ and 6 ″, or is formed by applying with an aqueous coating solution containing an aqueous urethane resin. , Generation of VOC can be further suppressed.
[0075]
The thickness of the transparent resin layer 6 is about 20 to 300 μm, and 15 to 400 g / m when formed with a coating solution. ² Apply at a coating amount of about.
[0076]
(Uneven pattern)
The uneven pattern 7 is also referred to as an embossed pattern, and is formed on the surface of the transparent resin layer 6 as necessary, as shown in FIG. In addition, 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 formed on the transparent resin layer other than the outermost surface. You can do it.
[0077]
The uneven pattern 7 is not particularly limited as long as it is a pattern according to the use of the decorative sheet 1. For example, wood grain conduit groove, wood grain annual ring irregularity, floatation annual ring irregularity, wood grain irregularity, sand grain, pear texture, hairline, line-shaped groove, granite cleaved surface stone texture irregularity, textured surface texture, leather squeezing, text, geometry Examples include academic patterns.
[0078]
Examples of means for forming the concavo-convex pattern 7 include an embossing method by heat and pressure and a T-die melt extrusion method. The embossing method by heat and pressure is a method in which the surface of the transparent resin layer 6 is heated and softened, the surface is pressed with an embossing plate to form an uneven pattern 7 of the embossing plate, and cooled and fixed. A known single-wafer or rotary embossing machine is used. When forming a concavo-convex pattern by the embossing method, embossing is performed in advance on the transparent resin layer sheet before lamination by laminating, or simultaneously embossing the transparent resin layer sheet (so-called doubling embossing method). To do. When the transparent resin layer 6 is laminated by the T-die melt extrusion method, a cooling roller that also serves as a shaping roller is used, and the uneven pattern 7 is formed simultaneously with the formation and lamination of the transparent resin layer 6. The embossed pattern can also be formed by hairline processing, sandblasting, or the like.
[0079]
(Partial colored layer)
The partially colored layer 8 is formed in the recessed portion 17 of the concavo-convex pattern 7 by a wiping method. In the wiping method, the coating liquid for the partially colored layer is applied to the entire surface including the recessed portion 17 by the doctor blade coating method or the knife coating method, and then the coating solution for the partially colored layer is applied from the surface other than the recessed portion 17. This is a method of forming the partially colored layer 8 only in the recessed portion 17 by removing the same. As the coating liquid for the partially colored layer, a coating composed of a colored pigment such as an organic pigment, an inorganic pigment, or a glitter pigment, and a binder resin such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation curable resin. Or an emulsion-type aqueous coating solution can be used.
[0080]
Moreover, the aqueous coating liquid which forms the above-mentioned solid coloring layer 3 and / or pattern coloring layer 4 can also be used preferably, and in such a case, it is more preferable at the point of environmental safety.
[0081]
(Protective layer)
The protective layer 9 is also referred to as a topcoat layer or an overprint layer (OP layer), and covers the surface of the recessed portion 17 that forms the concavo-convex pattern 7 or the partially colored layer 8 that is formed in the recessed portion 17 so as to cover the decorative sheet 1. It is provided for the purpose of protecting. Specifically, the decorative sheet 1 is protected by improving surface physical 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 adhesive layer described above, and in particular, the decorative sheet 1 having a protective layer excellent in weather resistance and light resistance. The decorative sheet 1 that can be provided and has improved environmental safety by suppressing the occurrence of VOC can be provided.
[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 crosslinking agent and a solvent, and the ultraviolet absorber, the light stabilizer and the solvent are provided at the adhesive layer. The same as described can be used. In addition, as a main ingredient, a polyurethane resin, a polyester resin, an acrylic resin, a vinyl resin, an epoxy resin etc., these copolymers, a mixture, etc. are mentioned, for example. Such a main agent is required to have a functional group that reacts with the crosslinking agent component. Examples of the crosslinking agent include isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, silanol group-containing compounds, and the like. Among these, it is preferable to use an isocyanate compound. Note that an ionizing radiation curable resin may be used for the aqueous coating solution. The mixing ratio of the main agent: 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 composed of the main agent, the crosslinking agent and the solvent (aqueous system) is taken as 100. When both the ultraviolet absorber and the light stabilizer are blended, the blending ratio of the ultraviolet absorber: the light stabilizer is not particularly limited. The mixing ratio of the main agent: crosslinking agent is 100: 0.5 to 100: 100, preferably 100: 5 to 100: 20. Moreover, the mixing | blending ratio of a solvent is mix | blended in the ratio of 50-400 when the sum of a main ingredient and a crosslinking agent is set to 100.
[0085]
In the case where the colored layer 11 and / or the adhesive layer 5 is formed of the aqueous coating solution of the present invention, the protective layer 9 is an aqueous coating solution containing no ultraviolet absorber or light stabilizer. Although it can be formed with a solvent-based coating solution or a solvent-free coating solution, it is most preferably formed using the water-based coating solution of the present invention. In particular, it is most preferable to form all of the colored layer 11, the adhesive layer 5, and the protective layer 9 with the aqueous coating solution of the present invention.
[0086]
Solvent-based coating liquids include acrylic resins, polyurethane resins, epoxy resins, and the like, copolymers of these, or mixtures thereof, and those using crosslinker components such as isocyanate compounds and epoxy compounds, or ionization. A material that is cured by irradiating with ionizing radiation after coating the curable radiation curable resin can be used. As the solventless coating solution, a coating solution 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 solution and a solvent-free coating solution in order to impart good weather resistance and light resistance to the protective layer 9.
[0087]
In the present invention, any of the colored layer 11, the adhesive layer 5, and the protective layer 9 is an aqueous coating solution containing a non-hydrophilic UV absorber and / or a non-hydrophilic light stabilizer. Is not formed. Therefore, this protective layer 9 is not formed with such an aqueous coating solution. As a result, the weather resistance and adhesive properties of the formed decorative sheet do not deteriorate.
[0088]
The protective layer 9 can be one that has been gloss-adjusted by adding a known matting agent such as silica to the coating solution, or one that has been given a design such as a feeling of painting. Examples of other additives include colorants, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, lubricants, antistatic agents, flame retardants, and the like.
[0089]
The protective layer 9 is formed by coating and forming the above-described various coating liquids 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 other coating methods. Moreover, it forms by well-known printing methods, 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 side of the substrate 2 for the purpose of facilitating bonding of the decorative sheet 1 of the present invention to various adherends 15. The primer layer 10 is formed using (meth) acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, or the like. From the viewpoint of environmental safety, it is preferable to use a water-based coating liquid that is preferably used to form 5.
[0091]
(Decorative sheet)
As described above, the decorative sheet 1 obtained by forming each layer (colored layer, adhesive layer, protective layer) using the aqueous coating liquid according to the present invention is a conventional aqueous coating liquid. As compared with the decorative sheet obtained by forming the layer, the weather resistance can be improved.
[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]
As the adherend 15, a three-dimensional article 41 as shown in FIG. 4, an article of various shapes such as a flat plate or curved plate 51, a sheet (or film) as shown in FIG. . Examples of the adherend 15 include a wood veneer such as a wood veneer, a wood plywood, a particle board, and a medium density fiber board (MDF), a wood board such as a wood fiber board, a metal such as iron and aluminum, (meth) acryl, Polyester, polystyrene, polyolefin, ABS resin, phenol resin, polyvinyl chloride resin, cellulose resin, rubber resin, glass, ceramics such as ceramics, non-cement ceramic materials such as gypsum, fine paper, Japanese paper, etc. Nonwoven fabrics or woven fabrics made of fibers such as carbon, asbestos, potassium titanate, glass, synthetic resin, and the like.
[0094]
In the relationship between the decorative sheet 1 and the adherend 15, when the adhesive sheet 1 can be directly bonded to the adherend 15 by heat fusion or the like depending on the type of the base material 2 or the primer layer 10 of the decorative sheet 1, the decorative sheet 1 and the adherend 15 are covered. Although it is possible to laminate the adherend 15 without using an adhesive, depending on the type of the base material 2 or the primer layer 10 of the decorative sheet 1, if it cannot be directly adhered to the adherend 15 by heat fusion or the like, Laminate using a suitable adhesive. Examples of the adhesive include vinyl acetate-based and urea-based adhesives.
[0095]
Further, as a general lamination method, for example, (a) a method of laminating the adherend 15 by pressing with a pressure roller via an adhesive, (b) Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43 As described in JP-A-27488, etc., the decorative sheet 1 is inserted between both male and female molds for injection molding, both molds are closed, the molten resin is injected and filled from the male mold gate, and then cooled. An injection molding simultaneous laminating method in which the decorative sheet 1 is adhered and laminated on the surface of the resin molded product at the same time, (c) an adhesive as described in JP-B-56-45768 and JP-B-60-58014 A vacuum press laminating method in which the decorative sheet 1 is opposed to the surface of the molded product through the pressure and the decorative sheet 1 is laminated on the molded product surface by a pressure difference due to vacuum suction from the molded product side, (d) Japanese Patent Publication No. 61-5895 Gazette, Japanese Patent Publication 3-26 As described in Japanese Patent Publication No. 6 etc., columnar adherence is provided by a plurality of differently oriented rollers while supplying the decorative sheet 1 via an adhesive in the long axis direction of a columnar adherend such as a cylinder or a polygonal column. Examples include a lapping process method in which the decorative sheet 1 is sequentially pressure-bonded and laminated on a plurality of side surfaces constituting the body.
[0096]
The various adherends 15 on which the decorative sheet 1 of the present invention is laminated are subjected to a predetermined molding process and the like, and are used as various decorative materials. For example, interior decorations for buildings such as walls, ceilings, floors, surface decorations for furniture such as window frames, doors, handrails, surface decorations for furniture or cabinets for light electrical / OA equipment, vehicle interiors such as cars and trains, aircraft interiors, windows Uses such as glass for cosmetics are listed.
[0097]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following, “part” means “part by weight”.
[0098]
Example 1
A polypropylene elastomer colored sheet PB013 (thickness: 60 μm) manufactured by Mitsubishi Chemical MKV Co., Ltd. is used as the base material 2, and a corona discharge treatment is performed thereon, and then a gravure plate with a line number of 54 lines / inch and a plate depth of 40 μm is prepared. A solid colored layer aqueous coating solution A and a pattern colored layer aqueous coating solution B having the following composition were sequentially applied and dried by a gravure printing method to obtain a solid colored layer 3 of about 3 μm and a patterned colored layer 4 of about 1 μm. Were sequentially formed.
Furthermore, using a gravure plate having a line number of 54 lines / inch and a plate depth of 40 μm, an aqueous coating solution a for an adhesive layer having the following composition is obtained by a gravure printing method at about 3 g / m ² It was applied and dried so that an adhesive layer 5 having a thickness of 3 μm was formed after drying.
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 further, a gravure plate having a line number of 54 lines / inch and a plate depth of 40 μm is used to form an aqueous coating for a protective layer having the following composition. The working liquid C was applied and dried by a gravure printing method to form a protective layer 9 of about 3 μm. Then, the decorative sheet of Example 1 was obtained by curing at a temperature of 25 ° C. for 7 days.
[0099]
Aqueous coating solution A for solid colored layers ;
Aqueous urethane-based white ink (no added UV absorber, etc .; made by The Inktec, Ode WKE white solid): 100 parts, water-dispersible isocyanate crosslinking agent (manufactured by Nikka Chemical Co., Ltd., X9003): 5 parts, water-dispersed UV absorber (Asahi Denka Kogyo Co., Ltd., LX-301): 1 part, water dispersible light stabilizer (Asahi Denka Kogyo Co., Ltd., LX-332): 1 part, water: 20 parts, isopropyl alcohol: 20 copies
Aqueous coating solution B for pattern colored layer ;
Water-based urethane yellow ink (no added UV absorber, etc .; manufactured by The Inktec, Ode WKE Yellow): 100 parts, water-dispersible UV absorber (Asahi Denka Kogyo Co., Ltd., LX-301): 1 part, water Dispersible light stabilizer (Asahi Denka Kogyo Co., Ltd., LX-332): 1 part, water: 20 parts, isopropyl alcohol: 20 parts
Aqueous coating solution for adhesive layer a ;
Aqueous urethane resin (no added UV absorber, etc .; manufactured by Nikka Chemical Co., Ltd., HO14): 100 parts, water-dispersible isocyanate crosslinking agent (manufactured by Nikka Chemical Co., Ltd., X9003): 5 parts, water-dispersible ultraviolet absorber (Asahi Denka Kogyo Co., Ltd., LX-301): 1 part, water dispersible light stabilizer (Asahi Denka Kogyo Co., Ltd., LX-332): 1 part, water: 20 parts, isopropyl alcohol: 20 parts
Water-based coating liquid for protective layer b ;
Aqueous urethane resin (no UV absorber added; Showa Ink Industries, Ltd., 135): 100 parts, water-dispersible isocyanate crosslinking agent (manufactured by Nikka Chemical Co., Ltd., X9003): 5 parts, water-dispersible UV absorption Agent (Asahi Denka Kogyo Co., Ltd., LX-301): 1 part, Water dispersible light stabilizer (Asahi Denka Kogyo Co., Ltd., LX-332): 1 part, Water: 20 parts, Isopropyl alcohol: 20 parts
[0100]
(Example 2)
Instead of the solvent-based coating solution a for the adhesive layer of Example 1, a solvent-based coating solution c for the adhesive layer having the following composition was used. Otherwise, the decorative sheet of Example 2 was obtained in the same manner as Example 1.
Solvent-based coating solution for adhesive layer c ;
100 parts of a polyester resin adhesive (containing an ultraviolet absorber and a light stabilizer; manufactured by Dainichi Seika Kogyo Co., Ltd., E295L-NT), 10 parts of an isocyanate cross-linking agent (manufactured by Dainichi Seika Kogyo Co., Ltd., C55), ethyl acetate : 80 parts
[0101]
(Example 3)
Instead of the adhesive layer aqueous coating solution a of Example 1, an adhesive layer aqueous coating solution d having the following composition was used. Otherwise, the decorative sheet of Example 3 was obtained in the same manner as Example 1.
Adhesive layer aqueous coating solution d ;
Aqueous urethane resin (no added UV absorber, etc .; manufactured by Nikka Chemical Co., Ltd., HO14): 100 parts, water-dispersible isocyanate crosslinking agent (manufactured by Nikka Chemical Co., Ltd., X9003): 5 parts Aqueous resin (Otsuka Chemical Co., Ltd., PUVA-30W): 1 part, water dispersible light stabilizer (Asahi Denka Kogyo Co., Ltd., LX332): 1 part, water: 20 parts, isopropyl alcohol: 20 parts
[0102]
Example 4
Instead of the protective layer aqueous coating solution b of Example 1, a protective layer aqueous coating solution e having the following composition was used. Otherwise, the decorative sheet of Example 4 was obtained in the same manner as Example 1.
Water-based coating liquid for protective layer e ;
Water-based urethane resin (no added UV absorber, etc .; Showa Ink Industries, Ltd., 135): 100 parts, water-dispersible isocyanate crosslinking agent (manufactured by Nikka Chemical Co., Ltd., X9003): 5 parts, molecular UV absorber Aqueous resin (Otsuka Chemical Co., Ltd., PUVA-30W): 1 part, water dispersible light stabilizer (Asahi Denka Kogyo Co., Ltd., LX332): 1 part, water: 20 parts, isopropyl alcohol: 20 Part
[0103]
(Example 5)
Instead of the method for forming the transparent resin layer 6 in Example 1, a method for forming by a melt extrusion method was used. Specifically, 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 on the adhesive layer 5, respectively. The resin was extruded in a molten state by a T-die, and a transparent resin layer 6 having a thickness of 80 μm was laminated by heat at 180 ° C. Otherwise, the decorative sheet of Example 5 was obtained in the same manner as Example 1.
[0104]
(Comparative Example 1)
Instead of the solid colored layer aqueous coating solution A and the pattern colored layer aqueous coating solution B of Example 1, the solid colored layer aqueous coating solution C and the pattern colored layer aqueous coating solution D of the following composition were used. Using. Otherwise, the decorative sheet of Comparative Example 1 was obtained in the same manner as Example 1.
Water-based coating liquid C for solid colored layers ;
Aqueous urethane-based white ink (no added UV absorber, etc .; made by The Inktec, Ode WKE white solid): 100 parts, water-dispersible isocyanate crosslinking agent (manufactured by Nikka Chemical Co., Ltd., X9003): 5 parts, UV absorbing Agent (Asahi Denka Kogyo Co., Ltd., LA-36): 0.3 parts, Light stabilizer (Asahi Denka Kogyo Co., Ltd., LA-62): 0.3 parts, Water: 20 parts, Isopropyl alcohol: 20 parts
Aqueous coating solution D for pattern colored layer ;
Aqueous urethane-based yellow ink (no UV absorber added; The Inktec, Ode WKE Yellow): 100 parts, UV absorber (Asahi Denka Kogyo Co., Ltd., LA-36): 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 adhesive layer aqueous coating solution a of Example 1, an adhesive layer aqueous coating solution f was used. Otherwise, the decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1.
Adhesive layer aqueous coating solution f ;
Aqueous urethane resin (no UV absorber added, Nikka Chemical Co., Ltd., HO14): 100 parts, water-dispersible isocyanate crosslinking agent (Nikka Chemical Co., Ltd., X9003): 5 parts, UV absorber (Asahi Denka Co., Ltd.) 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 protective layer aqueous coating solution b in Example 1, a protective layer aqueous coating solution g having the following composition was used. Otherwise, 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 (no UV absorber added; Showa Ink Industries, Ltd., 135): 100 parts, water-dispersible isocyanate crosslinking agent (Nikka Chemical Co., Ltd., X9003): 5 parts, UV 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)
Evaluation of interlayer adhesion of each decorative sheet obtained in Examples 1-4 and Comparative Examples 1-3, interlayer adhesion after a weather resistance test, and scratch resistance was performed by the following methods. The obtained results are shown in Table 1.
[0108]
(Interlayer adhesion evaluation method)
The decorative sheet 1 cut to 1 inch in width was used as a test piece, and the base material 2 and the transparent resin layer 6 of the test piece were used in an INSTRON 5500 tensile tester in a 25 ° C. atmosphere at a tensile rate of 100 mm / min. The film was pulled under the condition of an opening angle of 180 ° between the film and the transparent resin layer 6 and evaluated by peel strength. Those having a peel strength of 19.6 N or higher were indicated as “good”, and those less than 19.6 N were indicated as “failed”.
[0109]
(Method for evaluating interlayer adhesion after weather resistance test)
The interlaminar adhesion after the weather resistance test was evaluated by evaluating the interlaminar adhesion described above after the weather resistance test. Among those rejected, those of less than 10N and 5N or more were represented by Δ, and those of less than 5N were represented by ×. In the weather resistance test, the test piece of the decorative sheet 1 was set on a sunshine tester “WEL-300” manufactured by Suga Test Instruments Co., Ltd. Under the conditions, it was performed by irradiating with ultraviolet rays for 1000 hours. The cycle with 18 minutes of rain in 120 minutes means that water that simulates rain is sprayed on a test piece in 18 minutes of 120 minutes.
[0110]
(Scratch resistance evaluation method)
Scratch resistance is obtained by bonding the obtained decorative sheet to a wooden base material for a decorative board using a urethane adhesive (made by NSC Japan, RL96), and performing a coin scratch test on the decorative board. evaluated. In the coin-in-scratch test, the edge of the coin is applied to the decorative sheet coating surface (the outermost protective layer 9) of the decorative plate so that the plane of the 10-yen coin is at an angle of 45 degrees and pressed while applying a load of 500 g. Thus, it pulled by the direction perpendicular | vertical to the plane of a 10 yen coin, and performed by observing and evaluating the external appearance of the decorative board surface. Coin scratch property evaluation criteria are: A: no scratch and no pattern interface peeling, B: minor scratch and no pattern interface peeling, C: scratched and no pattern interface peeling, D: pattern interface peeling, A and B The result was represented by “◯”, and C and D were represented by “C” and “D”, respectively.
[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 can be applied to a colored layer, an adhesive 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 adhesive properties can be formed between the base material and the transparent resin layer. Furthermore, since the aqueous coating liquid is an aqueous coating liquid, the volatilization amount of VOC in the working environment and the VOC remaining amount in the decorative sheet can be reduced as much as possible. As a result, environmental safety can be further improved. Furthermore, according to the present invention, any of the colored layer, the adhesive layer, and the protective layer is a non-hydrophilic UV absorber and / or a non-hydrophilic layer that is contained in a conventional solvent-based coating solution. Since it is not formed with an aqueous coating solution containing a light stabilizer, there is no problem that the weather resistance and adhesive properties of the decorative sheet are deteriorated.
[0113]
Further, according to the aqueous coating solution 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 showing an example of a layer structure of a decorative sheet of the present invention.
FIG. 2 is a cross-sectional view showing another example of the layer structure of the decorative sheet of the present invention.
FIG. 3 is a cross-sectional view showing still another example of the layer structure of the decorative sheet of the present invention.
FIG. 4 is a cross-sectional view showing an example of an embodiment of a decorative sheet of the present invention.
FIG. 5 is a cross-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 shaped articles
51 Board material

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,
The colored layer, the adhesive layer, and the protective layer are water-dispersible ultraviolet absorbers obtained by hydrophilically treating a compound of the following formula (1) with an emulsifier, or an ultraviolet absorber component comprising the compound of the following formula (2) And an aqueous resin obtained by radical polymerization of a hydrophilic component and methyl methacrylate , and a water-dispersible light stabilizer treated with a compound represented by the following formula (3) by an emulsifier: The ultraviolet absorber and the light stabilizer are uniformly dissolved or dispersed in an aqueous coating solution, and
The colored layer, the adhesive layer, and the protective layer are not formed with a water-based coating liquid containing a non-hydrophilic ultraviolet absorber and a non-hydrophilic light stabilizer,
The adhesive sheet and the protective layer contain a water-based urethane resin and a water-dispersible isocyanate cross-linking agent.

The transparent resin layer is configured by laminating two or more layers,
Of the transparent resin layer, the protective layer side layer is formed of a resin mainly composed of a fluororesin, and the substrate side layer is formed of a thermoplastic methacrylic resin. The decorative sheet according to claim 1.

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