JP2004009630A - Decorative sheet and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet and its manufacturing method in which no organic solvent is substantially used. <P>SOLUTION: A masking layer is formed on the surface of a resin-made base sheet, and then a printed pattern layer is formed on the masking layer using water-based print ink. A surface sheet is placed on the face of the base sheet with the printed pattern layer provided, and the base sheet is interlayer-glued to the surface resin sheet via a water-based or solventless adhesive. The surface sheet is embossed to have embossed patterns formed, and recesses of the embossed patterns are filled with a water-based coloring agent. <P>COPYRIGHT: (C)2004,JPO

Description

【００２８】
上記のジイソシアネート化合物の例としては、フェニレンジイソシアネート、トリレンジイソシアネート、キシレンジイソシアネート、テトラメチルキシレンジイソシアネート、ナフチレンジイソシアネート、ジフェニルメタンジイソシアネート等及びこれらの異性体からなる芳香族ジイソシアネート、１，６−ヘキサメチレンジイソシアネート、１，１２−ドデカンジイソシアネート等の脂肪族イソシアネート、シクロヘキサンジイソシアネートシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート、水添キシレンジイソシアネート、１，４−ジイソシアネートシクロヘキサン等の脂環式ジイソシアネート及びこれらの混合物等を挙げることができ、特に脂肪族、脂環式及びこれらの混合物が好ましい。
【００２９】
また、親水性基を導入した化合物における親水性基はイオン別に大別され、カチオン型、ノニオン型、アニオン型に分けられる。カチオン性基としては、アミノ基、イミノ基、３級アミノ基、エーテル基、４級アンモニウム基、ヒドラジノ基等が挙げられる。またノニオン性基としては、ヒドロキシル基、エーテル基、アミド基等が挙げられる。更にアニオン性基としては、カルボキシル基、スルホン基、硫酸エステル基、燐酸エステル基等が挙げられる。前記した親水性基の中ではエーテル基が特に好ましい。
【００３０】
上記の水性接着剤の塗布方法としては、例えば、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の方法が挙げられる。その塗布量としては乾燥状態で、２〜３ｇ／ｍ^２が望ましい。
【００３１】
次に、本発明において無溶剤接着剤としては、例えば、熱硬化型、紫外線硬化型、あるいは電子線硬化型の接着剤を使用することができ、そのビヒクルの主成分を構成する素材としては、例えば、（メタ）アクリル系、ポリアリール／ポリアリル化合物系、エポキシ系、ポリエステル系、ポリウレタン系、或いはそれらの混合乃至複合系を主体とするものを使用することができる。
【００３２】
また、無溶剤接着剤として、特に無溶剤系の感熱溶融型接着剤で耐熱性、耐溶剤性に優れ、初期接着力が高く短時間で接着が完了する、湿気硬化性感熱溶融型接着剤、反応性ホットメルト型接着剤がより好ましいものである。
【００３３】
湿気硬化性感熱溶融型接着剤も反応型ホットメルト性接着剤の一種である。湿気硬化性感熱溶融型接着剤は、自然放置により空気中の水分で硬化反応が進行するので、作業安定性の点でラミネート直前に施す。また、湿気硬化性感熱溶融型接着剤は、ラミネート直後は通常の感熱溶融型接着剤と同様の接着力であるが、自然放置により空気中の水分で架橋・硬化反応が徐々に進行するために、最終的にクリープ変形及び熱溶融がなく、耐熱性に優れ、大きな接着力が得られる。但し、ラミネート終了後に湿気で接着剤の架橋・硬化を進行させるため、湿気を含む空気中にラミネート後の化粧材を放置して養生する。養生の際の好ましい雰囲気条件は、大体、相対湿度５０％ＲＨ以上、気温１０℃以上である。湿度・相対湿度とも高い方がよいが、より短時間で硬化が完了する。標準的な硬化完了時間は、通常の場合、２０℃、６０％ＲＨの雰囲気の中で１０時間程度である。
【００３４】
湿気硬化性感熱溶融型接着剤は、分子末端にイソシアネート基を有するプレポリマーを必須成分とする組成物である。前記プレポリマーは、通常は分子両末端に各々イソシアネート基を１個以上有するポリイソシアネートプレポリマーであり、室温で固体の熱可塑性樹脂の状態にあるものである。イソシアネート基同士が空気中の水分により反応して鎖延長反応を起こして、その結果、分子鎖中に尿素結合を有する反応物を生じて、この尿素結合に更に分子末端のイソシアネート基が反応して、ビウレット結合を起こして分岐し、架橋反応を起こす。分子末端にイソシアネート基を有するフレポリマーの分子鎖の骨格構造は任意であるが、具体的には、ウレタン結合を有するポリウレタン骨格、エステル結合を有するポリエステル骨格、ポリブタジエン骨格等である。適宜これら１種又は２種以上の骨格構造を採用することで、接着剤物性を調整できる。なお、分子鎖中にウレタン結合のある場合は、このウレタン結合とも末端のイソシアネート基が反応して、アロファネート結合を生じて、このアロファネート結合によっても架橋反応を起こす。
【００３５】
ポリイソシアネートフレポリマーの具体例としては、例えば、ポリオールに過剰のポリイソシアネートを反応させた分子末端イソシアネート基を有し、且つ分子鎖中にウレタン結合を有するポリウレタン骨格のウレタンポリポリマーがある。また、ポリイソシアネートにポリエステルポリオールと、ポリブタジエン骨格を有するポリオールとを任意の順序で加え付加反応させ得られた、ポリエステル骨格とポリブタジエン骨格とがウレタン結合により結合された構造を有し且つ分子末端にイソシアネート基を有する結晶性ウレタンプレポリマー、或いは、ポリカーボネート系ポリオールとポリイソシアネートを反応させて得られる分子中に２個以上のイソシアネート基を有するポリカーボネート系ウレタンプレポリマー、ポリエステル系ポリオールとポリイソシアネートを反応させて得られる分子中に２個以上のイソシアネート基を有するポリエステル系ウレタンプレポリマー等が挙げられる。
【００３６】
また、湿気硬化性感熱溶融型接着剤としては、上記各種ポリイソシアネートプレポリマーの他に、各種物性を調整するために、上記必須反応成分中に更に、必要に応じて、熱可塑性樹脂、粘着付与剤、可塑剤、充填剤等の各種副材料を添加することもできる。これら副材料としては、例えば、エチレン−酢酸ビニル共重合体、低分子量ポリエチレン、変性ポリオレフィン、アタクチックポリプロピレン、線状ポリエステル、エチレン−エチルアクリレート（ＥＡＡ）等の熱可塑性樹脂、テルペン−フェノール樹脂、アビエチン酸ロジンエステル等の粘着付与剤、炭酸カルシウム、硫酸バリウム、シリカ、アルミナ等の微粉末からなる充填剤、着色顔料、硬化触媒、水分除去剤、貯蔵安定剤、老化防止剤等である。
【００３７】
反応性ホットメルト型接着剤を施すには、ダイコーター等による溶融塗工法によればよい。ホットメルト型接着剤として使用する場合は無溶剤なので、接着直前の塗工でも溶剤乾燥が不要で高速生産ができる。なお、接着剤の塗布量は、接着剤の組成、被接着基材の種類及び表面状態で異なるが、通常１０〜２００ｇ／ｍ^２程度である。
【００３８】
上記の無溶剤接着剤の塗布法としては、例えば、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、キスコート法さの他の方法が挙げられる。その塗布量としては、乾燥状態で２〜３ｇ／ｍ^２が望ましい。
【００３９】
次に、第２の実施の形態における印刷模様層５を構成する水性インキ組成物について説明する。水性インキ組成物としてはベヒクルの主成分とし、これに、ワックス類、分散剤、消泡剤、レベリング剤、安定剤、充填剤、潤滑剤、滑剤、その他の添加剤を任意に添加し、水等からなる溶剤を使用してミキサー等によって十分に混練してなる水性インキ組成物を使用することができる。水性インキ用樹脂としては、溶解型、ハイドロゾル型、エマルジョン型の天然樹脂、或いは、合成樹脂、更にはそれらの変性樹脂の一種乃至複数種の混合物を使用することができる。具体的には、水性インキ用樹脂としては、例えば、アクリル酸エステル、メタクリル酸エステル、ヒドロキシルエチルメタクリレート等の（メタ）アクリル系モノマー、アクリロニトリル、メタクリルアミド等のアミド系モノマー、このアミド系モノマーのＮ−アルコキシ置換体、同Ｎ−メチロール置換体、スチレン、ビニルトルエン、α−メチルスチレン、ジビニルベンゼン等のスチレン系モノマー、ジアリルフタレート、アリルグリシジルエーテル、トリアリルイソシアヌレート等のアリル系モノマー、酢酸ビニル、Ｎ−ビニルピロリドン等の重合性二重結合を有するモノマー等の一種又は複数種と、カルボキシル基を有するアクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマール酸、イタコン酸、その他の不飽和カルボン酸の一種乃至複数種の共重合体からなるアルカリ溶液可溶性（メタ）アクリル系共重合体を使用する事ができる。更に、本発明において、水性インキ組成物として、例えば、ポリアルキルアミド系樹脂、ポリ（メタ）アクリル酸系樹脂、ポリエチレンオキシド系樹脂、ポリＮ−ビニルピロリドン系樹脂、水溶性ポリウレタン系樹脂（水溶性２液硬化型ポリウレタン系樹脂）、水溶性ポリエステル系樹脂、水溶性ポリアミド系樹脂、水溶性アミノ系樹脂、水溶性フェノール系樹脂、その他の水溶性合成樹脂、ポリヌクレオチド、ポリペプチド、多糖類等の水溶性天然高分子その他も使用することができる。
【００４０】
また、本発明において、水性インキ用樹脂としては、例えば、天然ゴム、合成ゴム、ポリ酢酸ビニル樹脂、（メタ）アクリル系樹脂、ポリ塩化ビニル樹脂、ポリウレタン系樹脂、ポリウレタン−ポリアクリル系樹脂変性乃至混合樹脂その他のエマルジョン型の樹脂を使用することができる。本発明においては前記した樹脂の一種又は複数種を使用し、使用する樹脂に適する溶解型、ハイドロゾル型、又はエマルジョン型の形態で使用することができる。
【００４１】
また、水溶性インキ用組成物に使用する水としては、通常の工業用水を使用することができ、また、水とアルコールからなる溶剤としては、水の他にエタノール、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、グリコール類及びそのエステル類等を使用して調整することができる。その場合、低級アルコール、グリコール類又はそのエステル類は５〜２０重量％位の割合で含有しているのが望ましい。また、前記した低級アルコール、グリコール類及びそのエステル類等の溶剤は、インキの流動性、インキの流動性改良、被印刷体への濡れの向上、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、使用量が決定されるものである。
【００４２】
上記のような水性インキ組成物を使用し、例えば、グラビア印刷方式或いはフレキソ印刷方式等により、基材フィルムの表面、裏面或いは両面に、例えば、文字、図形、記号、その他の所望の印刷模様層５を形成することができる。
【００４３】
次に、図２の化粧シートの製造方法について説明する。
【００４４】
基材シート１の表面に遮蔽層４は、印刷模様層５と同様に水性をインキを用いて印刷により基材シート１上に形成することができる。或いは、白色ポリエチレンのような有色樹脂シートにグラビアコーターにて水性ドライラミネート接着剤を塗工し、乾燥後に基材シート１と合わせてドライラミネートすることにより隠蔽層２を形成する。次いで、隠蔽層２上に水性インキを用いてグラビア印刷等により印刷模様層５を形成する。印刷模様を施した基材シート１を水性接着剤又は無溶剤接着剤を用いて接着することにより図２に示す化粧シートを得ることができる。
【００４５】
次に、図３に本発明の化粧シートの第３の実施の形態を示す。
【００４６】
この化粧シートは、基材シート１の上に遮蔽層４を設け、遮蔽層４上に印刷模様層５を設けた印刷模様付き基材シート４を表面シート３を水性接着剤又は無溶剤接着剤２を介して積層し、表面シート２にはエンボス加工を施して凹凸模様６を形成しこの凹凸模様６の凹部に水性インキ７を充填してなるものである。
【００４７】
表面シート２のエンボス加工は、ロールエンボス機や平版エンボス機など、既知のエンボス手段により行うことができる。基材シート２に印刷模様が施されている場合、エンボスと印刷模様とが同調していることが好ましいことはいうまでもないことである。
【００４８】
凹凸模様６の凹部に充填する水性インキ７は、水溶性の樹脂又は各種の樹脂エマルジョンに顔料等の添加剤を分散したものである。希釈剤として水にアルコールを少量添加して乾燥を速やかにすることができる。
【００４９】
凹凸模様６の凹部に充填する水性インキ７に用いるエマルジョンの例を挙げれば、ウレタンエマルジョン、ウレタン−アクリルエマルジョン、アクリルエマルジョン、塩化ビニルエマルジョン、酢酸ビニルエマルジョン、エポキシエマルジョン、エチレン−酢酸ビニル共重合体エマルジョン、酢酸ビニル−アクリル共重合体エマルジョン、アクリル−スチレン共重合体エマルジョン、ビニリデンエマルジョンでありそのほかにＳＢＲラテックスやＮＢＲラテックスを用いることができる。水溶性樹脂として水溶性アクリル樹脂が挙げられる。
【００５０】
エマルジョンの成分で分子内に活性水素を有するものは、アジリジン、エポキシ、メラミン、カルボジイミド、オキサゾリン等の硬化剤と反応して硬化し、インキ層の耐溶剤性、耐スクラッチ性、耐水性、耐薬品性を向上させる。
【００５１】
着色剤には、有機顔料、例えばアゾ顔料、フタロシアニン顔料を使用することができ、また無機顔料、例えば二酸化チタン、弁柄、カーボンブラック、炭酸カルシウム等も使用することができる。
【００５２】
インキ層をつや消しにしたいときは、上記の着色顔料の他に、つや消し材、例えばマイクロシリカや樹脂ビームを添加すればよい。
【００５３】
水性インキに沈降性硫酸バリウムのような体質顔料を分散しておくと、インキの乾燥性及び転移性を向上できる。
【００５４】
上記の水性インキには、添加材の分散時に発泡しやすいので、消泡材を添加しておくことが望ましい。消泡材はシリコーン系など、既知のものを使用することができる。
【００５５】
インキ層の強度を高めるために、前記した硬化剤、例えばアジリジン系硬化剤を添加してもよい。硬化剤の配合量はインキ１００重量部に対し３〜４重量部程度でよい。
【００５６】
凹凸模様６の凹部への水性インキの充填は、ナイフコーター、バーコーター等を用いた既知のワイピング法により行うことができる。
【００５７】
次に、図４は本発明の化粧シートの第４の実施の形態を示す。
【００５８】
この化粧シートは、表面に水性インキを用いて印刷により隠蔽層４を形成し隠蔽層４上に同様に水性インキを用いて印刷により印刷模様５を形成した基材シート１に水性接着剤２を介して表面シート３を積層して積層シートを得、この積層シートにダブリングエンボスを施し、表面シート３の表面に形成された凹凸模様６の凹部に水性インキ７を充填し、しかる後、表面シート３上に水性インキを用いて印刷により表面コート層８を形成してなるものである。
【００５９】
（実施例１）
基材シートとして、アイソタクチックポリプロピレンからなるハードセグメント１００重量部、スチレン−ブタジエンゴムからなるソフトセグメント１００重量部、無機充填材（炭酸カルシウム粉末）３０重量部、顔料１０重量部を配合したものを溶融混練した後に押し出ししてなる８０μｍのポリオレフィンシートを用意し、その両面にコロナ放電処理を施した。この基材シートに下記の組成Ａからなる水性インキを用いてグラビア印刷により隠蔽性着色べた層を形成し、次に組成Ｂからなる水性インキを用い、グラビア印刷により抽象柄の絵柄印刷層を形成し、印刷シートを得た。
【００６０】
水性インキ（組成Ａ）
水分散ポリウレタン樹脂含有白色水性インキ　　　　　　　１００重量部
（オーデＷＫＥ白、ザ・インクテック製）
水　　　　　　　　　　　　　　　　　　　　　　　　　　　１６重量部
エタノール　　　　　　　　　　　　　　　　　　　　　　　１２重量部
ノルマルプロパノール　　　　　　　　　　　　　　　　　　１２重量部
【００６１】
水性インキ（組成Ｂ）
水分散ポリウレタン樹脂含有赤色水性インキ　　　　　　　１００重量部
（オーデＷＫＥ赤、ザ・インクテック製）
水　　　　　　　　　　　　　　　　　　　　　　　　　　　１６重量部
エタノール　　　　　　　　　　　　　　　　　　　　　　　１２重量部
ノルマルプロパノール　　　　　　　　　　　　　　　　　　１２重量部
【００６２】
一方、表面シートとして、アイソタクチックポリプロピレンからなるハードセグメント１６０重量部と、アタクチツクポリプロピレンからなるソフトセグメント４０重量部の混合物に、ベンゾトリアゾール系紫外線吸収剤０．２重量％添加したものを溶融混練した後、押し出してなる８０μｍのポリオレフィン系樹脂シートを用意し、その両面にコロナ放電処理を施した。
【００６３】
次に、上記印刷シートの印刷面に下記組成Ｃの水性ドライラミネート接着剤をグラビアコーターにて約３ｇ／ｍ^２塗工し、乾燥後、塗工面に上記表面シートを重ね、ニップローラー間で加圧して積層シートからなる化粧シートを得た。この化粧シートを常温下においてエージングを行った。その後、接着強度及びポットライフについて調べたところ、接着強度は十分ありまたドライラミネート接着剤を配合後（主剤に架橋剤添加後）４時間以上経てもゲル化せずポットライフは十分にあることが分かった。
【００６４】
水性ドライラミネート接着剤（組成Ｃ）
水分散ポリウレタン樹脂　　　　　　　　　　　　　　　　１００重量部
（エバファールＨＯ１４、日華化学製）
イソシアヌレート骨格含有イソシアネート化合物　　　　　　　９重量部
（Ｘ９００３、日華化学製）
水　　　　　　　　　　　　　　　　　　　　　　　　　　　１０重量部
イソプロパノール　　　　　　　　　　　　　　　　　　　　１０重量部
【００６５】
（実施例２）
さらに、実施例１で得られた積層シートを、ニップローラの出口に設置された予熱機により加熱し、直ちにエンボスロールを利用して積層シートの表面シート側にエンボス加工を行い凹凸模様を形成した。
【００６６】
形成した凹凸模様の凹部にナイフコーターを使用して下記組成Ｄの水性インキを充填し化粧シートを得た。
【００６７】
水性インキ（組成Ｄ）
アニオン型ウレタンエマルジョン部　　　　　　　　　　　　５０重量部
無黄変エステル系、ＮＶ３０％）
沈降性硫酸バリウム　　　　　　　　　　　　　　　　　　　２０重量部
カーボンブラック　　　　　　　　　　　　　　　　　　　　１０重量部
マイクロシリカ　　　　　　　　　　　　　　　　　　　　　　４重量部
消泡剤（シリコーン系）　　　　　　　　　　　　　　　　０．５重量部
希釈剤（水）　　　　　　　　　　　　　　　　　　　　　　１６重量部
【００６８】
（実施例３）
実施例１と同様にして積層シートを作製し、この積層シートにダブリングエンボスを施した。
【００６９】
表面シートの表面に形成された凹凸模様の凹部に実施例１と同様に水性インキを充填した後に、表面シートの表面に下記組成Ｅの水性インキをグラビアコートして表面コート層を形成し、乾燥させて本発明の化粧シートを得た。
【００７０】
水性インキ（組成Ｅ）
アニオン型ウレタンエマルジョン　　　　　　　　　　　　　５０重量部
ウレタン−アクリルエマルジョン　　　　　　　　　　　　　１５重量部
マイクロシリカ　　　　　　　　　　　　　　　　　　　　　　４重量部
ワックス（ポリエチレン系）　　　　　　　　　　　　　　　　２重量部
レベリング剤（シリコーン系）　　　　　　　　　　　　　０．５重量部
消泡剤（シリコーン系）　　　　　　　　　　　　　　　　０．５重量部
増粘剤　　　　　　　　　　　　　　　　　　　　　　　　　　４重量部
希釈剤（水）　　　　　　　　　　　　　　　　　　　　　　２４重量部
【００７１】
（実施例４）
実施例１と同様にして、但し水性ドライラミネート接着剤として下記の組成Ｆからなるものを用いて化粧シートを得た。この化粧シートを常温下においてエージングを行った。その後、接着強度及びポットライフについて調べたところ、接着強度は十分あることがわかった。しかし、ドライラミネート接着剤を配合後（主剤に架橋剤添加後）１０分でゲル化し、ポットライフは十分でないことが分かった。
【００７２】
水性ドライラミネート接着剤（組成Ｆ）
水分散ポリウレタン樹脂　　　　　　　　　　　　　　　　１００重量部
（エバファールＨＯ１４、日華化学製）
ビウレット骨格含有イソシアネート化合物　　　　　　　　　　９重量部
（デュラネートＷＴ３０−１００、旭化成工業製）
水　　　　　　　　　　　　　　　　　　　　　　　　　　　１０重量部
イソプロパノール　　　　　　　　　　　　　　　　　　　　１０重量部
【００７３】
（実施例５）
実施例１における組成Ｃの水性ドライラミネート接着剤を反応性ホットメルト接着剤（日本フーラー（株）製、ＨＬ−８８０５）に換えて同様に化粧シートを得た。接着剤の塗工条件は、１３５℃に加熱して溶融した反応性ホットメルト接着剤をダイコーターにて印刷シートの印刷面に塗布量４０〜７０ｇ／ｍ^２で行った。
【００７４】
（比較例）
実施例１と同様にして、但し水性ドライラミネート接着剤として下記の組成Ｆからなるものを用いた。常温下でエージング後に接着強度を調べた結果、組成Ｇの接着剤はインキ化困難であったこともあって十分な接着強度は認められなかった。また、ポットライフについて調べたところ、ドライラミネート接着剤を配合後（主剤に架橋剤添加後）４時間未満でゲル化しポットライフは十分でないことが分かった。
【００７５】
水性ドライラミネート接着剤（組成Ｇ）
水分散ポリウレタン樹脂　　　　　　　　　　　　　　　　１００重量部
（エバファールＨＯ１４、日華化学製）
アダクトタイプイソシアネート化合物　　　　　　　　　　　　９重量部
（デユラネートＰ・３０１・７５Ｅ、旭化成工業製）
水　　　　　　　　　　　　　　　　　　　　　　　　　　　１０重量部
イソプロパノール　　　　　　　　　　　　　　　　　　　　１０重量部
【００７６】
【発明の効果】
以上詳細に説明したように、本発明の化粧シート及びその製造方法において溶剤型インキ及び溶剤型接着剤は用いられていないので、印刷後の乾燥放出される溶剤による大気汚染等の公害問題等のない安全性の高い化粧シートの提供を可能とするものであり、また作業環境は改善され、且つ、工場設備を防爆設備としなければならない必要性もなくなる。
【図面の簡単な説明】
【図１】本発明の第１の実施の形態の化粧シートを示す断面図である。
【図２】本発明の第２の実施の形態の化粧シートを示す断面図である。
【図３】本発明の第３の実施の形態の化粧シートを示す断面図である。
【図４】本発明の第４の実施の形態の化粧シートを示す断面図である。
【符号の説明】
１　基材シート
２　水性接着剤層又は無溶剤接着剤層
３　表面シート
４　隠蔽層
５　印刷模様層
６　凹凸模様
７　水性インキ
８　表面コート層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative sheet used for decoration of building materials, furniture, cabinets of home appliances, and the like, and a method for manufacturing the same.
[0002]
[Prior art]
As a decorative sheet used for this type of application, for example, a concealing layer is formed on a plastic base sheet, a printed pattern layer is formed by printing on the concealing layer, and the printed pattern layer is adhered onto the base sheet. What laminated | stacked the transparent surface sheet through the layer is put into practical use.
[0003]
Ink and interlayer adhesives used in conventional decorative sheets are obtained by dissolving and dispersing additives such as synthetic resin vehicles and pigments in organic solvents. When inks and paints using organic solvents as diluents are used in this way, they must be handled as hazardous materials, and the factory equipment including the application means must be explosion-proof. In addition, after printing, there is a problem of pollution such as air pollution due to a solvent released by drying.
[0004]
[Problems to be solved by the invention]
This invention is made | formed in view of such a problem, The place made into the objective is to provide the decorative sheet which does not use an organic solvent substantially, and its manufacturing method.
[0005]
[Means for Solving the Problems]
Invention of Claim 1 solves the subject regarding said decorative sheet, The surface sheet is laminated | stacked through the water-based adhesive or the solventless adhesive on the surface of the resin-made base material sheet, It is characterized by the above-mentioned. The gist of the decorative sheet is as follows. Since the base sheet and the top sheet are laminated via a water-based adhesive or a solventless adhesive and no organic solvent is used, the problem of pollution caused by the solvent released from the adhesive is avoided. Moreover, not only does it not have to handle dangerous solvents during production, but there is no need for the factory equipment including the application means to be explosion-proof.
[0006]
In the decorative sheet of the present invention, a masking layer may be formed on the surface of the base material sheet, and then a printed pattern layer may be formed on the masking layer using an aqueous printing ink. Since the printed pattern layer is also formed using water-based ink, the problem of pollution caused by the solvent released from the adhesive is completely avoided.
[0007]
In the decorative sheet according to the present invention, the topsheet may be embossed to form a concavo-convex pattern, or both the topsheet and the base sheet may be embossed so that the concavo-convex pattern is the topsheet and It may be formed on both of the base sheet. Moreover, the water-based colorant may be filled in the concaves and convexes formed on the surface sheet. And the surface coat layer may be adhere | attached and formed through the water-based adhesive or a solventless adhesive on the surface sheet in which the uneven | corrugated pattern was formed.
[0008]
In the decorative sheet according to the present invention, a urethane dry laminate adhesive may be used as the aqueous adhesive. In this case, the urethane-based dry laminate adhesive used as the water-based adhesive is preferably a water-dispersed or water-soluble adhesive containing an isocyanate compound having two or more isocyanate groups in the molecule. The isocyanate compound preferably contains an isocyanurate skeleton.
[0009]
In the decorative sheet according to the present invention, a reactive hot-melt adhesive may be used as the solventless adhesive.
[0010]
In the decorative sheet according to the present invention, the concealing layer preferably contains an isocyanate compound. In this case, the isocyanate compound may be an isocyanate compound having two or more isocyanate groups in the molecule, or the isocyanate compound may contain an isocyanurate skeleton.
[0011]
In the decorative sheet according to the present invention, the base sheet and the top sheet are preferably made of polyolefin.
[0012]
Invention of Claim 14 solves the subject regarding said manufacturing method, forms a masking layer on the surface of a resin-made base material sheet, and then forms a printing pattern layer on the masking layer using aqueous printing ink. The gist of the method is a method for producing a decorative sheet, which is formed, a surface sheet is disposed thereon, and the base sheet is bonded to the surface resin sheet using an aqueous or solventless adhesive.
[0013]
In the method for producing a decorative sheet of the present invention, the shielding layer can be formed by printing using water-based ink. In that case, it is desirable to form the masking layer using a water-based ink containing an isocyanate compound. Moreover, it can replace with water-based ink and can form a shielding layer by adhere | attaching a colored resin sheet through a water-based adhesive layer or a solventless adhesive layer.
[0014]
In the method for producing a decorative sheet of the present invention, an aqueous dry laminate adhesive can be used as the adhesive, and the base sheet can be laminated on the surface sheet by dry lamination. Moreover, a solventless adhesive can be used as the adhesive, and the solventless adhesive can be applied to the base sheet surface and then adhered to the topsheet.
[0015]
In the manufacturing method of the decorative sheet of the present invention, the surface sheet is embossed to form a concavo-convex pattern, and the concavo-convex pattern is formed in the surface sheet by filling the concave portion of the concavo-convex pattern with water-based ink by a wiping method. A decorative sheet filled with can be obtained. Filling the recessed portions of the formed uneven pattern with water-based ink can be performed by a known wiping method such as a knife coater or a bar coater.
[0016]
Furthermore, in the method for producing a decorative sheet of the present invention, a surface sheet is laminated on a base sheet, a printed pattern is formed on the surface sheet with water-based ink, and then an overcoat layer is formed on the surface sheet. By embossing in synchronization with the printed pattern and forming a concavo-convex pattern, a decorative sheet can be obtained in which the concavo-convex pattern extending to the base sheet is synchronized with the pattern applied to the top sheet.
[0017]
In the decorative sheet and the method for producing the same according to the present invention, solvent-based ink and solvent-based adhesive are not used, and therefore, highly safe makeup that does not cause pollution problems such as air pollution due to the solvent released by drying after printing. The seat can be provided, the working environment is improved, and the necessity of having the factory equipment as an explosion-proof equipment is eliminated.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the decorative sheet and the manufacturing method thereof according to the present invention will be described in detail with reference to the drawings.
[0019]
FIG. 1 shows a first embodiment of a decorative sheet of the present invention. The decorative sheet shown in FIG. 1 is obtained by laminating a surface sheet 3 on a base sheet 1 with an aqueous adhesive layer or a solventless adhesive layer 2 interposed therebetween.
[0020]
FIG. 2 shows a second embodiment of the decorative sheet of the present invention. The decorative sheet shown in FIG. 2 is provided with a concealing layer 4 on a substrate sheet 1, a printed pattern layer 5 is formed thereon using water-based ink, and the substrate sheet 1 provided with the printed pattern layer 5 is water-based bonded. The surface sheet 3 is laminated through the agent layer or the solventless adhesive layer 2.
[0021]
The material used for the base sheet 1 and the top sheet 3 in the decorative sheet as described above is most preferably a synthetic resin sheet in terms of moldability and coating suitability. For example, polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, vinyl resins such as ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, polyesters such as polyethylene terephthalate and polybutylene terephthalate, Polystyrene, acrylic styrene copolymer, styrene resin such as ABS resin, polycarbonate, nylon, ionomer resin and the like can be used. Particularly, polyolefin resins include high crystalline non-elastomeric polyolefins such as polyethylene (low density, medium density, or high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, etc. Resins or various olefinic thermoplastic elastomers can be used. With regard to these, desired physical properties may be derived by controlling crystallinity and stretchability.
[0022]
The shielding layer 4 can be formed on the base material sheet 1 by printing using water-based ink in the same manner as the printed pattern layer 5. Alternatively, it can be formed by dry laminating a colored resin sheet such as white polyethylene on the base sheet.
[0023]
In the first and second embodiments, as the aqueous adhesive layer, for example, an aqueous adhesive resin is a main component of the vehicle, and waxes, a dispersant, an antifoaming agent, a leveling agent, a stabilizer, A filler, lubricant, lubricant, other additives can be added arbitrarily, and water or a water-based adhesive that is sufficiently kneaded with a mixer using a solvent composed of water and alcohol, etc. it can. Examples of the water-based adhesive resin include polyalkylamide resins, poly (meth) acrylic acid resins, polyethylene oxide resins, poly N-vinylpyrrolidone resins, water-soluble polyurethane resins (water-soluble two-component curable resins). Polyurethane resins), water-soluble polyester resins, water-soluble polyamide resins, water-soluble amino resins, water-soluble phenol resins, other water-soluble synthetic resins, polynucleotides, polypeptides, polysaccharides, and other water-soluble natural polymers Molecules and other soluble resins can be used.
[0024]
In the present invention, examples of the water-based adhesive resin include natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane resin (two-component curable polyurethane resin). ), Polyurethane-polyacrylic resin modified or mixed resins and other emulsion type resins can be used. Furthermore, the alkali solution-soluble (meth) acrylic copolymer described above can be used.
[0025]
In the present invention, the urethane-based dry laminate adhesive used as the aqueous dry laminate adhesive is preferably a water-dispersed or water-soluble adhesive containing an isocyanate compound having two or more isocyanate groups in the molecule.
[0026]
In the decorative sheet according to the present invention, the water-dispersed or water-soluble isocyanate compound contained in the aqueous dry laminate adhesive and having two or more isocyanate groups in the molecule is based on the reaction between the diisocyanate compound and the active hydrogen group-containing compound. Examples thereof include compounds in which a hydrophilic group is further introduced into a terminal isocyanate group-containing compound by reaction of a terminal isocyanate group-containing compound or a diisocyanate compound. Examples of terminal isocyanate group-containing compounds by reaction between diisocyanate compounds and active hydrogen group-containing compounds, or terminal isocyanurate group compounds by reaction with diisocyanate compounds include terminal isocyanate group-containing compounds having a urethane structure, urea structures Terminal isocyanate group-containing compound, terminal isocyanate group-containing compound having uretdione structure, terminal isocyanate group-containing compound having isocyanate structure, terminal isocyanate group-containing compound having carbodiimide structure, terminal isocyanate group-containing compound having uretonimine structure, biuretimine structure Examples thereof include terminal isocyanate group-containing compounds having terminal isocyanate groups, compounds having terminal isocyanate groups having an allophanate structure, and mixtures thereof. Terminal isocyanate group-containing compound having an isocyanate structure as shown are preferred.
[0027]
[Chemical 1]

[0028]
Examples of the diisocyanate compound include phenylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate and the like, and aromatic diisocyanates composed of these isomers, 1,6-hexamethylene diisocyanate, Aliphatic isocyanates such as 1,12-dodecane diisocyanate, cyclohexane diisocyanate cyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, cycloaliphatic diisocyanate such as 1,4-diisocyanate cyclohexane, and mixtures thereof can be mentioned. Aliphatic, alicyclic and mixtures thereof are preferred.
[0029]
In addition, hydrophilic groups in a compound into which a hydrophilic group has been introduced are roughly classified according to ions, and are classified into a cation type, a nonion type, and an anion type. Examples of the cationic group include an amino group, an imino group, a tertiary amino group, an ether group, a quaternary ammonium group, and a hydrazino group. Examples of the nonionic group include a hydroxyl group, an ether group, and an amide group. Furthermore, examples of the anionic group include a carboxyl group, a sulfone group, a sulfate ester group, and a phosphate ester group. Among the hydrophilic groups described above, an ether group is particularly preferable.
[0030]
Examples of the application method of the aqueous adhesive include a gravure coating method, a reverse roll coating method, a knife coating method, a kiss coating method, and other methods. The coating amount is 2 to 3 g / m in a dry state.²Is desirable.
[0031]
Next, as the solventless adhesive in the present invention, for example, a thermosetting, ultraviolet curable, or electron beam curable adhesive can be used, and as a material constituting the main component of the vehicle, For example, (meth) acrylic, polyaryl / polyallyl compound-based, epoxy-based, polyester-based, polyurethane-based, or a mixture or composite thereof can be used.
[0032]
In addition, as a solvent-free adhesive, a moisture-curable heat-sensitive melt adhesive that is excellent in heat resistance and solvent resistance, particularly a solvent-free heat-sensitive melt adhesive, has a high initial adhesive force, and can be bonded in a short time. A reactive hot melt adhesive is more preferred.
[0033]
A moisture-curable heat-sensitive adhesive is also a kind of reactive hot-melt adhesive. The moisture-curable heat-sensitive melt adhesive is applied immediately before lamination from the viewpoint of work stability because the curing reaction proceeds with moisture in the air when left standing naturally. Moisture curable heat-sensitive adhesives have the same adhesive strength as normal heat-sensitive adhesives immediately after lamination, but the crosslinking / curing reaction gradually proceeds with moisture in the air when left unattended. Finally, there is no creep deformation and heat melting, excellent heat resistance, and a large adhesive force can be obtained. However, since the crosslinking and curing of the adhesive proceeds with moisture after the lamination is completed, the laminated cosmetic material is left in the air containing moisture to be cured. Preferable atmospheric conditions during curing are generally a relative humidity of 50% RH or higher and a temperature of 10 ° C. or higher. Higher humidity and relative humidity are better, but curing is completed in a shorter time. The standard curing completion time is usually about 10 hours in an atmosphere of 20 ° C. and 60% RH.
[0034]
The moisture curable thermosensitive adhesive is a composition containing a prepolymer having an isocyanate group at the molecular end as an essential component. The prepolymer is usually a polyisocyanate prepolymer having one or more isocyanate groups at both molecular ends, and is in the state of a solid thermoplastic resin at room temperature. Isocyanate groups react with each other by moisture in the air to cause chain extension reaction. As a result, a reaction product having a urea bond in the molecular chain is generated, and the isocyanate group at the molecular end further reacts with this urea bond. , Biuret bond is caused to branch, causing a crosslinking reaction. The skeleton structure of the molecular chain of the fluorpolymer having an isocyanate group at the molecular terminal is arbitrary, and specifically, a polyurethane skeleton having a urethane bond, a polyester skeleton having an ester bond, a polybutadiene skeleton, and the like. Adhesive properties can be adjusted by appropriately adopting one or more of these skeleton structures. When a urethane bond is present in the molecular chain, the terminal isocyanate group reacts with this urethane bond to form an allophanate bond, and this allophanate bond also causes a crosslinking reaction.
[0035]
Specific examples of the polyisocyanate furpolymer include a polyurethane polymer having a polyurethane skeleton having a molecular terminal isocyanate group obtained by reacting an excess polyisocyanate with a polyol and having a urethane bond in the molecular chain. In addition, a polyester polyol and a polyol having a polybutadiene skeleton are added to polyisocyanate in any order and subjected to an addition reaction. The polyester skeleton and the polybutadiene skeleton have a structure bonded by a urethane bond, and the molecular terminal has an isocyanate. A crystalline urethane prepolymer having a group, or a polycarbonate urethane prepolymer having two or more isocyanate groups in a molecule obtained by reacting a polycarbonate polyol and a polyisocyanate, and reacting a polyester polyol with a polyisocyanate. Examples thereof include polyester urethane prepolymers having two or more isocyanate groups in the resulting molecule.
[0036]
In addition to the above-mentioned various polyisocyanate prepolymers, the moisture-curable thermosensitive melt-type adhesive may further include a thermoplastic resin and a tackifier, if necessary, in the essential reaction components in order to adjust various physical properties. Various sub-materials such as an agent, a plasticizer, and a filler can also be added. Examples of these auxiliary materials include ethylene-vinyl acetate copolymer, low molecular weight polyethylene, modified polyolefin, atactic polypropylene, linear polyester, ethylene-ethyl acrylate (EAA), and other thermoplastic resins, terpene-phenol resins, and abietin. Examples include tackifiers such as acid rosin esters, fillers made of fine powders such as calcium carbonate, barium sulfate, silica, and alumina, color pigments, curing catalysts, moisture removing agents, storage stabilizers, and antioxidants.
[0037]
The reactive hot melt adhesive may be applied by a melt coating method using a die coater or the like. When used as a hot melt adhesive, it is solvent-free, so solvent drying is not required even during coating immediately before bonding, and high-speed production is possible. The amount of adhesive applied varies depending on the composition of the adhesive, the type of substrate to be bonded, and the surface condition, but is usually 10 to 200 g / m.²Degree.
[0038]
Examples of the application method of the solventless adhesive include other methods such as gravure coating, reverse roll coating, knife coating, and kiss coating. The coating amount is 2 to 3 g / m in a dry state.²Is desirable.
[0039]
Next, the water-based ink composition constituting the printed pattern layer 5 in the second embodiment will be described. The water-based ink composition is the main component of the vehicle, and optionally added with waxes, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, lubricants, and other additives, and water. It is possible to use a water-based ink composition that is sufficiently kneaded with a mixer or the like using a solvent comprising the above. As the resin for water-based inks, a soluble type, hydrosol type, emulsion type natural resin, synthetic resin, or a mixture of one or more of these modified resins can be used. Specifically, as the resin for water-based ink, for example, (meth) acrylic monomers such as acrylic acid esters, methacrylic acid esters, and hydroxylethyl methacrylate, amide monomers such as acrylonitrile and methacrylamide, and N of this amide monomer -Alkoxy substituted, N-methylol substituted, styrene monomer such as styrene, vinyltoluene, α-methylstyrene, divinylbenzene, allyl monomer such as diallyl phthalate, allyl glycidyl ether, triallyl isocyanurate, vinyl acetate, One or more monomers having a polymerizable double bond such as N-vinylpyrrolidone, and acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and other unsaturated carboxylic acids having a carboxyl group A kind or alkali solution-soluble (meth) acrylic copolymer comprising a plurality of kinds of copolymers can be used for. Furthermore, in the present invention, as the water-based ink composition, for example, polyalkylamide resins, poly (meth) acrylic acid resins, polyethylene oxide resins, poly N-vinylpyrrolidone resins, water-soluble polyurethane resins (water-soluble resins) Two-component curable polyurethane resins), water-soluble polyester resins, water-soluble polyamide resins, water-soluble amino resins, water-soluble phenol resins, other water-soluble synthetic resins, polynucleotides, polypeptides, polysaccharides, etc. Water-soluble natural polymers and others can also be used.
[0040]
In the present invention, the water-based ink resin includes, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane resin, polyurethane-polyacrylic resin modified or Mixed resins and other emulsion type resins can be used. In the present invention, one or a plurality of the above-described resins can be used, and can be used in the form of a solution type, a hydrosol type, or an emulsion type suitable for the resin to be used.
[0041]
Moreover, as water used for the composition for water-soluble ink, normal industrial water can be used, and as a solvent comprising water and alcohol, in addition to water, ethanol, isopropyl alcohol, N-propyl alcohol Etc. can be prepared using lower alcohols such as, glycols and esters thereof. In that case, it is desirable to contain the lower alcohol, glycols or esters thereof in a proportion of about 5 to 20% by weight. The above-mentioned solvents such as lower alcohols, glycols and esters thereof are used for the purpose of improving the fluidity of the ink, improving the fluidity of the ink, improving the wetness of the printing medium, and adjusting the drying property. The type and amount used are determined according to the purpose.
[0042]
Using the above water-based ink composition, for example, a gravure printing method or a flexographic printing method, on the front surface, back surface or both surfaces of the base film, for example, characters, figures, symbols, and other desired printed pattern layers 5 can be formed.
[0043]
Next, the manufacturing method of the decorative sheet of FIG. 2 will be described.
[0044]
The shielding layer 4 on the surface of the base sheet 1 can be formed on the base sheet 1 by printing with water-based ink in the same manner as the printed pattern layer 5. Alternatively, the concealing layer 2 is formed by applying an aqueous dry laminating adhesive to a colored resin sheet such as white polyethylene with a gravure coater and drying and laminating together with the base material sheet 1 after drying. Next, a printed pattern layer 5 is formed on the concealing layer 2 by gravure printing using water-based ink. The decorative sheet shown in FIG. 2 can be obtained by adhering the base sheet 1 on which the printed pattern has been applied using a water-based adhesive or a solventless adhesive.
[0045]
Next, FIG. 3 shows a third embodiment of the decorative sheet of the present invention.
[0046]
In this decorative sheet, a base material sheet 4 with a printing pattern in which a shielding layer 4 is provided on a base material sheet 1 and a printing pattern layer 5 is provided on the shielding layer 4 is used. The surface sheet 2 is embossed to form a concavo-convex pattern 6 and the concave portion of the concavo-convex pattern 6 is filled with water-based ink 7.
[0047]
The embossing of the top sheet 2 can be performed by known embossing means such as a roll embossing machine or a lithographic embossing machine. Needless to say, when the printed pattern is applied to the base material sheet 2, it is preferable that the embossed pattern and the printed pattern are synchronized.
[0048]
The water-based ink 7 filled in the recesses of the uneven pattern 6 is obtained by dispersing an additive such as a pigment in a water-soluble resin or various resin emulsions. A small amount of alcohol can be added to water as a diluent to speed up drying.
[0049]
Examples of emulsions used in the water-based ink 7 that fills the recesses of the concavo-convex pattern 6 are urethane emulsion, urethane-acrylic emulsion, acrylic emulsion, vinyl chloride emulsion, vinyl acetate emulsion, epoxy emulsion, ethylene-vinyl acetate copolymer emulsion. , Vinyl acetate-acrylic copolymer emulsion, acrylic-styrene copolymer emulsion, and vinylidene emulsion. In addition, SBR latex and NBR latex can be used. Water-soluble acrylic resin is mentioned as water-soluble resin.
[0050]
Emulsion components with active hydrogen in the molecule are cured by reaction with curing agents such as aziridine, epoxy, melamine, carbodiimide, oxazoline, etc., and solvent resistance, scratch resistance, water resistance, chemical resistance of the ink layer Improve sexiness.
[0051]
As the colorant, organic pigments such as azo pigments and phthalocyanine pigments can be used, and inorganic pigments such as titanium dioxide, petals, carbon black, calcium carbonate and the like can also be used.
[0052]
When it is desired to make the ink layer matt, a matting material such as microsilica or a resin beam may be added in addition to the color pigment.
[0053]
If an extender pigment such as precipitated barium sulfate is dispersed in the water-based ink, the drying property and transferability of the ink can be improved.
[0054]
It is desirable to add an antifoaming agent to the water-based ink because it easily foams when the additive is dispersed. As the defoaming material, a known material such as silicone can be used.
[0055]
In order to increase the strength of the ink layer, the above-described curing agent, for example, an aziridine-based curing agent may be added. The blending amount of the curing agent may be about 3 to 4 parts by weight with respect to 100 parts by weight of the ink.
[0056]
Filling the concave portions of the concavo-convex pattern 6 with water-based ink can be performed by a known wiping method using a knife coater, a bar coater or the like.
[0057]
Next, FIG. 4 shows a fourth embodiment of the decorative sheet of the present invention.
[0058]
This decorative sheet is formed by applying a water-based adhesive 2 to a base sheet 1 on which a concealing layer 4 is formed by printing using a water-based ink on a surface and a printing pattern 5 is formed on the concealing layer 4 using a water-based ink. The surface sheet 3 is laminated to obtain a laminated sheet. The laminated sheet is subjected to doubling embossing, and the concave portion of the concavo-convex pattern 6 formed on the surface of the surface sheet 3 is filled with the water-based ink 7. The surface coat layer 8 is formed on the substrate 3 by printing using water-based ink.
[0059]
Example 1
As a base sheet, 100 parts by weight of a hard segment made of isotactic polypropylene, 100 parts by weight of a soft segment made of styrene-butadiene rubber, 30 parts by weight of an inorganic filler (calcium carbonate powder), and 10 parts by weight of a pigment are blended. An 80 μm polyolefin sheet obtained by extrusion after melt-kneading was prepared, and corona discharge treatment was performed on both sides thereof. On this base sheet, a concealed colored solid layer is formed by gravure printing using a water-based ink comprising the following composition A, and then an abstract pattern printing layer is formed by gravure printing using the water-based ink comprising composition B. A printed sheet was obtained.
[0060]
Water-based ink (Composition A)
Water-dispersed polyurethane resin-containing white water-based ink 100 parts by weight
(Ode WKE white, manufactured by The Ink Tech)
Water water 16 parts by weight
Ethanol 12 parts by weight
Normal propanol 12 parts by weight
[0061]
Water-based ink (Composition B)
Red water-based ink containing water-dispersed polyurethane resin 100 parts by weight
(Ode WKE red, made by The Ink Tech)
Water water 16 parts by weight
Ethanol 12 parts by weight
Normal propanol 12 parts by weight
[0062]
On the other hand, as a surface sheet, a mixture of 160 parts by weight of a hard segment made of isotactic polypropylene and 40 parts by weight of a soft segment made of atactic polypropylene was melt kneaded with 0.2 wt% of a benzotriazole UV absorber. Then, an extruded 80 μm polyolefin resin sheet was prepared, and corona discharge treatment was performed on both sides thereof.
[0063]
Next, an aqueous dry laminate adhesive having the following composition C is applied to the printing surface of the printing sheet with a gravure coater at about 3 g / m²After coating and drying, the above surface sheet was layered on the coated surface and pressed between nip rollers to obtain a decorative sheet made of a laminated sheet. This decorative sheet was aged at room temperature. Thereafter, when the adhesive strength and pot life were examined, the adhesive strength was sufficient, and after blending the dry laminate adhesive (after adding the cross-linking agent to the main agent), it did not gel and the pot life was sufficient. I understood.
[0064]
Water-based dry laminate adhesive (Composition C)
Water-dispersed polyurethane resin 100 parts by weight
(Evafar HO14, manufactured by Nikka Chemical)
Isocyanurate skeleton-containing isocyanate compound 9 parts by weight
(X9003, manufactured by Nikka Chemical)
Water 10 parts by weight of water
Isopropanol 10 parts by weight isopropanol
[0065]
(Example 2)
Furthermore, the laminated sheet obtained in Example 1 was heated by a preheater installed at the exit of the nip roller, and immediately embossed using an embossing roll to form an uneven pattern on the surface sheet side of the laminated sheet.
[0066]
Using the knife coater, the formed concave and convex portions were filled with water-based ink having the following composition D to obtain a decorative sheet.
[0067]
Water-based ink (Composition D)
Anion type urethane emulsion part 50 parts by weight
Non-yellowing ester, NV30%)
Precipitated barium sulfate 20 parts by weight
Carbon black 10 parts by weight
Microsilica 4 parts by weight
Defoamer (silicone) 0.5 parts by weight
Diluent (water) 16 parts by weight
[0068]
Example 3
A laminated sheet was produced in the same manner as in Example 1, and doubling embossing was applied to the laminated sheet.
[0069]
After filling the concave portions of the concavo-convex pattern formed on the surface of the surface sheet with water-based ink in the same manner as in Example 1, the surface coating layer was gravure coated on the surface of the surface sheet to form a surface coat layer and dried. The decorative sheet of the present invention was obtained.
[0070]
Water-based ink (Composition E)
Anionic urethane emulsion 50 parts by weight
Urethane-acrylic emulsion 15 parts by weight
Microsilica 4 parts by weight
Wax (polyethylene-based) 2 parts by weight
Leveling agent (silicone type) 0.5 parts by weight
Defoamer (silicone) 0.5 parts by weight
Thickener: 4 parts by weight of thickener
Diluent (water) 24 parts by weight
[0071]
(Example 4)
A decorative sheet was obtained in the same manner as in Example 1, except that an aqueous dry laminate adhesive having the following composition F was used. This decorative sheet was aged at room temperature. Then, when it investigated about adhesive strength and pot life, it turned out that adhesive strength is enough. However, after blending the dry laminate adhesive (after adding the crosslinking agent to the main agent), it gelled in 10 minutes, and it was found that the pot life was not sufficient.
[0072]
Aqueous dry laminate adhesive (Composition F)
Water-dispersed polyurethane resin 100 parts by weight
(Evafar HO14, manufactured by Nikka Chemical)
Biuret skeleton-containing isocyanate compound 9 parts by weight
(Duranate WT30-100, manufactured by Asahi Kasei Corporation)
Water 10 parts by weight of water
Isopropanol 10 parts by weight isopropanol
[0073]
(Example 5)
A decorative sheet was obtained in the same manner by replacing the aqueous dry laminate adhesive of composition C in Example 1 with a reactive hot melt adhesive (manufactured by Nippon Fuller Co., Ltd., HL-8805). The coating condition of the adhesive was such that the reactive hot melt adhesive melted by heating to 135 ° C. was applied on the printing surface of the printing sheet with a die coater 40 to 70 g / m²I went there.
[0074]
(Comparative example)
In the same manner as in Example 1, except that an aqueous dry laminate adhesive having the following composition F was used. As a result of examining the adhesive strength after aging at room temperature, sufficient adhesive strength was not recognized because the adhesive of composition G was difficult to ink. Moreover, when the pot life was investigated, it turned out that it gelled in less than 4 hours after mix | blending a dry laminate adhesive (after adding a crosslinking agent to a main ingredient), and pot life was not enough.
[0075]
Aqueous dry laminate adhesive (Composition G)
Water-dispersed polyurethane resin 100 parts by weight
(Evafar HO14, manufactured by Nikka Chemical)
Adduct type isocyanate compound 9 parts by weight
(Deyuranate P ・ 301 ・ 75E, manufactured by Asahi Kasei Corporation)
Water 10 parts by weight of water
Isopropanol 10 parts by weight isopropanol
[0076]
【The invention's effect】
As described above in detail, since the solvent-based ink and the solvent-based adhesive are not used in the decorative sheet of the present invention and the method for producing the same, the problem of pollution such as air pollution due to the solvent released by drying after printing, etc. The present invention makes it possible to provide a decorative sheet with high safety, and the working environment is improved, and there is no need to make the factory facility an explosion-proof facility.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a decorative sheet according to a first embodiment of the present invention.
FIG. 2 is a cross-sectional view showing a decorative sheet according to a second embodiment of the present invention.
FIG. 3 is a cross-sectional view showing a decorative sheet according to a third embodiment of the present invention.
FIG. 4 is a cross-sectional view showing a decorative sheet according to a fourth embodiment of the present invention.
[Explanation of symbols]
1 Base sheet
2 Water-based adhesive layer or solventless adhesive layer
3 Surface sheet
4 Concealment layer
5 Print pattern layer
6 Uneven pattern
7 Water-based ink
8 Surface coat layer

Claims (22)

A decorative sheet, wherein a surface sheet is laminated on the surface of a resin base sheet with an aqueous adhesive or a solventless adhesive interposed therebetween. The decorative sheet according to claim 1, wherein a masking layer is formed on the surface of the base material sheet, and then a printed pattern layer is formed on the masking layer using an aqueous printing ink. The decorative sheet according to claim 1 or 2, wherein the surface sheet is embossed to form an uneven pattern. The decorative sheet according to claim 1 or 2, wherein both the surface sheet and the base sheet are embossed, and an uneven pattern is formed on both the surface sheet and the base sheet. The decorative sheet according to claim 3 or 4, wherein an aqueous colorant is filled in a concave-convex pattern formed on the top sheet. The decorative sheet according to claim 4, wherein a surface coat layer is formed on the surface sheet on which the uneven pattern is formed. The decorative sheet according to any one of claims 1 to 6, wherein a urethane-based dry laminate adhesive is used as the aqueous adhesive. 8. The decorative sheet according to claim 7, wherein the urethane-based dry laminate adhesive contains an isocyanate compound having two or more isocyanate groups in the molecule and is water-dispersible or water-soluble. The decorative sheet according to claim 8, wherein the isocyanate compound contains an isocyanurate skeleton. A reactive hot-melt adhesive is used as the solvent-free adhesive, and the decorative sheet according to any one of claims 1 to 6. The decorative sheet according to claim 2, wherein the masking layer contains an isocyanate compound. The decorative sheet according to claim 11, wherein the isocyanate compound is an isocyanate compound having two or more isocyanate groups in the molecule. The decorative sheet according to claim 11, wherein the isocyanate compound contains an isocyanurate skeleton. The decorative sheet according to any one of claims 1 to 13, wherein the base sheet and the top sheet are made of polyolefin. A concealing layer is formed on the surface of the resin base sheet, and then a printed pattern layer is formed on the concealing layer using a water-based printing ink. A method for producing a decorative sheet, which comprises adhering to an adhesive using an aqueous or solvent-free adhesive. The method for producing a decorative sheet according to claim 15, wherein the shielding layer is formed using water-based ink. The method for producing a decorative sheet according to claim 15, wherein the hiding layer is formed using a water-based ink containing an isocyanate compound. The method for producing a decorative sheet according to claim 15, wherein the shielding layer is formed by adhering a colored resin sheet to the base sheet through an aqueous adhesive layer or a solventless adhesive layer. The method for producing a decorative sheet according to claim 16, wherein an aqueous dry laminate adhesive is used as the adhesive, and the base sheet is laminated on the top sheet by dry lamination. The method for producing a decorative sheet according to claim 15, wherein a solventless adhesive is used as an adhesive, and the solventless adhesive is applied to the surface of the base sheet, and then the base sheet is bonded to the top sheet. . The method for producing a decorative sheet according to claim 15, wherein the surface sheet is embossed to form a concavo-convex pattern, and the concave portion of the concavo-convex pattern is filled with water-based ink by a wiping method. Laminating a surface sheet on the base sheet, forming a printed pattern with water-based ink on the surface sheet, then forming an overcoat layer on the surface sheet, and then embossing in synchronization with the printed pattern, The method for producing a decorative sheet according to claim 15, wherein an uneven pattern is formed.

Images