JP4030170B2 - Composite decorative sheet and method for producing the same - Google Patents

Description

【００５３】
（式中、Ｒ、Ｒ’は、炭化水素基（アルキル基）を表す。）
【００５４】
なお、上記反応式において、アゾジオール、ジオールおよびジイソシアネートを低温で付加反応させて生成する上記のポリウレタンアゾ高分子は、ポリウレタン−アクリルブロック共重合体の原料であり、また、重合反応の開始剤としても作用する。
上記の重合開始剤２０重量％とｎ−ブチルメタクリレート８０重量％をメチルエチルケトン中で８０℃、２０時間重合させると上記のポリウレタン−アクリルブロック共重合体を得ることができる。
【００５５】
本発明で使用されるポリウレタン−アクリルブロック共重合体は、従来の低分子重合開始剤を用いて合成されたアクリル樹脂と比較して、伸び率、抗張力がいずれも向上しており、塗膜性能（乾燥性、耐溶剤性、透湿性、耐候性）も優れている。
上記の樹脂をバインダーとするインキを、５〜１０ｇ／ｍ² 程度全面に塗布して下地隠蔽インキ層を形成した後、樹脂の硬化反応を促進するため、必要に応じて塗工後に加熱してもよい。
【００５６】
なお、インキ中にトルエンやキシレン等の芳香族溶剤が含有されると、芳香族溶剤により下地のポリオレフィン系樹脂の膨潤が起こり、印刷位置の見当（レジスタ）が合わなくなる場合があるので、芳香族化合物からなる溶剤を用いるのは避けるのが好ましい。
【００５７】
絵柄層は、下地隠蔽インキ層と同様にポリウレタン−アクリルブロック共重合体を用いて形成する。絵柄層のポリウレタン−アクリルブロック共重合体にも、ヘキサメチレンジイソシアネート等のイソシアネート化合物の架橋剤を添加することもできる。
絵柄層の形成は、通常、グラビア印刷、オフセット印刷、シルクスクリーン印刷、転写シートからの転写印刷等、公知の印刷法を用いて行う。絵柄としては、木目柄、石目柄、布目柄、幾何学模様、文字等、任意の絵柄を選択できる。
【００５８】
絵柄層と、その上層に形成されるオレフィン系樹脂からなるトップオレフィン層とを接着するため、絵柄層上層に接着剤層を形成する。接着剤樹脂としては、好ましくは、二液硬化型ポリエステルウレタン系樹脂等、汎用されている二液硬化型ポリウレタン系樹脂からなるドライラミネート接着剤を用いることができる。
【００５９】
通常、オレフィン層を有する積層体を形成する方法としては、あらかじめオレフィンフィルムを所定の厚さに成膜しておき、そのフィルムを被接着面にウレタン系樹脂やエポキシ系樹脂等の接着剤を用いて貼り合わせるドライラミネート法と、接着層として溶融オレフィンを用いて被接着面とオレフィンフィルムをサンドラミネートするポリサンド法がある。
【００６０】
しかしながら、ポリサンド法でオレフィン層を十分に接着させるには３００℃程度の加熱工程が必要であり、高分子の一部が分解する可能性がある。そのため、オレフィン層を異種の樹脂層と接着させるにはドライラミネート法が最も確実である。
【００６１】
トップオレフィン層（表面保護層）は、上記ベースオレフィン層と同様に、プロピレン等のオレフィン系樹脂からなり、通常、透明シートが用いられる。膜厚もベースオレフィン層と同様に、５０〜１５０μｍ程度が好ましい。
【００６２】
また、必要に応じて、トップオレフィン層の表面には、耐磨耗性・耐擦傷性の向上、表面光沢の調整、トップオレフィン層中に含有される紫外線吸収剤（特に、ブリードし易い有機系のもの）の経時的なブリード防止等の目的から、上塗塗膜を形成する。
【００６３】
上塗塗膜に用いる塗料としては、上記の上塗塗膜の用途、また、オレフィン系樹脂との密着性を考慮すると、二液硬化型ウレタン樹脂を成分とするものが好ましい。上塗塗膜の膜厚は、通常、１〜１０μｍ程度であり、ロールコータ、グラビアロールコータ等、公知の塗工法により上塗塗膜を形成する。
【００６４】
本発明の複合化粧シートは、壁、床、天井等の建築物内装材、窓枠、扉枠、扉、手摺等の建具、箪笥等の家具、家電製品やＯＡ機器のキャビネット、車輛、船舶、航空機等の乗物内装材等の表面化粧材として使用される。
【００６５】
【実施例】
以下に、本発明の複合化粧シートおよびその製造方法の実施の形態について、図面を参照して説明する。
【００６６】
（実施例１）
図１に、実施例１の複合化粧シートの断面図を示す。
本実施例の複合化粧シートは、ベースオレフィン層１１上に絵柄層１２が形成され、さらに接着剤層１３を介して透明なトップオレフィン層１４が積層された構造を有する。
【００６７】
以下に、本実施例の複合化粧シートの製造方法について説明する。
まず、オレフィン系熱可塑性エラストマーフィルムからなるベースオレフィン層１１を易接着性とするため、表面にコロナ放電処理を施して、フィルム表面の濡れを大きくし、臨界表面張力を５０（ｄｙｎｅ／ｃｍ）程度とする。
【００６８】
オレフィン系熱可塑性エラストマーフィルムは、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とアタクチックポリプロピレンからなるソフトセグメントとを８０：２０重量比で混合した組成のものを用いる。
フィルムの膜厚は８０μｍとする。
【００６９】
また、本実施例においては下地隠蔽インキ層（全面ベタ印刷層）を設けないので、あらかじめオレフィン系樹脂に顔料を混和させ不透明に着色しておく。顔料としては例えばチタン白、弁柄およびカーボンブラック等を用いる。
【００７０】
次に、アゾジオール、ジオールおよびジイソシアネートとを付加反応させたポリウレタンアゾ高分子２０重量％とｎ−ブチルアクリレート８０重量％とを重合させたポリウレタン−アクリルブロック共重合体からなるバインダーに顔料を添加したインキを、前記ベースオレフィン層１１上に塗工して、絵柄層１２を形成する。
塗工は、例えばグラビア印刷法により行い、木目柄等の模様を印刷する。
【００７１】
さらに、アクリルポリオールとヘキサメチレンジイソシアネートからなる二液硬化型ポリウレタン樹脂の接着剤層１３を、１０μｍ厚で塗工する。
その上層に、あらかじめ接着面がコロナ処理により易接着化されているポリプロピレン系樹脂フィルム（膜厚８０μｍ）をトップオレフィン層１４として積層する。トップオレフィン層１４には、ヒンダードアミン系ラジカル捕捉剤を０．５重量％添加、ベンゾトリアゾール系紫外線吸収剤を０．５重量％添加した、ベースオレフィン層１１と同じ組成の樹脂を用いることができる。
以上により、本実施例の複合化粧シートを製造することができる。
【００７２】
（実施例２）
図２に、本実施例の複合化粧シートの断面図を示す。
本実施例の複合化粧シートは、ベースオレフィン層２１上にプライマー層２２が形成され、その上層に絵柄層２３が形成され、さらに接着剤層２４を介してトップオレフィン層２５が積層された構造を有する。
【００７３】
以下に、本実施例の複合化粧シートの製造方法について説明する。
まず、オレフィン系熱可塑性エラストマーフィルムからなるベースオレフィン層２１を易接着性とするため、表面にコロナ放電処理を施して、フィルム表面の濡れを大きくし、臨界表面張力を５０（ｄｙｎｅ／ｃｍ）程度とする。
【００７４】
オレフィン系熱可塑性エラストマーフィルムは、高密度ポリエチレン１００重量部にゴム３０重量部、炭酸カルシウム粉末からなる体質顔料（充填剤）を１０重量部、チタン白顔料を６重量部添加した組成のものを用いる。
また、フィルムの膜厚は８０μｍとする。
【００７５】
プライマー層２２としては、ポリエステルポリオールとヘキサメチレンジイソシアネートとからなる二液硬化型ポリウレタン樹脂を用い、樹脂を塗料化し、グラビアコート法、リバースロールコート法、カーテンフローコート法等の既知の方法により塗布してプライマー層２２を形成する。
【００７６】
次に、アゾジオール、ジオールおよびジイソシアネートとを付加反応させたポリウレタンアゾ高分子２０重量％とｎ−ブチルアクリレート８０重量％とを重合させたポリウレタン−アクリルブロック共重合体からなるバインダーに顔料を添加したインキを、前記プライマー層２２上に塗工して、絵柄層２３を形成する。塗工は、例えばグラビア印刷法により行い、石目柄等の模様を印刷する。
さらに、アクリルポリオールとヘキサメチレンジイソシアネートからなる二液硬化型ポリウレタン樹脂の接着剤層２４を、１０μｍ厚で塗工する。
【００７７】
その上層に、あらかじめ接着面がコロナ処理により易接着化されているポリプロピレン系樹脂フィルム（膜厚８０μｍ）からなるトップオレフィン層２５を積層する。トップオレフィン層１４には、ヒンダードアミン系ラジカル捕捉剤を０．５重量％添加、ベンゾトリアゾール系紫外線吸収剤を０．５重量％添加した、ベースオレフィン層２１と同じ組成の樹脂を用いることができる。
以上により、本実施例の複合化粧シートを製造することができる。
【００７８】
（実施例３）
図３に、本実施例の複合化粧シートの断面図を示す。
本実施例の複合化粧シートは、ベースオレフィン層３１上にプライマー層３２が形成され、その上層に、ポリウレタン−アクリルブロック共重合体をバインダーとする下地隠蔽インキ層（ベタ層）３３、および木目柄の絵柄層３４が形成され、さらに接着剤層３５を介してトップオレフィン層３６が積層された構造を有する。
【００７９】
上記の実施例１および２に示す各製造工程を組み合わせることにより、上記の本実施例の複合化粧シートの構成とすることができる。本発明の複合化粧シートにおいては、本実施例のように、ベースオレフィン層３１と絵柄層３４との層間に、プライマー層３２と下地隠蔽インキ層３３の両方を設けることもできる。
【００８０】
（実施例４）
図４に、本実施例の複合化粧シートの断面図を示す。
本実施例の複合化粧シートは、ベースオレフィン層４１上にプライマー層４２が形成され、その上層に下地隠蔽インキ層（ベタ層）４３、絵柄層４４が形成され、さらに接着剤層４５を介してトップオレフィン層４６が積層された構造を有する。
【００８１】
上記の層構成の材料および製法は、実施例３と同様であるが、本実施例においては、以上に加えてさらに、以下の構成を有する。
トップオレフィン層４６表面には、エンボス加工により木目導管溝の凹凸模様が施され、凹部にワイピングインキ４８が埋め込まれている。ワイピングインキ４８としては、アクリルポリオールとヘキサメチレンジイソシアネートからなるバインダーにカーボンブラックの顔料を添加してなるものを用いる。
【００８２】
トップオレフィン層４６上層にはアクリルポリオールとヘキサメチレンジイソシアネート１００対１０重量比で混合してなる二液硬化型ウレタン樹脂からなる上塗塗膜４７が形成されている。
【００８３】
ベースオレフィン層４１裏面には、ヘキサメチレンジイソシアネートを架橋剤としてポリエステルポリオールをウレタン結合で架橋した二液硬化型ウレタン樹脂を基材とする裏面プライマー層４０が形成されている。裏面プライマー層４０は、基材である二液硬化型ウレタン樹脂に、シリカ粉末を２５重量％添加して塗料化したものを、グラビアコート法、リバースロールコート法、カーテンフローコート法等の既知の方法により塗布して形成する。
【００８４】
上記の実施例１および２に示す各製造工程を組み合わせることにより、トップオレフィン層４６以下の層を積層した後、トップオレフィン層４６表面にコロナ放電処理を施してから上塗塗膜４７を形成し、上塗塗膜４７表面にエンボス加工を施す。全面に着色インキを塗布した後、ただちに表面をドクターブレード、ゴムロール等で掻き取って余分なインキを除去し、エンボス凹部のみに着色インキを残してワイピングインキ４８部を形成する。
【００８５】
本発明の複合化粧シートおよびその製造方法は、上記の実施の形態に限定されない。例えば、ベースオレフィン層やトップオレフィン層の膜厚は、適宜変更できる。また、トップオレフィン層または上塗塗膜表面に施される装飾処理は、ワイピングインキを塗布せず、エンボス加工のみであってもよい。
本発明においては、上記実施例に限定されることなく、本発明の要旨を逸脱しない範囲で、種々の変更が可能である。
【００８６】
【比較例】
（比較例１）〜（比較例４）
前記の実施例１〜実施例４において、下地隠蔽インキ層のバインダーをアクリルポリオールとヘキサメチレンジイソシアネートの混合物とし、絵柄層のバインダーをアクリル樹脂と塩化ビニル−酢酸ビニル共重合体との１対１重量比混合物に変更し、それ以外の層は実施例１〜実施例４と同様である複合化粧シートを製造し、それぞれ比較例１〜比較例４とした。
【００８７】
耐光密着性の評価
各実施例および各比較例の複合化粧シートのトップオレフィン層側から紫外線を照射し、屋外曝露の促進劣化試験を行った。試験法としては、紫外線光源として、岩崎電気（株）製アイスーパーＵＶテスター（型式ＳＵＶ−Ｗ１３）を用い、紫外線照射量（紫外線強度）６０ｍＷ／ｃｍ² の照射２０時間と、非照射、結露した条件での放置４時間を１サイクルとして行った。この操作を繰り返すと、１００時間が屋外曝露１年程度に相当する。
【００８８】
促進劣化試験の経過時間１００時間と４００時間の２段階で判定を行い、各照射時間後の試料について、トップオレフィン層とベースオレフィン層との層間剥離強度を測定し、耐光密着性を評価した。
【００８９】
剥離試験は、１インチ幅の試験片について引張試験機により、トップオレフィン層とベースオレフィン層とのなす角を１８０℃にして引っ張り、剥離時の張力で耐光密着性を評価した。
【００９０】
評価結果
実施例１〜実施例４は、照射時間１００時間、４００時間とも、剥離時の張力はいずれも３〜３．５ｋｇ／インチであったが、比較例１〜比較例４は、照射時間１００時間でいずれも１ｋｇ／インチ以下、照射時間４００時間で、いずれも０．６ｋｇ／インチ以下となった。
【００９１】
【発明の効果】
以上説明したように、本発明の複合化粧シートは、オレフィン系樹脂を主材とする従来の複合化粧シートに較べ、屋外曝露時の紫外線に対する耐光密着性が著しく向上したものである。
【００９２】
また、従来の複合化粧シートでは、促進劣化試験で屋外曝露１年相当の紫外線照射でベースオレフィン層とプライマー層との層間で剥離が生じるが、上記の本発明の製造方法によれば、同様な促進劣化試験で屋外曝露４年相当の紫外線照射を行っても、層間の剥離または印刷インキの顕著な退色の生じない複合化粧シートを製造することができる。
【００９３】
さらに、本発明の複合化粧シートは、塩化ビニル樹脂を主材とする複合化粧シートでみられるような、焼却時の塩素化物ガスの問題もなく、耐光密着性も優れるため、耐候性が必要とされる建築材等に好ましく用いることができる。
【図面の簡単な説明】
【図１】本発明の実施例１に示す複合化粧シートの断面図である。
【図２】本発明の実施例２に示す複合化粧シートの断面図である。
【図３】本発明の実施例３に示す複合化粧シートの断面図である。
【図４】本発明の実施例４に示す複合化粧シートの断面図である。
【図５】従来の複合化粧シートの断面図である。
【符号の説明】
１１、２１、３１、４１、５１…ベースオレフィン層、１２、２３、３４、４４、５４…絵柄層、１３、２４、３５、４５、５５…接着剤層、１４、２５、３６、４６、５６…トップオレフィン層、２２、３３、４３、５３…下地隠蔽インキ層、３２、４２、５２…プライマー層、４０…裏面プライマー層、４７…上塗塗膜、４８…ワイピングインキ。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a composite decorative sheet and a method for producing the same, and in particular, in a composite decorative sheet mainly composed of an olefin-based resin, by forming a polyurethane resin having excellent extensibility and weather resistance as a pattern layer, the weather resistance and The present invention relates to a composite decorative sheet having improved light resistance and a method for producing the same.
[0002]
[Prior art]
Conventionally, vinyl chloride resins have been widely used as the main material of composite decorative sheets. Since vinyl chloride resin contains an electrically negative chlorine atom, it has good affinity with plasticizers and colorants. Various effects can be achieved by changing the degree of polymerization of the resin and adding additives such as plasticizers and fillers. Products with unique properties can be made.
For example, when 5% by weight or more of a plasticizer is added, it becomes a semi-rigid or soft vinyl chloride resin.
[0003]
The semi-rigid or soft vinyl chloride resin as described above can freely color the resin by mixing with a colorant, and can be subjected to decorative treatment such as embossing on the surface, and the raw material is also inexpensive. It is used for soft products such as sheets.
[0004]
However, semi-rigid or soft vinyl chloride resin has low heat resistance and has the property of decomposing and releasing hydrogen chloride at high temperatures (150 ° C. or higher). In general, heat resistance is lowered by adding a plasticizer, so that a soft vinyl chloride resin having a high plasticizer content used for a sheet or the like is easily pyrolyzed, and a chlorinated gas such as hydrogen chloride is generated during incineration.
[0005]
In addition, the composite decorative sheet mainly composed of vinyl chloride resin is used to elution (bleed out) the heat stabilizer and plasticizer added to the resin when the sheet is used. Or in the case of a laminated body, the adhesive force between layers may fall. Furthermore, it is difficult to recycle resin waste due to the thermal decomposition of vinyl chloride resin at high temperatures.
For these reasons, composite decorative sheets in which the main material is replaced with an olefin resin from a vinyl chloride resin have come to be used (JP-A-6-16832, JP-A-6-7980, etc.). ).
[0006]
FIG. 5 shows an example of a cross-sectional view of a conventional composite decorative sheet mainly composed of an olefin resin. In this composite decorative sheet, a primer layer 52, a base concealing ink layer 53, a picture layer 54, a dry laminate adhesive layer 55, and a top olefin layer 56 are laminated on the base olefin layer 51 in this order.
[0007]
Polypropylene resin is used for the base olefin layer 51 and two-component curable urethane resin is used for the primer layer 52. The base concealing ink layer 53 uses a two-component curable urethane resin composed of an acrylic polyol and an isocyanate such as hexamethylene diisocyanate as a binder, and the pattern layer 54 includes an acrylic resin and a vinyl chloride-vinyl acetate copolymer. What used the mixture of 1 to 1 to 8 to 2 weight ratio as a binder is used. A two-component curable urethane resin is used for the dry laminate adhesive layer 55, and an olefin resin mainly made of polypropylene is used for the top olefin layer 56.
[0008]
[Problems to be solved by the invention]
However, in the above conventional composite decorative sheet, the light resistance (weather) adhesion is not sufficient, and when the accelerated deterioration test of the outdoor exposure is performed by irradiating ultraviolet rays using a deuterium lamp or the like as the light source, the outdoor exposure 1 There is a problem that peeling occurs between the base olefin layer 51 and the primer layer 52 in an irradiation time corresponding to about a year.
[0009]
With regard to the above light-resistant adhesion, when at least one of the base concealing ink layer 53 and the pattern layer 54 contains a vinyl chloride-vinyl acetate copolymer as a general-purpose ink binder, the pattern layer 54 and the primer layer It has been confirmed that the adhesiveness between the layers with 52 decreases. On the other hand, when the printing layer is formed by unifying the acrylic resin, the light-resistant adhesion is slightly improved, but peeling occurs due to ultraviolet irradiation equivalent to two years of outdoor exposure, and sufficient light-resistant adhesion cannot be obtained.
[0010]
The present invention has been made in view of the above problems, and aims to provide a composite decorative sheet having improved light-resistant adhesion and a method for producing the same in a composite decorative sheet mainly composed of an olefin resin. To do.
[0011]
[Means for Solving the Problems]
  To achieve the above object, the composite decorative sheet of the present invention comprises a base olefin layer made of an olefin resin, a primer layer made of a two-component curable polyurethane formed on the upper layer of the base olefin layer, and an upper layer of the primer layer. A pattern layer made of an ink having a polyurethane-acrylic block copolymer obtained by polymerizing a formed polyurethane azo polymer, which is an addition product of azodiol, diol and diisocyanate, and an acrylic monomer, and the upper layer of the pattern layer At least an adhesive layer made of two-component curable polyurethane formed on the adhesive layer and a top olefin layer made of an olefin resin formed on the upper layer of the adhesive layer.The two-component curable polyurethane used for the primer layer is an acrylic polyol and an aliphatic or alicyclic isocyanate.It is characterized by that.
[0014]
By adopting such a composite decorative sheet, the light-resistant adhesion of the composite decorative sheet mainly composed of an olefin resin is improved as compared with the conventional composite decorative sheet. Further, the improvement in light-resistant adhesion eliminates the need for a primer layer provided between the pattern layer and the adhesive layer, which is required for conventional sheets. Therefore, a composite decorative sheet with improved light resistance can be produced with fewer production steps.
[0015]
In general, polyurethane resins have excellent flexibility and extensibility, and acrylic resins have high weather resistance and hardness. A block copolymer having composite characteristics of polyurethane resin and acrylic resin and having the characteristics of each resin has been synthesized.
[0016]
The polyurethane-acrylic block copolymer is superior in drying property, solvent resistance, moisture permeability, and weather resistance as compared with an acrylic resin polymerized using a conventional low molecular weight polymerization initiator. When used as a printing layer of the composite decorative sheet, the light-resistant adhesion of the composite decorative sheet can be improved.
[0017]
  Furthermore, in order to achieve the above object, the method for producing a composite decorative sheet of the present invention includes a step of forming a primer layer made of a two-component curable polyurethane on a base layer made of an olefin resin, And a step of forming by printing a pattern layer comprising an ink having a polyurethane-acrylic block copolymer obtained by polymerizing an acrylic monomer and a polyurethane azo polymer, which is an addition reaction product of azodiol, diol and diisocyanate. And a step of forming an adhesive layer made of a two-component curable polyurethane on the pattern layer by coating, and a step of laminating and forming a top olefin layer made of an olefin resin on the adhesive layer.The two-component curable polyurethane used for the primer layer is an acrylic polyol and an aliphatic or alicyclic isocyanate.It is characterized by that.
[0018]
In the method for producing a composite decorative sheet according to the present invention, preferably, the printing step for forming the pattern layer includes a step of printing in an unreacted state the polyurethane-acrylic block copolymer with an isocyanate compound added thereto. And a step of reacting the polyurethane-acrylic block copolymer with the isocyanate compound to form a urethane bond.
[0019]
By adopting such a production method, it is possible to produce a composite decorative sheet having an olefin-based resin as a main material and improved light-resistant adhesion. When a conventional composite decorative sheet mainly composed of an olefin resin is irradiated with ultraviolet rays using a deuterium lamp or the like as a light source, there is a problem that peeling occurs between the base olefin layer and the primer layer within 100 hours of irradiation. However, according to the production method of the present invention described above, a composite decorative sheet can be produced in which peeling between layers and remarkable discoloration of printing ink do not occur even when ultraviolet irradiation is performed for 400 hours in the same manner.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
Below, each layer which comprises the composite sheet of this invention is demonstrated.
[0021]
The olefin resin used for the base olefin layer (base material layer) includes both thermoplastic olefin elastomers and non-elastomeric olefin resins, but is generally flexible because it is used for composite decorative sheets. Moldability is required, and a thermoplastic olefin elastomer is particularly preferable.
[0022]
Specifically, the non-elastomeric olefin-based resin is a crystalline polymer composed of a homopolymer composed of one olefin among olefins such as ethylene, propylene, butene and pentene, and a copolymer composed of two or more olefins. For example, polyethylene (low density or high density), ethylene-olefin copolymers such as ethylene-propylene copolymer and ethylene-1-butene copolymer, polypropylene, polymethylpentene, polybutene, propylene-butene copolymer A polymer, a propylene-ethylene random or block copolymer, etc. are mentioned.
In addition to the above, olefins used for copolymerization include olefins having 5 to 8 carbon atoms, such as 1-pentene, 1-hexene, 1-heptene, 1-octene and the like.
[0023]
Specific examples of thermoplastic elastomers include:
(1) described in Japanese Patent Publication No. 6-23278
(A) 10 to 90% by weight of atactic polypropylene soluble in boiling heptane having a number average molecular weight Mn of 25,000 or more as a soft segment and a ratio Mw / Mn ≦ 7 of the weight average molecular weight Mw and the number average molecular weight Mn; ,
(B) 90 to 10% by weight of isotactic polypropylene insoluble in boiling heptane having a melt index of 0.1 to 4 g / 10 min as a hard segment
Soft polypropylene consisting of a mixture of
[0024]
In particular, when it is molded into various shapes by heating and pressurizing or surface decoration such as embossing is applied, it is composed of a mixture of isotactic polypropylene and atactic polypropylene, and the weight ratio of atactic polypropylene is 10 to 10. 50% by weight is preferred.
[0025]
In the case of polypropylene-based olefin-based thermoplastic elastomers used for packaging containers and the like, strength is important, and the weight ratio of atactic polypropylene serving as a soft segment is often less than 5% by weight.
However, when an olefin-based resin is used in a composite decorative sheet as in the present invention, flexibility and workability are required, so the weight ratio of atactic polypropylene is 10% by weight or more, preferably 20%. % Or more.
[0026]
On the other hand, when the weight ratio of atactic polypropylene is excessive, the sheet itself is easily deformed, and when the sheet is passed through a printing machine, the sheet is deformed and the pattern is distorted, or it is registered in the case of multi-color printing (register). The problem of not being able to fit occurs.
Further, it is not preferable because it is easily broken during sheet molding.
[0027]
About the upper limit of the weight ratio of atactic polypropylene, the pattern layer is printed using a normal rotary printing machine such as rotary gravure printing, and when embossing, vacuum forming, etc. of the sheet is adopted, 50% by weight or less, Preferably, the content is 40% by weight or less.
[0028]
(2) A thermoplastic elastomer comprising an ethylene-propylene-butene copolymer containing at least one of three structural isomers of 1-butene, 2-butene and isobutylene as butene. The copolymer is a random copolymer and includes a part of an amorphous part.
[0029]
Preferable specific examples of the ethylene-propylene-butene copolymer include the following (A) to (C).
(A) A random copolymer of an ethylene-propylene-butene terpolymer described in JP-A-9-1111055. The weight ratio of the monomer components is 90% by weight or more of propylene. The melt flow rate is preferably 1 to 50 g / 10 min at 230 ° C. and 23.16 kg.
[0030]
0.1 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 based on 100 parts by weight of the ternary random copolymer as described above. What melt-kneads 003-0.3 weight part.
[0031]
(B) An ethylene-propylene-butene terpolymer described in JP-A-5-77371, wherein the propylene component content is 50% by weight or more in an amorphous polymer of 20 to 100% by weight. A product obtained by adding 80 to 0% by weight of high quality polypropylene.
[0032]
(C) As described in JP-A-7-316358. An ethylene-propylene-butene terpolymer, which is a crystal such as isotactic polypropylene with respect to 20 to 100% by weight of a low crystalline polymer having a propylene and / or 1-butene content of 50% by weight or more. A product obtained by adding 0.5% by weight of an oil gelling agent such as an N-acylamino acid amine salt or N-acylamino acid ester to 100 parts by weight of a composition obtained by mixing 80 to 0% by weight of a conductive polyolefin.
[0033]
The ethylene-propylene-butene copolymer resin may be used alone or may be used by further mixing other polyolefin resins as necessary with the resins (A) to (C).
[0034]
In addition to the above-mentioned phosphoric acid aryl ester compound, talc or aluminum benzoate may be added to the olefin resin as a transparent nucleating agent. Further, when particularly high transparency is required, a sorbitol-based transparent nucleating agent may be added.
[0035]
Furthermore, in order to improve the dispersibility of the transparent nucleating agent in the resin, at least one selected from an alkali metal salt of an organic carboxylic acid, a β-diketonate alkali metal salt, and a β-ketoacetate alkali metal salt. A seed dispersant may be added.
[0036]
Either one or both of an ultraviolet absorber and a light stabilizer can be commonly added to the olefin resin layer. The addition amount is usually about 0.1 to 5% by weight for both the ultraviolet absorber and the light stabilizer, and generally the ultraviolet absorber and the light stabilizer are used in combination.
[0037]
As the ultraviolet absorber, organic substances such as benzotriazole, benzophenone, benzoate, and salicylic acid ester, or inorganic substances such as fine particles of zinc oxide, cerium oxide, and titanium oxide having a diameter of 0.2 μm or less can be used.
As the light stabilizer, a hindered amine radical scavenger or a piperidine radical scavenger can be used.
[0038]
The thickness of the olefin resin film forming the base olefin layer is usually 50 to 200 μm, preferably 50 to 150 μm.
The olefin resin film may be transparent or opaque colored with a colorant such as a pigment or a dye.
[0039]
Examples of pigments or dyes include inorganic pigments such as titanium white, zinc white, cobalt blue, titanium yellow, and carbon black, organic dyes such as isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, and aniline black; Examples include pearlescent pigments made of titanium-coated mica foil powder.
[0040]
One side or both sides of the olefin-based resin film may be subjected to a surface treatment for improving the laminating property (easy-adhesive property) and adhesive application property of the olefin-based resin film. Examples of the surface treatment method include corona discharge treatment, plasma treatment, flame treatment, ozone treatment, acid treatment and the like, and any method can be used in the present invention.
[0041]
Of these methods, continuous treatment is possible, and since it can be easily performed before the winding process of the film production process, plasma treatment, flame treatment and corona discharge treatment are preferred, and corona from the viewpoint of simplicity. Discharge treatment is particularly preferred.
[0042]
In the upper layer of the base olefin layer, a primer layer is formed using a two-component curable polyurethane as necessary.
The pattern layer can be directly formed on a base olefin layer made of a pre-colored olefin resin film, but a primer layer made of a two-component curable polyurethane is formed on the base olefin layer, and an upper layer thereof is formed. By forming the pattern layer, the adhesion between the pattern layer and the base olefin layer can be further strengthened.
[0043]
In the conventional composite decorative sheet, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, two-component curable urethane resin, chlorinated polyolefin resin such as chlorinated polypropylene and chlorinated polyethylene as the resin that forms the primer layer, One kind or a mixture of two or more kinds was used.
[0044]
However, when a vinyl chloride-vinyl acetate copolymer is used, the light-resistant adhesion is lowered, and the polyester resin is not sufficiently dry, so that the primer layer is also made of a two-component curable polyurethane in the composite decorative sheet of the present invention. It is preferable to increase the affinity of the pattern layer with the resin.
[0045]
The two-part curable acrylic urethane resin used for the primer layer is mainly composed of polyol such as acrylic polyol, polyester polyol, polyether polyol, and polycarbonate polyol, and isocyanate as a crosslinking agent (curing agent).
[0046]
In particular, acrylic polyol is preferred as the polyol in terms of light resistance (weather) adhesion.
As the acrylic polyol, a condensation product of acrylic acid or methacrylic acid or a derivative thereof and a polyol having two or more hydroxyl groups in the molecule is used.
[0047]
As the isocyanate, a polyisocyanate having two or more isocyanate groups in the molecule is used. For example, 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tris (isocyanatephenyl) methane, tris Aromatic isocyanates such as (isocyanate phenyl) thiophosphate, or aliphatic or alicyclic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate are used. From the viewpoint of thermal discoloration prevention and weather resistance, It is desirable to use an aliphatic (or alicyclic) isocyanate.
[0048]
As the polyisocyanate, adducts and multimers can also be used. Examples thereof include adducts of tolylene diisocyanate and trimers of tolylene diisocyanate.
You may add the ultraviolet absorber and light stabilizer similar to what is used for said olefin resin to the two-component curable urethane resin of a primer layer.
[0049]
A highly concealing pigment such as titanium white or carbon black may be added to the base concealing ink layer. The binder for the base concealing ink layer is composed of a polyurethane-acrylic block copolymer obtained by polymerizing a polyurethane azo polymer, which is an addition reaction product of azodiol, diol and diisocyanate, and an acrylic monomer, and further necessary. Depending on the case, a resin to which an isocyanate compound is added is used.
[0050]
When adding an isocyanate compound, an isocyanate compound such as hexamethylene diisocyanate is added to the polyurethane-acrylic block copolymer as a crosslinking agent in an amount of about 5% by weight. Thereby, the toughness of a base concealing ink layer and light-resistant adhesiveness can be improved.
[0051]
  The polyurethane-acrylic block copolymer isAs described in Japanese Patent Laid-Open No. 7-3110 which is a known document,For example, it can be manufactured as follows. That is, it is possible to produce a polyurethane azo polymer by addition reaction of azodiol, diol and diisocyanate, and then polymerize the polyurethane azo polymer and an acrylic monomer.
[0052]
[Chemical 1]

[0053]
(In the formula, R and R ′ represent a hydrocarbon group (alkyl group).)
[0054]
In the above reaction formula, the above-mentioned polyurethane azo polymer produced by addition reaction of azodiol, diol and diisocyanate at a low temperature is a raw material for the polyurethane-acrylic block copolymer, and also serves as an initiator for the polymerization reaction. Works.
When 20% by weight of the polymerization initiator and 80% by weight of n-butyl methacrylate are polymerized in methyl ethyl ketone at 80 ° C. for 20 hours, the polyurethane-acrylic block copolymer can be obtained.
[0055]
The polyurethane-acrylic block copolymer used in the present invention is improved in both elongation and tensile strength compared to an acrylic resin synthesized using a conventional low molecular weight polymerization initiator. (Drying property, solvent resistance, moisture permeability, weather resistance) are also excellent.
5-10 g / m of ink having the above resin as a binder²After coating the entire surface to form a base concealing ink layer, in order to accelerate the curing reaction of the resin, it may be heated after coating, if necessary.
[0056]
If the ink contains an aromatic solvent such as toluene or xylene, the underlying polyolefin resin may swell due to the aromatic solvent, and the register (register) of the printing position may not match. It is preferable to avoid using a solvent comprising a compound.
[0057]
The pattern layer is formed using a polyurethane-acrylic block copolymer in the same manner as the base concealing ink layer. A crosslinking agent of an isocyanate compound such as hexamethylene diisocyanate can also be added to the polyurethane-acrylic block copolymer of the pattern layer.
The pattern layer is usually formed using a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, or the like. As the pattern, an arbitrary pattern such as a grain pattern, a stone pattern, a cloth pattern, a geometric pattern, a character, or the like can be selected.
[0058]
In order to bond the picture layer and the top olefin layer made of an olefin resin formed thereon, an adhesive layer is formed on the picture layer upper layer. As the adhesive resin, it is preferable to use a dry laminate adhesive made of a widely used two-component curable polyurethane resin such as a two-component curable polyester urethane resin.
[0059]
Usually, as a method of forming a laminate having an olefin layer, an olefin film is previously formed to a predetermined thickness, and an adhesive such as a urethane resin or an epoxy resin is used on the surface to be bonded. There are a dry laminating method in which the bonded surface and an olefin film are sand-laminated using a molten olefin as an adhesive layer.
[0060]
However, in order to sufficiently adhere the olefin layer by the polysand method, a heating step of about 300 ° C. is necessary, and a part of the polymer may be decomposed. Therefore, the dry lamination method is the most reliable for bonding the olefin layer to a different resin layer.
[0061]
Similar to the base olefin layer, the top olefin layer (surface protective layer) is made of an olefin resin such as propylene, and a transparent sheet is usually used. The film thickness is preferably about 50 to 150 μm, similarly to the base olefin layer.
[0062]
In addition, if necessary, the surface of the top olefin layer is improved in wear resistance and scratch resistance, surface gloss is adjusted, and the UV absorber contained in the top olefin layer (especially an organic system that is easy to bleed). In order to prevent bleeding over time, a top coat film is formed.
[0063]
As the coating material used for the top coating film, in consideration of the use of the top coating film and the adhesion to the olefin resin, those having a two-component curable urethane resin as a component are preferable. The film thickness of the top coat film is usually about 1 to 10 μm, and the top coat film is formed by a known coating method such as a roll coater or a gravure roll coater.
[0064]
The composite decorative sheet of the present invention includes a building interior material such as a wall, a floor, and a ceiling, a window frame, a door frame, a door, a fitting such as a handrail, furniture such as a bag, a cabinet for home appliances and office automation equipment, a vehicle, a ship Used as a surface decorative material for vehicle interior materials such as aircraft.
[0065]
【Example】
Embodiments of a composite decorative sheet and a method for producing the same according to the present invention will be described below with reference to the drawings.
[0066]
Example 1
In FIG. 1, sectional drawing of the composite decorative sheet of Example 1 is shown.
The composite decorative sheet of this example has a structure in which a pattern layer 12 is formed on a base olefin layer 11 and a transparent top olefin layer 14 is laminated via an adhesive layer 13.
[0067]
Below, the manufacturing method of the composite decorative sheet of a present Example is demonstrated.
First, in order to make the base olefin layer 11 made of an olefin-based thermoplastic elastomer film easily adhesive, the surface is subjected to corona discharge treatment to increase the wetting of the film surface, and the critical surface tension is about 50 (dyne / cm). And
[0068]
The olefin-based thermoplastic elastomer film has a composition in which a hard segment made of isotactic polypropylene and a soft segment made of atactic polypropylene are mixed in an 80:20 weight ratio.
The film thickness is 80 μm.
[0069]
Further, in this embodiment, since the base concealing ink layer (entire solid printing layer) is not provided, the pigment is mixed with the olefin resin in advance to make it opaque. As the pigment, for example, titanium white, petiole, carbon black and the like are used.
[0070]
Next, an ink obtained by adding a pigment to a binder comprising a polyurethane-acrylic block copolymer obtained by polymerizing 20% by weight of a polyurethane azo polymer obtained by addition reaction of azodiol, diol and diisocyanate and 80% by weight of n-butyl acrylate Is coated on the base olefin layer 11 to form the pattern layer 12.
Coating is performed by, for example, a gravure printing method, and a pattern such as a wood grain pattern is printed.
[0071]
Further, an adhesive layer 13 of a two-component curable polyurethane resin composed of acrylic polyol and hexamethylene diisocyanate is applied with a thickness of 10 μm.
On the upper layer, a polypropylene resin film (thickness: 80 μm) whose surface is easily bonded by corona treatment is laminated as a top olefin layer 14 in advance. For the top olefin layer 14, a resin having the same composition as the base olefin layer 11, to which 0.5 wt% of a hindered amine radical scavenger and 0.5 wt% of a benzotriazole ultraviolet absorber are added, can be used.
As described above, the composite decorative sheet of this example can be manufactured.
[0072]
(Example 2)
In FIG. 2, sectional drawing of the composite decorative sheet of a present Example is shown.
The composite decorative sheet of this example has a structure in which a primer layer 22 is formed on a base olefin layer 21, a pattern layer 23 is formed thereon, and a top olefin layer 25 is laminated via an adhesive layer 24. Have.
[0073]
Below, the manufacturing method of the composite decorative sheet of a present Example is demonstrated.
First, in order to make the base olefin layer 21 made of an olefin-based thermoplastic elastomer film easily adhesive, the surface is subjected to corona discharge treatment to increase the wetting of the film surface, and the critical surface tension is about 50 (dyne / cm). And
[0074]
The olefin-based thermoplastic elastomer film has a composition in which 100 parts by weight of high-density polyethylene is added to 30 parts by weight of rubber, 10 parts by weight of an extender pigment (filler) made of calcium carbonate powder, and 6 parts by weight of titanium white pigment. .
The film thickness is 80 μm.
[0075]
As the primer layer 22, a two-component curable polyurethane resin composed of polyester polyol and hexamethylene diisocyanate is used, and the resin is made into a paint and applied by a known method such as a gravure coating method, a reverse roll coating method, or a curtain flow coating method. Thus, the primer layer 22 is formed.
[0076]
Next, an ink obtained by adding a pigment to a binder comprising a polyurethane-acrylic block copolymer obtained by polymerizing 20% by weight of a polyurethane azo polymer obtained by addition reaction of azodiol, diol and diisocyanate and 80% by weight of n-butyl acrylate Is applied onto the primer layer 22 to form the pattern layer 23. The coating is performed, for example, by a gravure printing method, and a pattern such as a stone pattern is printed.
Further, an adhesive layer 24 of a two-component curable polyurethane resin composed of acrylic polyol and hexamethylene diisocyanate is applied with a thickness of 10 μm.
[0077]
A top olefin layer 25 made of a polypropylene resin film (film thickness: 80 μm) whose adhesion surface has been made easy to adhere by corona treatment is laminated on the upper layer. For the top olefin layer 14, a resin having the same composition as the base olefin layer 21 to which 0.5% by weight of a hindered amine radical scavenger and 0.5% by weight of a benzotriazole ultraviolet absorber are added can be used.
As described above, the composite decorative sheet of this example can be manufactured.
[0078]
(Example 3)
In FIG. 3, sectional drawing of the composite decorative sheet of a present Example is shown.
In the composite decorative sheet of this example, a primer layer 32 is formed on a base olefin layer 31, and a base concealing ink layer (solid layer) 33 having a polyurethane-acrylic block copolymer as a binder is formed on the primer layer 32, and a wood grain pattern. The pattern layer 34 is formed, and the top olefin layer 36 is further laminated via the adhesive layer 35.
[0079]
By combining the manufacturing steps shown in Examples 1 and 2 above, the composite decorative sheet of this example can be configured. In the composite decorative sheet of the present invention, both the primer layer 32 and the base concealing ink layer 33 can be provided between the base olefin layer 31 and the picture layer 34 as in this embodiment.
[0080]
Example 4
In FIG. 4, sectional drawing of the composite decorative sheet of a present Example is shown.
In the composite decorative sheet of this embodiment, a primer layer 42 is formed on a base olefin layer 41, a base concealing ink layer (solid layer) 43 and a pattern layer 44 are formed thereon, and an adhesive layer 45 is further interposed therebetween. The top olefin layer 46 has a laminated structure.
[0081]
The material and manufacturing method of the above layer structure are the same as those in Example 3. In this example, the following structure is further provided in addition to the above.
The surface of the top olefin layer 46 is embossed with an uneven pattern of wood grain conduit grooves, and a wiping ink 48 is embedded in the recesses. As the wiping ink 48, an ink obtained by adding a carbon black pigment to a binder made of acrylic polyol and hexamethylene diisocyanate is used.
[0082]
An upper coating film 47 made of a two-component curable urethane resin formed by mixing acrylic polyol and hexamethylene diisocyanate at a weight ratio of 100 to 10 is formed on the top olefin layer 46.
[0083]
On the back surface of the base olefin layer 41, a back surface primer layer 40 is formed using a two-component curable urethane resin in which a polyester polyol is crosslinked with a urethane bond using hexamethylene diisocyanate as a crosslinking agent. The back primer layer 40 is obtained by adding 25% by weight of silica powder to a two-component curable urethane resin as a base material to form a paint, such as a gravure coating method, a reverse roll coating method, a curtain flow coating method, and the like. It is formed by coating by a method.
[0084]
By laminating the layers below the top olefin layer 46 by combining the manufacturing steps shown in Examples 1 and 2 above, the top olefin layer 46 surface is subjected to corona discharge treatment and then the top coat film 47 is formed. The surface of the top coat 47 is embossed. After the colored ink is applied to the entire surface, the surface is immediately scraped off with a doctor blade, rubber roll or the like to remove excess ink, and 48 parts of wiping ink is formed leaving the colored ink only in the embossed recesses.
[0085]
The composite decorative sheet of the present invention and the manufacturing method thereof are not limited to the above-described embodiment. For example, the film thickness of the base olefin layer or the top olefin layer can be changed as appropriate. Further, the decoration treatment applied to the top olefin layer or the top coat film surface may be embossing only without applying the wiping ink.
The present invention is not limited to the above embodiments, and various modifications can be made without departing from the scope of the present invention.
[0086]
[Comparative example]
(Comparative Example 1) to (Comparative Example 4)
In Examples 1 to 4, the binder for the base concealing ink layer is a mixture of acrylic polyol and hexamethylene diisocyanate, and the binder for the pattern layer is 1: 1 weight of acrylic resin and vinyl chloride-vinyl acetate copolymer. It changed into the specific mixture, and the other layer manufactured the composite decorative sheet which is the same as that of Example 1- Example 4, and was set as Comparative Example 1- Comparative Example 4, respectively.
[0087]
Evaluation of light resistance
Ultraviolet rays were irradiated from the top olefin layer side of the composite decorative sheet of each example and each comparative example, and an accelerated deterioration test of outdoor exposure was performed. As a test method, an ultraviolet light source is used as an I-super UV tester (model SUV-W13) manufactured by Iwasaki Electric Co., Ltd., and an ultraviolet irradiation amount (ultraviolet intensity) is 60 mW / cm.²A cycle of 20 hours of irradiation and 4 hours of non-irradiation and dew condensation was performed as one cycle. If this operation is repeated, 100 hours corresponds to about one year of outdoor exposure.
[0088]
Judgment was performed in two stages of an elapsed time of 100 hours and 400 hours in the accelerated deterioration test, and the delamination strength between the top olefin layer and the base olefin layer was measured for the samples after each irradiation time to evaluate the light resistance.
[0089]
In the peeling test, a test piece having a width of 1 inch was pulled with a tensile tester at an angle formed by the top olefin layer and the base olefin layer at 180 ° C., and light-resistant adhesion was evaluated by the tension at the time of peeling.
[0090]
Evaluation results
In Examples 1 to 4, the irradiation time was 100 hours and 400 hours, and the tension at the time of peeling was 3 to 3.5 kg / inch. In Comparative Examples 1 to 4, the irradiation time was 100 hours. In either case, 1 kg / inch or less and irradiation time of 400 hours were all 0.6 kg / inch or less.
[0091]
【The invention's effect】
As described above, the composite decorative sheet of the present invention has significantly improved light-resistant adhesion to ultraviolet rays when exposed outdoors as compared to conventional composite decorative sheets mainly composed of olefinic resins.
[0092]
Further, in the conventional composite decorative sheet, peeling occurs between the base olefin layer and the primer layer due to ultraviolet irradiation equivalent to one year of outdoor exposure in the accelerated deterioration test, but according to the manufacturing method of the present invention described above, It is possible to produce a composite decorative sheet that does not cause delamination between layers or significant discoloration of printing ink even when ultraviolet irradiation equivalent to 4 years of outdoor exposure is performed in the accelerated deterioration test.
[0093]
Furthermore, the composite decorative sheet of the present invention has no problem of chlorinated gas at the time of incineration, as seen in a composite decorative sheet mainly composed of vinyl chloride resin, and has excellent light-resistant adhesion, so that weather resistance is required. It can be preferably used for building materials and the like.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a composite decorative sheet shown in Example 1 of the present invention.
FIG. 2 is a cross-sectional view of a composite decorative sheet shown in Example 2 of the present invention.
FIG. 3 is a cross-sectional view of a composite decorative sheet shown in Example 3 of the present invention.
FIG. 4 is a cross-sectional view of a composite decorative sheet shown in Example 4 of the present invention.
FIG. 5 is a cross-sectional view of a conventional composite decorative sheet.
[Explanation of symbols]
11, 21, 31, 41, 51 ... base olefin layer, 12, 23, 34, 44, 54 ... picture layer, 13, 24, 35, 45, 55 ... adhesive layer, 14, 25, 36, 46, 56 ... top olefin layer, 22, 33, 43, 53 ... base concealing ink layer, 32, 42, 52 ... primer layer, 40 ... back primer layer, 47 ... top coat, 48 ... wiping ink.

Claims (4)

A base olefin layer made of an olefin resin;
A primer layer made of a two-component curable polyurethane formed on the base olefin layer, and
A pattern layer made of an ink having a polyurethane-acrylic block copolymer obtained by polymerizing an acrylic monomer and a polyurethane azo polymer, which is an addition product of azodiol, diol and diisocyanate, formed on the primer layer. ,
An adhesive layer made of a two-component curable polyurethane formed on the pattern layer;
Formed in said adhesive layer upper, at least organic and top olefin layer comprising an olefin-based resin,
The two-component curable polyurethane used for the primer layer is an acrylic polyol and an aliphatic or alicyclic isocyanate ,
Composite decorative sheet. The composite decorative sheet according to claim 1 , wherein the ink used for the pattern layer further contains an isocyanate compound. Forming a primer layer made of a two-component curable polyurethane on a base layer made of an olefin resin;
On the primer layer, a pattern layer made of an ink containing a polyurethane-acrylic block copolymer obtained by polymerizing a polyurethane azo polymer, which is an addition reaction product of azodiol, diol and diisocyanate, and an acrylic monomer, is printed by printing. Forming, and
Forming an adhesive layer made of two-component curable polyurethane on the pattern layer by coating;
It said adhesive layer, at least have the laminating forming the top olefin layer comprising an olefin-based resin,
The two-component curable polyurethane used for the primer layer is an acrylic polyol and an aliphatic or alicyclic isocyanate ,
A method for producing a composite decorative sheet. The printing step for forming the pattern layer is a step of printing the polyurethane-acrylic block copolymer with an isocyanate compound added in an unreacted state;
A step of reacting the polyurethane-acrylic block copolymer with the isocyanate compound to form a urethane bond,
The manufacturing method of the composite decorative sheet of Claim 3 .

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