JP3839258B2 - Printing resin film for laminating highly weather-resistant decorative board, high weather-resistant decorative board and storage for laminating the resin film - Google Patents

Printing resin film for laminating highly weather-resistant decorative board, high weather-resistant decorative board and storage for laminating the resin film Download PDF

Info

Publication number
JP3839258B2
JP3839258B2 JP2000600841A JP2000600841A JP3839258B2 JP 3839258 B2 JP3839258 B2 JP 3839258B2 JP 2000600841 A JP2000600841 A JP 2000600841A JP 2000600841 A JP2000600841 A JP 2000600841A JP 3839258 B2 JP3839258 B2 JP 3839258B2
Authority
JP
Japan
Prior art keywords
resin layer
layer
decorative board
film
resistant decorative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP2000600841A
Other languages
Japanese (ja)
Inventor
寛之 岩下
哲男 中本
幸治 田熊
義之 杉本
芳樹 武居
行治 藤井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Kohan Co Ltd
Original Assignee
Toyo Kohan Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Kohan Co Ltd filed Critical Toyo Kohan Co Ltd
Application granted granted Critical
Publication of JP3839258B2 publication Critical patent/JP3839258B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/14—Printing or colouring
    • B32B38/145—Printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/08—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)

Description

【０００１】
【技術分野】
本発明は、高耐候性化粧板積層用印刷樹脂フィルムおよびその樹脂フィルムを積層した高耐候性化粧板に関し、より詳しくは物置やカーポートの屋根等の建築物の外装、および自動車等のように特に高耐候性を要求される用途に適した積層用樹脂フィルム、その樹脂フィルムを積層した高耐候性化粧板及び物置に関する。
【０００２】
【背景技術】
従来、各種の物置やカーポート等の建築物の外装材に使用される高耐候性化粧板としては、（１）溶融亜鉛めっき鋼板に有機質系の塗料を塗装した着色亜鉛めっき鋼板
（２）ポリ塩化ビニル樹脂フィルムの上に通常の方法を用いて印刷を施した後、ポリ塩化ビニル樹脂フィルムや二軸延伸ポリエステル樹脂フィルムを積層した化粧フィルムを、接着剤を介して亜鉛めっき鋼板、合板、またはＭＤＦなどの基板に積層したもの
（３）基材となる樹脂層に印刷を施した後、接着剤層を介してアクリル樹脂フィルムを積層した化粧フィルムを、接着剤を介して亜鉛めっき鋼板、合板、またはＭＤＦなどの基板に積層したものなどが知られている。
【発明が解決しようとする課題】
【０００３】
しかしながら、上記（１）の着色亜鉛めっき鋼板は、屋外用途においては３〜６年で塗装面に異常をきたし、塗膜の剥離やブリスターなどが生じ、下地の亜鉛めっき層の腐食が進むことがあるために、再塗装をすることが必要となる。
（２）の化粧フィルムを積層した化粧板は、ポリ塩化ビニル樹脂フィルムが用いられているため、耐汚染性、耐溶剤性などの表面物性が劣り、また焼却して廃棄処理する際に、塩化水素ガスのような有毒ガス、およびそれに起因する有害物質が発生して環境を汚染したり、焼却する際に焼却炉を傷めたりするおそれがあるなどの問題を抱えている。
（３）のアクリル樹脂フィルム積層板は、太陽光による紫外線や熱に対する耐久性は優れていることが知られているが、加工部や施工時に発生するキズ部の耐食性が劣り、フィルムの剥離やブリスターなどを生じ、下地の基材層の腐食や劣化などが進むことがあり、屋外用途に用いる材料としては必ずしも満足できるものではなかった。
本発明は上記の問題を解決することを目的として、従来のポリ塩化ビニル樹脂フィルムを用いた高耐候性化粧シートと同等以上の意匠性に優れた絵柄模様を有し、耐候性、耐汚染性、耐溶剤性などの表面物性に優れた高耐候性化粧板積層用印刷樹脂フィルムおよびその樹脂フィルムを積層した高耐候性化粧板を提供することを課題とする。
【発明の開示】
【０００４】
請求項１の高耐候性化粧板積層用印刷樹脂フィルムは、接着樹脂層、基材樹脂層、ベタ印刷層、絵柄印刷層、表面樹脂層が下から順次積層された樹脂フィルムであって、
接着樹脂層とポリブチレンテレフタレート樹脂からなる基材樹脂層とを積層したフィルムの基材樹脂層面に、ポリアクリレートフィルムからなる透明な表面樹脂層の下面に設けた絵柄印刷層とベタ印刷層からなる印刷層を重ね合わせ、熱ロール間に通して圧着するとともに熱融着して積層したことを特徴とする。
請求項２の高耐候性化粧板積層用印刷樹脂フィルムは、接着樹脂層、着色樹脂層、絵柄印刷層、基材樹脂層、表面樹脂層が下から順次積層された樹脂フィルムであって、
接着樹脂層と着色樹脂層との積層したフィルムの着色樹脂層面に、絵柄印刷層を施し、
その上にポリブチレンテレフタレート樹脂からなる基材樹脂層を重ね合わせ、
熱ロール間に通して圧着するとともに熱融着して積層し、
さらに前記基材樹脂層の上に接着剤層を介してポリアクリレートフィルムからなる透明な表面樹脂層を積層してなることを特徴とする。
請求項３の高耐候性化粧板積層用印刷樹脂フィルムは、接着樹脂層、着色樹脂層、ベタ印刷層、絵柄印刷層、基材樹脂層、表面樹脂層が下から順次積層された樹脂フィルムであって、
接着樹脂層と着色樹脂層との積層したフィルムの着色樹脂層面にベタ印刷層を設け、その上に絵柄印刷層を施し、
その上にポリブチレンテレフタレート樹脂からなる基材樹脂層を重ね合わせ、
熱ロール間に通して圧着するとともに熱融着して積層し、
さらに前記基材樹脂層の上に接着剤層を介してポリアクリレートフィルムからなる透明な表面樹脂層を積層してなることを特徴とする。
請求項４の高耐候性化粧板積層用印刷樹脂フィルムは、請求項２または３において、エン ボスロールを用いて前記基材樹脂層の表面にエンボス加工を施し、
該エンボス加工により形成されたエンボス凹部にインキが充填されてなるワイピング印刷層を有することを特徴とする。
請求項５の高耐候性化粧板積層用印刷樹脂フィルムは、請求項１〜４のいずれかにおいて、前記表面樹脂層の表面がエンボス加工によるエンボス凹部を有することを特徴とする。
請求項６の高耐候性化粧板は、樹脂フィルムを積層する基板の少なくとも片面に、請求項１〜５のいずれかに記載の高耐候性化粧板積層用印刷樹脂フィルムを積層したことを特徴とする。
請求項７の高耐候性化粧板は、請求項６において、前記基板と前記高耐候性化粧板積層用印刷樹脂フィルムの間に接着剤層を介して積層したことを特徴とする。
請求項８の高耐候性化粧板は、請求項６または７において、前記基板が金属板であることを特徴とする。
請求項９の高耐候性化粧板は、請求項６または７において、前記基板が木質板であることを特徴とする。
請求項１０の高耐候性化粧板は、請求項６または７において、前記基板がボードであることを特徴とする。
請求項１１の物置は、請求項８に記載の高耐候性化粧板を用いて成形したことを特徴とする。
【発明を実施するための最良の形態】
【０００５】
本発明の発明者等は、焼却時に有毒ガスおよびそれに起因する有害物質が発生して環境を汚染するおそれがあるポリ塩化ビニル樹脂フィルムに替わる、高耐候性および意匠性に優れた絵柄模様を有し、かつ耐汚染性、耐溶剤性などの表面物性に優れた印刷可能な化粧板積層用の高耐候性樹脂フィルムについて鋭意検討した結果、接着樹脂層として共重合ポリエステル樹脂フィルムを、選択的に積層される着色樹脂層ならびに印刷下地となる基材樹脂層としてポリブチレンテレフタレート樹脂フィルムを用い、それに絵柄印刷層、または絵柄印刷層とベタ印刷層を形成し、さらに表面樹脂層としてアクリル樹脂フィルム等を下から順次積層することにより、上記の要求特性を満足する化粧板に積層する樹脂フィルムが得られることを見出した。
【０００６】
また、基材樹脂層にエンボス加工を施してエンボス凹部を形成した後、ワイピング法を用いてエンボス凹部にインキを充填してなるワイピング印刷層を設けてもよい。
さらに、上記の樹脂フィルムを金属板、合板、ボードなどに積層した高耐候性化粧板は、樹脂フィルムの上記の優れたフィルム物性に加えて、意匠性にも優れていることを見出した。
【０００７】
以下に本発明についてその内容を説明する。
図１は本発明の高耐候性化粧板積層用印刷樹脂フィルムの一例を示す断面図、図２および図３は本発明の高耐候性化粧板積層用印刷樹脂フィルムの他の例を示す断面図、図４および図５は本発明の高耐候性化粧板の例を示す断面図である。１は高耐候性化粧板積層用印刷樹脂フィルム、２は基板、３は接着剤層、４は接着樹脂層、５は着色樹脂層、６ａは絵柄印刷層、６ｂはベタ印刷層、７は基材樹脂層、８はワイピング印刷用エンボス凹部、９はワイピング印刷層、１０は接着剤層、１１は表面樹脂層、１２はエンボス凹部、１３は高耐候性化粧板をそれぞれ表している。
【０００８】
本発明の高耐候性化粧板積層用印刷樹脂フィルム１は、図１に示すように接着樹脂層４の上面に、基材樹脂層７が積層されており、基材樹脂層７の上面に、裏面全面に絵柄印刷層６ａとベタ印刷層６ｂが裏面全体に設けられた表面樹脂層１１が積層されている。
また、本発明の高耐候性化粧板積層用印刷樹脂フィルム１は、図２に示すように接着樹脂層４の上面に、絵柄印刷層６ａが施された着色樹脂層５が積層されており、その上面にエンボス加工により形成されたエンボス凹部８に、ワイピングインキが充填されたワイピング印刷層９が設けられた基材樹脂層７がさらに積層されており、その基材樹脂層７の上面に接着剤層１０を介して、表面樹脂層１１が積層されたものであってもよい。
【０００９】
さらに、本発明の高耐候性化粧板積層用印刷樹脂フィルム１は、図３に示すように、図２の高耐候性化粧板積層用印刷樹脂フィルム１の着色樹脂層５に、絵柄印刷層６ａとベタ印刷層６ｂの両方が設けられ、さらに表面樹脂層１１の表面にエンボス凹部１２が設けられていてもよい。
図４は、図２に示した高耐候性化粧板積層用印刷樹脂フィルム１を、接着剤層３を介して基板２に積層した高耐候性化粧板１３を示す。
図５は、図３に示した高耐候性化粧板積層用印刷樹脂フィルム１を、接着剤層３を介して基板２に積層した高耐候性化粧板１３を示す。
【００１０】
本発明の基材樹脂層７および着色樹脂層５の樹脂としては、１．０〜２．０の固有粘度（ＩＶ値）を有するポリブチレンテレフタレート樹脂フィルムを用いることが好ましいが、固有粘度は製膜性の面から１．５以下、耐水経時性（耐水劣化性）の面から １．２以上であることがより好ましい。また、着色樹脂層５と同様に、基材樹脂層７も押出機を用いて製膜する際に、樹脂中に着色顔料を混練して着色樹脂層としてもよい。
【００１１】
絵柄印刷層６ａは、例えば、木目、石目、天然皮革の表面柄、布目、抽象柄などの模様を表現した印刷層であり、ベタ印刷層６ｂは基材樹脂層７の全面を隠蔽し絵柄印刷層６ａの印刷下地色を与える印刷層であると共に、基材樹脂層７と表面樹脂層１１との熱接着性を付与する層でもある。印刷層６ａおよび６ｂを形成するインキのビヒクルとしては、例えばニトロセルロース、酢酸セルロースなどのセルロース誘導体、ポリエステルウレタン樹脂などの公知のものが使用できるが、なかでも密着及び熱接着性の両観点からニトロセルロース−アルキド樹脂系インキが好ましい。
【００１２】
また、基材樹脂層７に選択的にエンボス加工を施してエンボス凹部８を形成した後、ワイピング法を用いてエンボス凹部８にインキを充填してなるワイピング印刷層９を設ける場合、エンボス凹部８に充填されるワイピングインキとしては、塗料もしくはインキが用いられる。
例えば、天然樹脂またはその変成樹脂類、セルロース誘導体類、ポリエステル系樹脂、アクリル系樹脂、ポリウレタン系樹脂等の合成樹脂類をビヒクルの構成材料とし、ビヒクル中に着色顔料、体質顔料等を添加して成る塗料もしくはインキが用いられる。使用されるビヒクルとしてはウレタン２液硬化型のものが好適に用いられる。ワイピング法としては、ドクターブレード法、ロールコート法など、従来から使用されているワイピング法のいずれによっても良い。
【００１３】
表面樹脂層１１としてはアクリル樹脂フィルム、ポリエステル樹脂フィルム、ポリカーボネートフィルム、ポリアリレートフィルムなどを用いることが好ましく、なかでもアクリル樹脂フィルムを用いることがより好ましい。これらの樹脂フィルムは、可塑剤及びハロゲン属元素を含まないことを特徴とする。
【００１４】
接着樹脂層４の樹脂としては、共重合ポリエステル樹脂を用いることが好ましい。
このポリエステル樹脂を構成する材料の一例としては、以下の組成を有する共重合ポリエステル樹脂などが好適に用いられる。すなわち、樹脂を形成するソフトセグメントとして、ポリエチレングリコール、ポリテトラメチレングリコールなどのポリオキシアルキレングリコール、あるいはポリε−カプロラクトン、アゼライン酸、セバシン酸、ドデカンジオン酸、ダイマー酸などのＨＯＯＣ−［ＣＨ２］Ｅ−ＣＯＯＨの分子構造を有する脂肪族ジカルボン酸と、脂肪族および／または脂環族ジオールからなる脂肪族ポリエステルなどが好適に用いられる。
【００１５】
また、樹脂を構成するハードセグメントとしては、エチレンテレフタレート、ブチレンテレフタレート、シクロヘキサンジメチレンテレフタレート、シクロヘキサンジメチレンシクロヘキサンジカルボキシレート、ブチレン２，６ナフタレンジカルボキシレートなどの芳香族および／または脂環族エステルユニットから選ばれた少なくとも一つから構成されていることが好ましい。
【００１６】
さらに、アルコール成分として、１，４ブタンジオール残基を含有していることが耐溶剤性の点で好ましく、共重合ポリエステルを形成する全アルコール成分に占める１，４ブタンジオール残基が４０モル％以上、６５モル％以下であることが好ましい。
【００１７】
基板との密着力がより強く要求される場合には、接着樹脂層４の樹脂成分の一部にアイオノマー樹脂成分を含有させるとよい。この場合、アイオノマー樹脂成分を全体樹脂成分の１〜５０重量％とすることが好ましい。
【００１８】
そして図１に示す本発明の高耐候性化粧板積層用印刷樹脂フィルム１は、次のようにして作成することができる。すなわち、共押出しにより２層フィルムとして製膜した接着樹脂層４と基材樹脂層７の積層フィルム上面に、表面樹脂層１１の下面に設けた絵柄印刷層６ａとベタ印刷層６ｂからなる印刷層を重ね合わせ、接着樹脂層４と基材樹脂層７の共押出し積層フィルムと表面樹脂層１１を重ね合せたまま１対の熱ロール間に通して挟み付けて圧着するとともに熱融着して積層し、一枚の積層フィルムを製造する。加熱しながら加圧することにより、表面樹脂層１１のベタ印刷層６ｂの面を基材樹脂層７に融着して一枚の高耐候性化粧板積層用印刷樹脂フィルム１を作るものである。
【００１９】
また、接着樹脂層４と顔料を混練した着色樹脂層５を共押出しにより２層フィルムとして製膜し、前記着色樹脂層５の上に絵柄印刷層６ａを施し、さらに、その上に基材樹脂層７を重ね合せたまま１対の熱ロール間に通して挟み付けて圧着するとともに熱融着して積層し、一枚の積層フィルムを製造する。なお、その際、前記の熱ロールとしてエンボスロールを使用することにより、積層とエンボス加工を同時に実施することができ、基材樹脂層７の表面にワイピング印刷用エンボス凹部８を形成し、ワイピングインキを充填してワイピング印刷層９を設けることにより、高意匠性の絵柄模様を付与することができる。さらに、その上に接着剤層１０を介して表面樹脂層１１を積層することによって、図２に示す高耐候性化粧板積層用印刷樹脂フィルム１を得ることができる。そして、着色樹脂層５および基材樹脂層７が寸法安定性に優れるため、張力や熱に起因する伸縮変動を抑えることが可能となり、印刷柄とエンボス柄が同調した、高意匠性を有するエンボス化粧フィルムとすることができる。上記の積層作業やエンボス加工などの工程は、従来のポリ塩化ビニル樹脂フィルムにおけるのと同じ条件で作業することが可能である。
【００２０】
さらに、図２の着色樹脂層５の表面にベタ印刷層６ｂを設け、その上に絵柄印刷層６ａを設けた樹脂フィルムを用いることにより、図３に示すように、意匠性をより一層向上させた化粧板積層用印刷樹脂フィルム１とすることもできる。
【００２１】
また、上記の方法によって得られた高耐候性化粧板積層用印刷樹脂フィルム１を、接着剤層３を介在させて基板２と貼合わせることにより、図４または図５に示すような高耐候性化粧板１３が得られる。基板２としては、例えば、木材単板、木材合板、パーチクルボード、ＭＤＦ等の木質板、鋼板、アルミニウム合金板、亜鉛や亜鉛合金をめっきした亜鉛めっき鋼板などの金属板、または石膏ボード、珪酸カルシウムボード、石綿スレートボードなどの無機質からなるボードが用いられる。
【００２２】
高耐候性化粧板積層用印刷樹脂フィルム１と基板２の貼合わせに用いられる接着剤層３の接着剤としては、一般的な接着剤、例えば、酢酸ビニル樹脂系、エチレン−ビニルアセテート樹脂系、尿素樹脂系、ウレタン樹脂系などのエマルジョン型接着剤が、火気に対して安全で、臭気もなく、価格的にも安価なため好ましく用いられる。
【００２３】
実施例
次に実施例により本発明をさらに詳細に説明する。
（実施例１）
市販の厚さ６０μｍの透明アクリル樹脂フィルムの片面に、ニトロセルロース−アルキド系インキ（昭和インク製、ＳＡＭ）を用い、絵柄印刷層および着色ベタ印刷層をグラビア輪転機によりインラインにて印刷したものと、市販のポリブチレンテレフタレート樹脂および共重合ポリエチレンテレフタレート樹脂を用いて押出製膜機により作成した厚さ７０μｍの２層未延伸フィルム（厚み比＝４：１）を重ねて、圧着用ロールの加熱温度：２００℃、樹脂フィルムの送り速度：２０ｍ／ｍｉｎ、圧着用ロールのニップ圧：１５ｋｇｆ／ｃｍ２の条件で両フィルムを加熱圧着して積層し、高耐候性化粧板積層用印刷樹脂フィルムを作製した。次に、厚さ０．５ｍｍの電気亜鉛めっき鋼板にポリエステル系接着剤を１０ｇ／ｍ２の塗布量で塗布し、前記の高耐候性化粧板積層用印刷樹脂フィルムを加熱温度：２１０℃、接着圧力：１５ｋｇｆ／ｃｍ２、圧着時間：５秒の条件で加熱圧着し、高耐候性化粧板を得た。
【００２４】
（実施例２）
市販のポリブチレンテレフタレート樹脂にクリーム色顔料２０重量％を混錬したものと共重合ポリエチレンテレフタレート樹脂を押出製膜機により、厚み比＝４：１で作成した厚さ５０μｍの２層未延伸フィルムの片面に、ニトロセルロース−アルキド系インキ（昭和インク製、ＳＡＭ）を用い、絵柄印刷層をグラビア輪転機によりインラインにて印刷したものと、市販のポリブチレンテレフタレート樹脂を押出製膜機により製膜した厚さ７０μｍの未延伸フィルムとを対向させ、実施例１の加熱圧着による積層条件と同条件にて透明ポリブチレンテレフタレート単層フィルム面をエンボスロール側として、エンボスロールとシリコンゴムロールからなる圧着用ロールの間に通して圧着することにより、透明ポリブチレンテレフタレートフィルム表面にエンボス凹部を有する３層フィルムを作成した。次いで、前記エンボス凹部を有する面に２液硬化型ウレタン系着色インキ（昭和インク製、ＰＷ−００１）をロールコート法によって塗工した後、ドクターブレードでエンボス凹部以外の部分に付着している着色インキを除去し、積層フィルムの表面に形成されているエンボス凹部内に着色インキを充填、固化させ、印刷樹脂フィルムを作製した。さらに、この印刷樹脂フィルムのエンボス加工面に、エポキシ−フェノール系接着剤を片面に塗布した厚さ６０μｍの透明アクリル樹脂フィルムの接着剤塗布面を対向させ、実施例１の加熱圧着による積層条件と同条件にて、一対のシリコンゴムロールからなる圧着用ロールの間に通して圧着することにより、意匠性に優れた高耐候性化粧フィルムを作製した。次に、厚さ６ｍｍの木材合板にポリウレタン系接着剤を５０ｇ／ｍ２の塗布量で塗布し、前記高耐候性化粧板積層用印刷樹脂フィルムを加熱温度：１６０℃、接着圧力：１２ｋｇｆ／ｃｍ２、圧着時間：１５秒の条件で加熱圧着し、高耐候性化粧板を得た。
【００２５】
（実施例３）
実施例２と同一のポリブチレンテレフタレート樹脂と共重合ポリエチレンテレフタレート樹脂の２層未延伸フィルムの片面に、着色ベタ印刷層がポリブチレンテレフタレート樹脂上に直接設けられ、その上に絵柄印刷層が設けられる以外は実施例２と同一の条件で印刷した。さらに、実施例２と全く同様に、前記２層未延伸フィルムとポリブチレンテレフタレートフィルムを積層しながらエンボス加工を施した後、ワイピング印刷し、厚さ６０μｍの透明アクリル樹脂フィルムを接着剤を介在させて積層し、意匠性に優れた高耐候性化粧フィルムを作成した。次に、厚さ８ｍｍの石膏ボードにポリウレタン系接着剤を８０ｇ／ｍ２の塗布量で塗布し、前記高耐候性化粧板積層用印刷樹脂フィルムを加熱温度：１８０℃、接着圧力：１０ｋｇｆ／ｃｍ２、圧着時間：２０秒の条件で、透明アクリル樹脂フィルム面をエンボスロール側としてエンボスロールとシリコンゴムロールからなる圧着用ロールの間に通して加熱圧着し、表面にエンボス凹部が形成された、立体感のある高耐候性化粧板を得た。
【００２６】
（実施例４）
実施例１の厚さ６０μｍの透明アクリル樹脂フィルムの替わりに市販の厚さ６０μｍの透明ポリエチレンテレフタレートフィルムを用いた以外は、実施例１と全く同様にして高耐候性化粧板を得た。
【００２７】
（実施例５）
実施例２と同様にして印刷樹脂フィルムを作製した後、この印刷樹脂フィルムのエンボス加工面に、エポキシ−フェノール系接着剤を片面に塗布した厚さ６０μｍの透明ポリカーボネートフィルム（帝人製）の接着剤塗布面を対向させ、実施例１の加熱圧着による積層条件と同条件で圧着することにより、意匠性に優れた高鮮映化粧フィルムを作製した。次いで、実施例２と同様にして厚さ６ｍｍの木材合板に前記高鮮映化粧板積層用印刷樹脂フィルムを加熱圧着し、高鮮映化粧板を得た。
【００２８】
（実施例６）
実施例３と同様にして印刷樹脂フィルムを作製した後、この印刷樹脂フィルムのエンボス加工面に、エポキシ−フェノール系接着剤を片面に塗布した厚さ６０μｍの透明ポリアリレートフィルムの接着剤塗布面を対向させ、実施例３の加熱圧着による積層条件と同条件で圧着することにより、意匠性に優れた高鮮映化粧フィルムを作製した。次いで、実施例３と同様にして厚さ８ｍｍの石膏ボードに前記高鮮映化粧板積層用印刷樹脂フィルムを加熱圧着し、高鮮映化粧板を得た。
【００２９】
（樹脂フィルムの特性評価）
実施例１、２、３、４、５および６で作成した高耐候性化粧板を、下記の特性について評価した。
【００３０】
（耐候性）
屋外耐候性の評価は、積層板の皮膜にカミソリ刃で基板に達するクロスカットを施し、サンシャインウェザオメータ試験（ＪＩＳ Ａ １４１５）を試験時間８０００時間にわたって実施した。
皮膜のクラック、変色などの異常やブリスターなどの発生を肉眼評価し、下記の基準で評価した。
◎：変色、クラック、ブリスターの発生は全く認められない。
○：クロスカット部に実用上問題ない程度の極くわずかなブリスターの発生が認められる。
△：クロスカット部に実用上問題となる程度の変色、クラック、ブリスターの発生が認められる。
×：全面にかなりの程度に変色、クラック、ブリスターの発生が認められる。
また、クロスカットを施したサンプルは、サンシャインウェザオメータ試験８０００時間後、塩水噴霧試験（ＪＩＳ Ｚ ２３７１）を３００時間にわたって行い、強制剥離による皮膜の剥離幅を評価した。
その結果、実施例１〜６のいずれの化粧板についても、剥離幅は１ｍｍ以内であり、優れた耐食性を示した。
【００３１】
（エンボス加工性）
本発明の高耐候性化粧板積層用印刷樹脂フィルムのワイピング印刷用エンボス加工性の良否は、エンボス加工を施した樹脂フィルムの基材樹脂層の表面粗さによって判断される。本発明においては、平均表面粗さ（Ｒａ）：１１μｍの凹凸が付与された砂目の彫刻ロールを用いてエンボス加工を施した樹脂フィルムの基材樹脂層表面を肉眼観察し、エンボス加工性の良否を下記の３段階の基準で評価した。
○：良好、
△：やや不良、
×：不良
なお、上記の評価基準は、ポリ塩化ビニル樹脂フィルムの表面粗さ（Ｒａ：μｍ）を東京精密社製ＳＵＲＦＣＯＭ表面粗さ計を用いてＪＩＳ Ｂ ０６０１に準拠して測定し、平均表面粗さが４μｍである場合をエンボス加工性の合格基準とし、平均表面粗さが４μｍのポリ塩化ビニル樹脂フィルムの表面と同等以上の外観を有するものを良好（○）とし、ポリ塩化ビニル樹脂フィルムの表面と比べてやや劣るが実用上問題ない外観を有するものをやや不良（△）とし、エンボス加工が入らないものを不良（×）として、判定した。
【００３２】
（耐汚染性）
実施例１、２、３、４、５および６で作成した高耐候性化粧板の最表層の樹脂フィルム面に、黒色の油性マジックインキで描画し２４時間放置した後、エタノールを含浸させた布で清拭し、樹脂フィルム面に残存するマジックインキの程度を肉眼観察し、下記の基準で評価した。
◎：マジックインキは全く認められない。
○：実用上問題ない程度の極くわずかなマジックインキの残存が認められる。
△：実用上問題となる程度のわずかなマジックインキの残存が認められる。
×：かなりの程度にマジックインキの残存が認められる。
【００３３】
（耐溶剤性）
実施例１、２、３、４、５および６で作成した高耐候性化粧板の最表層の樹脂フィルム面に、メチルエチルケトンを含浸させたスポンジを載せ、２４時間放置した後、フィルム表面の変色および膨れの発生の程度を肉眼観察し、下記の基準で評価した。
◎：変色および膨れの発生は全く認められない。
○：実用上問題ない程度の極くわずかな変色または膨れの発生が認められる。
△：実用上問題となる程度のわずかな変色または膨れの発生が認められる。
×：かなりの程度に変色および膨れが認められる。
【００３４】
（耐水劣化性）
本発明の高耐候性化粧板を高温多湿の状態で長時間経時させた場合を想定し、長時間水と接した場合の樹脂フィルムの耐水劣化性をデュポン衝撃試験法で評価した。
実施例１、２、３、４、５および６で作成した高耐候性化粧板積層用印刷樹脂フィルムを、厚さ０．５ｍｍの亜鉛めっき鋼板に積層し試験片とした。この試験片を６０ｍｍ×６０ｍｍの大きさに切り出し、３８±２℃の温度に保持された脱塩水中に１カ月間浸漬した後室温で乾燥し、デュポン衝撃試験機を用い、ＪＩＳ Ｋ ５４００に準拠した条件（衝撃部の大きさ１／２ｉｎｃｈφ、重さ１ｋｇ、落下高さ５０ｃｍ）で衝撃を負荷した。衝撃を負荷した後の樹脂フィルムの状態を肉眼観察し、下記の５段階で評価した。
◎：樹脂フィルムに割れが認められない。
△：樹脂フィルムのエンボス加工部全体に細かい割れが認められる。
×：樹脂フィルムのエンボス加工部全体に大きな割れが認められる。
××：樹脂フィルム全体に割れが著しい。
上記の評点において、◎および○は使用上の問題はない。なお、この試験は１０枚の試験片について実施した。これらの樹脂フィルムの特性評価を下記に示す。
【表１】

Figure 0003839258
上記に示すように、本発明の化粧板積層用印刷樹脂フィルムは、耐候性、エンボス加工性、耐汚染性、耐溶剤性、耐水劣化性のいずれにおいても優れた特性を示す。
【産業上の利用可能性】
【００３５】
本発明の高耐候性化粧板積層用印刷樹脂フィルムは上記のように構成されており、アクリル樹脂フィルムからなる表面樹脂層が太陽光の紫外線や熱に対する耐久性に優れているために屋外耐候用途に適用可能な積層樹脂フィルムを得ることが出来る。また、印刷フィルムとしても、ポリブチレンテレフタレートフィルムからなる基材樹脂層および着色樹脂層が熱や張力に対する伸縮変動が少なく、優れた寸法安定性を有しているため、印刷見当精度の良いものとなる。
さらに、従来のポリ塩化ビニル樹脂フィルムと同様の製造方法および製造条件で化粧フィルムが得られるために、新規設備の増設や設備の改造などの設備投資を必要とせず、従来のポリ塩化ビニル樹脂フィルムと同様の、印刷柄とエンボス柄が同調した意匠性に優れた鮮鋭な絵柄模様を表現することができる。
またさらに、基材樹脂層や表面樹脂層を構成する樹脂中に可塑剤を含有していないために、可塑剤のブリードによる表面汚染などの問題が生じることなく、耐汚染性、耐溶剤性、耐水性などの表面物性に優れている上に、焼却廃棄する際に、塩化水素ガスのような有毒ガスの発生がないため、環境を汚染する心配もなく環境保全性においても優れている。
【図面の簡単な説明】
【００３６】
図１は、本発明の高耐候性化粧板積層用印刷樹脂フィルムの一例を示す断面図である。図２は、本発明の高耐候性化粧板積層用印刷樹脂フィルムの他の一例を示す断面図である。図３は、本発明の高耐候性化粧板積層用印刷樹脂フィルムの他の一例を示す断面図である。図４は、本発明の高耐候性化粧板の一例を示す断面図である。図５は、本発明の高耐候性化粧板の他の一例を示す断面図である。[0001]
【Technical field】
The present invention relates to a printing resin film for laminating a highly weather-resistant decorative board and a highly weather-resistant decorative board in which the resin film is laminated, and more specifically, for exteriors of buildings such as storerooms and carport roofs, and automobiles. In particular, the present invention relates to a resin film for lamination suitable for applications requiring high weather resistance, a highly weather-resistant decorative board and a storeroom in which the resin films are laminated.
[0002]
[Background]
Conventionally, as a weatherproof decorative plate used for exterior materials of buildings such as various storerooms and carports, (1) Colored galvanized steel plate coated with organic paint on hot dip galvanized steel plate
(2) After printing on a polyvinyl chloride resin film using a normal method, a decorative film in which a polyvinyl chloride resin film or a biaxially stretched polyester resin film is laminated is galvanized steel sheet via an adhesive. , Laminated on a substrate such as plywood or MDF
(3) After printing on the resin layer as a base material, a decorative film in which an acrylic resin film is laminated via an adhesive layer is laminated on a substrate such as a galvanized steel sheet, plywood, or MDF via an adhesive. What is done is known.
[Problems to be solved by the invention]
[0003]
However, the colored galvanized steel sheet of the above (1) causes abnormalities on the painted surface in outdoor use in 3 to 6 years, and peeling of the coating film, blistering, etc. may occur, and corrosion of the underlying galvanized layer may proceed. For this reason, it is necessary to repaint.
Since the decorative film laminated with the decorative film of (2) uses a polyvinyl chloride resin film, the surface properties such as contamination resistance and solvent resistance are inferior, and when it is incinerated for disposal, There are problems such as the generation of toxic gas such as hydrogen gas and harmful substances resulting from it, which may pollute the environment and damage the incinerator during incineration.
The acrylic resin film laminate of (3) is known to be excellent in durability against ultraviolet rays and heat from sunlight, but the corrosion resistance of scratched parts generated during processing and construction is inferior. As a result, blistering and the like may cause corrosion and deterioration of the underlying base material layer, which is not always satisfactory as a material used for outdoor use.
In order to solve the above-mentioned problems, the present invention has a design pattern excellent in design properties equivalent to or better than a highly weather-resistant decorative sheet using a conventional polyvinyl chloride resin film, and has weather resistance and stain resistance. Another object of the present invention is to provide a printing resin film for laminating a highly weather-resistant decorative plate excellent in surface properties such as solvent resistance and a highly weather-resistant decorative plate laminated with the resin film.
DISCLOSURE OF THE INVENTION
[0004]
The printed resin film for laminating highly weather-resistant decorative board according to claim 1 is a resin film in which an adhesive resin layer, a base resin layer, a solid print layer, a pattern print layer, and a surface resin layer are sequentially laminated from the bottom,
It consists of a pattern printing layer and a solid printing layer provided on the bottom surface of a transparent surface resin layer made of a polyacrylate film on the base resin layer surface of a film in which an adhesive resin layer and a base resin layer made of polybutylene terephthalate resin are laminated. It is characterized in that the printed layers are superposed, pressed through heat rolls, and bonded by heat fusion.
The printed resin film for laminating highly weather-resistant decorative board according to claim 2 is a resin film in which an adhesive resin layer, a colored resin layer, a pattern printing layer, a base resin layer, and a surface resin layer are sequentially laminated from the bottom,
On the colored resin layer surface of the laminated film of the adhesive resin layer and the colored resin layer, a pattern printing layer is applied,
A base resin layer made of polybutylene terephthalate resin is overlaid thereon,
Passing between the heat rolls and crimping, heat-sealing and laminating,
Furthermore, a transparent surface resin layer made of a polyacrylate film is laminated on the base resin layer via an adhesive layer.
The printed resin film for laminating a highly weather-resistant decorative board according to claim 3 is a resin film in which an adhesive resin layer, a colored resin layer, a solid print layer, a pattern print layer, a base resin layer, and a surface resin layer are sequentially laminated from the bottom. There,
A solid printing layer is provided on the colored resin layer surface of the laminated film of the adhesive resin layer and the colored resin layer, and a pattern printing layer is applied thereon,
A base resin layer made of polybutylene terephthalate resin is overlaid thereon,
Passing between the heat rolls and crimping, heat-sealing and laminating,
Furthermore, a transparent surface resin layer made of a polyacrylate film is laminated on the base resin layer via an adhesive layer.
The printed resin film for laminating a highly weather-resistant decorative board according to claim 4 is the resin film according to claim 2 or 3. Embossing the surface of the base resin layer using a boss roll,
It has a wiping printing layer in which an embossed recess formed by the embossing is filled with ink.
The printed resin film for laminating highly weather-resistant decorative board according to claim 5 is characterized in that in any one of claims 1 to 4, the surface of the surface resin layer has an embossed recess formed by embossing.
The high weather resistant decorative board according to claim 6 is characterized in that the printed resin film for high weather resistant decorative board lamination according to any one of claims 1 to 5 is laminated on at least one surface of a substrate on which the resin film is laminated. To do.
The high weather resistant decorative board according to claim 7 is characterized in that, in claim 6, the high weather resistant decorative board is laminated between the substrate and the printed resin film for laminating the high weather resistant decorative board via an adhesive layer.
The high weather resistant decorative board according to claim 8 is characterized in that, in claim 6 or 7, the substrate is a metal plate.
The high weather resistant decorative board according to claim 9 is characterized in that, in claim 6 or 7, the substrate is a wood board.
The high weather resistant decorative board according to claim 10 is characterized in that, in claim 6 or 7, the substrate is a board.
The storeroom of claim 11 is formed by using the highly weather-resistant decorative board according to claim 8.
BEST MODE FOR CARRYING OUT THE INVENTION
[0005]
The inventors of the present invention have a design pattern with excellent weather resistance and design that replaces a polyvinyl chloride resin film that may contaminate the environment due to the generation of toxic gases and harmful substances resulting from the incineration. In addition, as a result of intensive studies on a highly weatherable resin film for laminating a printable decorative board excellent in surface properties such as stain resistance and solvent resistance, a copolymer polyester resin film is selectively used as an adhesive resin layer. A polybutylene terephthalate resin film is used as a colored resin layer to be laminated and a base resin layer as a printing base, and a pattern printing layer, or a pattern printing layer and a solid printing layer are formed on the polybutylene terephthalate resin film. It was found that a resin film laminated on a decorative board satisfying the above-mentioned required properties can be obtained by laminating layers from below.
[0006]
Moreover, after embossing is performed on the base resin layer to form an embossed recess, a wiping print layer in which ink is filled into the embossed recess using a wiping method may be provided.
Furthermore, the high weather-resistant decorative board which laminated | stacked said resin film on the metal plate, the plywood, the board, etc. discovered that it was excellent also in the designability in addition to the said outstanding film physical property of a resin film.
[0007]
The contents of the present invention will be described below.
FIG. 1 is a cross-sectional view showing an example of a printing resin film for laminating a highly weather-resistant decorative board according to the present invention. FIGS. 2 and 3 are cross-sectional views showing other examples of the printing resin film for laminating a highly weather-resistant decorative board according to the present invention. 4 and 5 are sectional views showing examples of the highly weather-resistant decorative board of the present invention. DESCRIPTION OF SYMBOLS 1 is printing resin film for highly weather-resistant decorative board lamination, 2 is a board | substrate, 3 is an adhesive layer, 4 is an adhesive resin layer, 5 is a colored resin layer, 6a is a pattern printing layer, 6b is a solid printing layer, 7 is a base The material resin layer, 8 is an embossed recess for wiping printing, 9 is a wiping print layer, 10 is an adhesive layer, 11 is a surface resin layer, 12 is an embossed recess, and 13 is a highly weather-resistant decorative board.
[0008]
The printed resin film 1 for laminating highly weather-resistant decorative board of the present invention has a base resin layer 7 laminated on the upper surface of the adhesive resin layer 4 as shown in FIG. A front surface resin layer 11 having a pattern printing layer 6a and a solid printing layer 6b provided on the entire back surface is laminated on the entire back surface.
Moreover, the printed resin film 1 for laminating a highly weather-resistant decorative board according to the present invention has a colored resin layer 5 on which an image printed layer 6a is applied on the upper surface of an adhesive resin layer 4 as shown in FIG. A base resin layer 7 provided with a wiping printing layer 9 filled with wiping ink is further laminated on an embossed recess 8 formed on the upper surface by embossing, and adhered to the upper surface of the base resin layer 7. The surface resin layer 11 may be laminated via the agent layer 10.
[0009]
Furthermore, as shown in FIG. 3, the printed resin film 1 for laminating highly weather-resistant decorative board according to the present invention has a pattern printed layer 6a on the colored resin layer 5 of the printed resin film 1 for laminating highly weather-resistant decorative board shown in FIG. And the solid print layer 6 b may be provided, and the embossed recess 12 may be provided on the surface of the surface resin layer 11.
FIG. 4 shows a high weather resistant decorative board 13 in which the printed resin film 1 for laminating the high weather resistant decorative board shown in FIG. 2 is laminated on the substrate 2 via the adhesive layer 3.
FIG. 5 shows a high weather resistant decorative board 13 in which the printed resin film 1 for laminating the high weather resistant decorative board shown in FIG. 3 is laminated on the substrate 2 via the adhesive layer 3.
[0010]
As the resin of the base resin layer 7 and the colored resin layer 5 of the present invention, it is preferable to use a polybutylene terephthalate resin film having an intrinsic viscosity (IV value) of 1.0 to 2.0. It is more preferably 1.5 or less from the viewpoint of film properties, and 1.2 or more from the viewpoint of water aging resistance (water deterioration resistance). Similarly to the colored resin layer 5, the base resin layer 7 may be formed into a colored resin layer by kneading a color pigment in the resin when forming the film using an extruder.
[0011]
The pattern print layer 6a is a print layer expressing patterns such as, for example, wood grain, stone grain, natural leather surface pattern, cloth pattern, abstract pattern, etc., and the solid print layer 6b covers the entire surface of the base resin layer 7 and covers the pattern. The print layer 6a is a print layer that gives a printing base color, and is a layer that imparts thermal adhesiveness between the base resin layer 7 and the surface resin layer 11. As the ink vehicle for forming the printing layers 6a and 6b, known ones such as cellulose derivatives such as nitrocellulose and cellulose acetate and polyester urethane resin can be used. A cellulose-alkyd resin-based ink is preferred.
[0012]
Further, when embossing is selectively performed on the base resin layer 7 to form the embossed recess 8, and then the wiping printing layer 9 is formed by filling the embossed recess 8 with ink using a wiping method, the embossed recess 8 As the wiping ink to be filled, paint or ink is used.
For example, natural resins or their modified resins, cellulose derivatives, polyester resins, acrylic resins, polyurethane resins, and other synthetic resins are used as vehicle constituent materials, and colored pigments, extender pigments, etc. are added to the vehicle. A paint or ink is used. As the vehicle used, a urethane two-component curable type is suitably used. As the wiping method, any of conventionally used wiping methods such as a doctor blade method and a roll coating method may be used.
[0013]
As the surface resin layer 11, an acrylic resin film, a polyester resin film, a polycarbonate film, a polyarylate film, or the like is preferably used, and an acrylic resin film is more preferably used. These resin films are characterized by not containing a plasticizer and a halogen group element.
[0014]
As the resin for the adhesive resin layer 4, it is preferable to use a copolyester resin.
As an example of the material constituting the polyester resin, a copolymerized polyester resin having the following composition is preferably used. That is, as a soft segment forming a resin, polyoxyalkylene glycol such as polyethylene glycol and polytetramethylene glycol, or HOOC- [CH such as poly ε-caprolactone, azelaic acid, sebacic acid, dodecanedioic acid, and dimer acid2An aliphatic polyester composed of an aliphatic dicarboxylic acid having an E-COOH molecular structure and an aliphatic and / or alicyclic diol is preferably used.
[0015]
The hard segment constituting the resin includes aromatic and / or alicyclic ester units such as ethylene terephthalate, butylene terephthalate, cyclohexane dimethylene terephthalate, cyclohexane dimethylene cyclohexane dicarboxylate, butylene 2,6 naphthalene dicarboxylate, etc. It is preferably composed of at least one selected from.
[0016]
Further, it is preferable that the alcohol component contains 1,4 butanediol residue from the viewpoint of solvent resistance, and 40 mol% of 1,4 butanediol residue occupies in all the alcohol components forming the copolymer polyester. As mentioned above, it is preferable that it is 65 mol% or less.
[0017]
When the adhesive strength with the substrate is required more strongly, an ionomer resin component may be contained in a part of the resin component of the adhesive resin layer 4. In this case, the ionomer resin component is preferably 1 to 50% by weight of the total resin component.
[0018]
And the printing resin film 1 for highly weatherable decorative board lamination of this invention shown in FIG. 1 can be produced as follows. That is, a printing layer comprising a pattern printing layer 6a and a solid printing layer 6b provided on the lower surface of the surface resin layer 11 on the upper surface of the laminated resin film of the adhesive resin layer 4 and the base resin layer 7 formed as a two-layer film by coextrusion. Are laminated, and the co-extruded laminated film of the adhesive resin layer 4 and the base resin layer 7 and the surface resin layer 11 are overlapped and sandwiched between a pair of hot rolls for pressure bonding and heat fusion bonded. And a single laminated film is produced. By applying pressure while heating, the surface of the solid print layer 6b of the surface resin layer 11 is fused to the base resin layer 7 to produce a single printed resin film 1 for laminating a highly weather-resistant decorative board.
[0019]
Further, the adhesive resin layer 4 and the colored resin layer 5 kneaded with the pigment are co-extruded to form a two-layer film, and a pattern printing layer 6a is applied on the colored resin layer 5, and further, a base resin is formed thereon. While the layers 7 are overlapped, they are passed between a pair of hot rolls and are pressed and pressure bonded, and heat bonded to form a laminated film. At that time, by using an embossing roll as the heat roll, lamination and embossing can be carried out at the same time, and an embossing recess 8 for wiping printing is formed on the surface of the base resin layer 7, thereby wiping ink. By providing the wiping printing layer 9 with filling, a highly designed pattern can be imparted. Furthermore, by laminating the surface resin layer 11 on the adhesive layer 10 thereon, the printed resin film 1 for laminating highly weather-resistant decorative board shown in FIG. 2 can be obtained. Since the colored resin layer 5 and the base resin layer 7 are excellent in dimensional stability, it is possible to suppress fluctuations in expansion and contraction caused by tension and heat, and embossing with high design in which the printed pattern and the embossed pattern are synchronized. It can be set as a decorative film. Steps such as the above laminating operation and embossing can be performed under the same conditions as in conventional polyvinyl chloride resin films.
[0020]
Furthermore, by providing a solid print layer 6b on the surface of the colored resin layer 5 in FIG. 2 and using a resin film on which the pattern print layer 6a is provided, the design is further improved as shown in FIG. It can also be set as the printing resin film 1 for decorative board lamination.
[0021]
Moreover, the high weather resistance as shown in FIG. 4 or FIG. 5 is obtained by laminating the printed resin film 1 for laminating highly weather-resistant decorative board obtained by the above method with the substrate 2 with the adhesive layer 3 interposed therebetween. A decorative board 13 is obtained. As the substrate 2, for example, a wood plate, a wood plywood, a particle board, a wood board such as MDF, a steel plate, an aluminum alloy plate, a metal plate such as a galvanized steel plate plated with zinc or a zinc alloy, a gypsum board, a calcium silicate board A board made of an inorganic material such as an asbestos slate board is used.
[0022]
Examples of the adhesive for the adhesive layer 3 used for laminating the printed resin film 1 for laminating a highly weatherable decorative board and the substrate 2 include general adhesives such as vinyl acetate resin, ethylene-vinyl acetate resin, Emulsion adhesives such as urea resin and urethane resin are preferably used because they are safe against fire, have no odor, and are inexpensive.
[0023]
Example
Next, the present invention will be described in more detail with reference to examples.
(Example 1)
A nitrocellulose-alkyd ink (Showa Ink, SAM) is used on one side of a commercially available transparent acrylic resin film having a thickness of 60 μm, and a pattern printing layer and a colored solid printing layer are printed inline by a gravure rotary press. The two-layer unstretched film (thickness ratio = 4: 1) having a thickness of 70 μm prepared by an extrusion film-forming machine using a commercially available polybutylene terephthalate resin and a copolymerized polyethylene terephthalate resin is stacked, and the heating temperature of the pressure-bonding roll : 200 ° C., resin film feed rate: 20 m / min, nip pressure of pressure bonding roll: 15 kgf / cm2Both films were heat-pressed and laminated under the above conditions to prepare a printed resin film for laminating highly weather-resistant decorative plates. Next, a 10 g / m polyester adhesive is applied to an electrogalvanized steel sheet having a thickness of 0.5 mm.2The above-mentioned printed resin film for laminating a highly weather-resistant decorative board is heated at 210 ° C., and the adhesion pressure is 15 kgf / cm.2Crimping time: Heat-bonded under conditions of 5 seconds to obtain a highly weather-resistant decorative board.
[0024]
(Example 2)
A 50 μm thick two-layer unstretched film prepared at a thickness ratio of 4: 1 using a commercially available polybutylene terephthalate resin kneaded with 20% by weight of a cream pigment and a copolymerized polyethylene terephthalate resin by an extrusion film forming machine. On one side, a nitrocellulose-alkyd ink (manufactured by Showa Ink, SAM) was used, and a pattern printing layer was printed inline by a gravure rotary press and a commercially available polybutylene terephthalate resin was formed by an extrusion film forming machine. A pressure-bonding roll comprising an embossing roll and a silicon rubber roll with an unstretched film having a thickness of 70 μm facing each other and the transparent polybutylene terephthalate single-layer film surface as the embossing roll side under the same conditions as the lamination conditions by thermocompression bonding in Example 1 Transparent polybutylene terephthalate fill by crimping between A three-layer film having an embossed recess on the surface was prepared. Next, a two-component curable urethane-based colored ink (Showa Ink, PW-001) is applied to the surface having the embossed recesses by a roll coating method, and then is attached to a portion other than the embossed recesses with a doctor blade. The ink was removed, and the embossed recess formed on the surface of the laminated film was filled with colored ink and solidified to produce a printed resin film. Further, the embossed surface of the printed resin film is opposed to the adhesive-coated surface of a transparent acrylic resin film having a thickness of 60 μm coated with an epoxy-phenolic adhesive on one side, and the lamination conditions by thermocompression bonding of Example 1 Under the same conditions, a highly weather-resistant decorative film excellent in design was produced by passing through and crimping between a pair of silicon rubber rolls. Next, a polyurethane adhesive is applied to a wood plywood having a thickness of 6 mm at 50 g / m.2The coating resin film for laminating the highly weather-resistant decorative board is heated at a temperature of 160 ° C. and an adhesive pressure is 12 kgf / cm.2Crimping time: Heat-bonded under conditions of 15 seconds to obtain a highly weather-resistant decorative board.
[0025]
(Example 3)
A colored solid printing layer is directly provided on the polybutylene terephthalate resin on one side of the two-layer unstretched film of the same polybutylene terephthalate resin and copolymer polyethylene terephthalate resin as in Example 2, and a pattern printing layer is provided thereon. Except for the above, printing was performed under the same conditions as in Example 2. Further, in exactly the same manner as in Example 2, after embossing while laminating the two-layer unstretched film and the polybutylene terephthalate film, wiping printing was performed, and a transparent acrylic resin film having a thickness of 60 μm was interposed with an adhesive. And a highly weather-resistant decorative film having excellent design properties. Next, 80 g / m of polyurethane adhesive is applied to a gypsum board with a thickness of 8 mm.2The above-mentioned printed resin film for laminating a highly weatherable decorative board is heated at a heating temperature of 180 ° C. and an adhesion pressure of 10 kgf / cm.2Crimping time: Under the condition of 20 seconds, the transparent acrylic resin film surface is passed through an embossing roll and a crimping roll made of a silicon rubber roll with the embossing roll side as the embossing roll. A highly weather-resistant decorative board having a thickness was obtained.
[0026]
(Example 4)
A highly weather-resistant decorative board was obtained in exactly the same manner as in Example 1, except that a commercially available transparent polyethylene terephthalate film having a thickness of 60 μm was used instead of the transparent acrylic resin film having a thickness of 60 μm in Example 1.
[0027]
(Example 5)
After producing a printed resin film in the same manner as in Example 2, an adhesive of 60 μm thick transparent polycarbonate film (manufactured by Teijin) in which an epoxy-phenol adhesive was applied on one side of the embossed surface of this printed resin film A high-definition decorative film excellent in design was produced by making the coated surfaces face each other and pressure-bonding under the same conditions as the lamination conditions by thermocompression bonding in Example 1. Next, in the same manner as in Example 2, the printed resin film for laminating high-definition decorative plate was heat-pressed on a 6 mm thick wood plywood to obtain a high-definition decorative plate.
[0028]
(Example 6)
After producing a printed resin film in the same manner as in Example 3, an adhesive-coated surface of a transparent polyarylate film having a thickness of 60 μm in which an epoxy-phenol adhesive was applied on one side was applied to the embossed surface of the printed resin film. A high-definition decorative film excellent in design was produced by facing and pressure-bonding under the same conditions as the lamination conditions by thermocompression bonding in Example 3. Next, in the same manner as in Example 3, the printed resin film for laminating high-definition decorative plate was heat-pressed on a gypsum board having a thickness of 8 mm to obtain a high-definition decorative plate.
[0029]
(Characteristic evaluation of resin film)
The high weather resistant decorative boards prepared in Examples 1, 2, 3, 4, 5 and 6 were evaluated for the following characteristics.
[0030]
(Weatherability)
For evaluation of outdoor weather resistance, a cross-cut reaching the substrate with a razor blade was applied to the film of the laminate, and a sunshine weatherometer test (JIS A 1415) was performed over a test time of 8000 hours.
Abnormalities such as cracks and discoloration of the film and the occurrence of blisters were evaluated with the naked eye and evaluated according to the following criteria.
A: No discoloration, cracks or blisters are observed.
○: The occurrence of a very small amount of blister at the cross-cut portion, which has no practical problem, is observed.
(Triangle | delta): Generation | occurrence | production of the discoloration, crack, blister of the grade which is a practical problem is recognized by the crosscut part.
X: Discoloration, cracks, and blisters are recognized to a considerable extent on the entire surface.
Moreover, the sample which gave the crosscut performed the salt spray test (JIS Z 2371) over 300 hours after 8000 hours of sunshine weatherometer tests, and evaluated the peeling width | variety of the film | membrane by forced peeling.
As a result, the peeling width was 1 mm or less for any of the decorative plates of Examples 1 to 6, and excellent corrosion resistance was exhibited.
[0031]
(Embossability)
The quality of the embossing property for wiping printing of the printing resin film for laminating a highly weather resistant decorative board of the present invention is judged by the surface roughness of the base resin layer of the embossed resin film. In the present invention, the surface of the base resin layer of the resin film embossed using an engraved roll having an average surface roughness (Ra): 11 μm of irregularities is observed with the naked eye. The quality was evaluated according to the following three criteria.
○: Good,
Δ: Somewhat bad,
×: Defect
In addition, said evaluation criteria measured the surface roughness (Ra: micrometer) of a polyvinyl chloride resin film based on JIS B0601 using the SURFCOM surface roughness meter by Tokyo Seimitsu Co., Ltd., and average surface roughness was The case of 4 μm is regarded as a pass standard for embossability, and the one having an appearance equal to or better than the surface of the polyvinyl chloride resin film having an average surface roughness of 4 μm is evaluated as good (◯). Those having an appearance that is slightly inferior to those of practical use but having no practical problem were determined as slightly defective (Δ), and those not embossed were determined as defective (×).
[0032]
(Contamination resistance)
A cloth impregnated with ethanol after drawing with black oil-based magic ink on the outermost resin film surface of the highly weather-resistant decorative board prepared in Examples 1, 2, 3, 4, 5 and 6 and leaving it to stand for 24 hours. The degree of magic ink remaining on the resin film surface was visually observed and evaluated according to the following criteria.
(Double-circle): Magic ink is not recognized at all.
○: A very slight amount of magic ink remained to the extent that there is no practical problem.
(Triangle | delta): Remaining slight magic ink which is a problem in practical use is recognized.
X: Remaining magic ink is recognized to a considerable extent.
[0033]
(Solvent resistance)
A sponge impregnated with methyl ethyl ketone was placed on the outermost resin film surface of the highly weatherable decorative board prepared in Examples 1, 2, 3, 4, 5 and 6, and left for 24 hours. The degree of blistering was visually observed and evaluated according to the following criteria.
A: No discoloration or swelling is observed.
◯: Generation of slight discoloration or swelling that is not problematic for practical use is recognized.
(Triangle | delta): Generation | occurrence | production of slight discoloration or swelling of the grade which is a problem practically is recognized.
X: Discoloration and swelling are recognized to a considerable extent.
[0034]
(Water degradation resistance)
Assuming that the highly weather-resistant decorative board of the present invention was allowed to age for a long time in a high-temperature and high-humidity state, the water-resistant deterioration resistance of the resin film when in contact with water for a long time was evaluated by the DuPont impact test method.
The printed resin film for laminating highly weather-resistant decorative plates prepared in Examples 1, 2, 3, 4, 5 and 6 was laminated on a galvanized steel sheet having a thickness of 0.5 mm to obtain a test piece. This test piece was cut into a size of 60 mm × 60 mm, immersed in demineralized water maintained at a temperature of 38 ± 2 ° C. for 1 month, dried at room temperature, and in compliance with JIS K 5400 using a DuPont impact tester. The impact was applied under the conditions (impact part size 1/2 inchφ, weight 1 kg, drop height 50 cm). The state of the resin film after the impact was loaded was observed with the naked eye and evaluated in the following five stages.
(Double-circle): A crack is not recognized by the resin film.
(Triangle | delta): A fine crack is recognized in the whole embossing part of a resin film.
X: A big crack is recognized in the whole embossing part of a resin film.
XX: The crack is remarkable in the whole resin film.
In the above ratings, ◎ and ○ are not problematic in use. In addition, this test was implemented about ten test pieces. The characteristic evaluation of these resin films is shown below.
[Table 1]
Figure 0003839258
As described above, the decorative resin laminate printing resin film of the present invention exhibits excellent properties in any of weather resistance, embossability, stain resistance, solvent resistance, and water resistance.
[Industrial applicability]
[0035]
The printed resin film for laminating highly weather-resistant decorative board according to the present invention is configured as described above, and the surface resin layer made of an acrylic resin film is excellent in durability against sunlight ultraviolet rays and heat, so that it is used for outdoor weather resistance. A laminated resin film applicable to the above can be obtained. Also, as the printing film, the base resin layer and the colored resin layer made of polybutylene terephthalate film have little fluctuation in expansion and contraction with respect to heat and tension, and have excellent dimensional stability, so that the printing registration accuracy is good. Become.
In addition, since a decorative film can be obtained with the same manufacturing method and manufacturing conditions as conventional polyvinyl chloride resin films, there is no need for capital investment such as expansion of new facilities or modification of existing facilities. It is possible to express a sharp pattern with excellent design properties in which the printed pattern and the embossed pattern are synchronized.
In addition, since the resin constituting the base resin layer and the surface resin layer does not contain a plasticizer, there is no problem such as surface contamination due to bleed of the plasticizer, contamination resistance, solvent resistance, In addition to excellent surface properties such as water resistance, there is no generation of toxic gases such as hydrogen chloride gas when incinerated, so there is no concern of polluting the environment and excellent environmental conservation.
[Brief description of the drawings]
[0036]
FIG. 1 is a cross-sectional view showing an example of a printing resin film for laminating a highly weather-resistant decorative board according to the present invention. FIG. 2 is a cross-sectional view showing another example of the printing resin film for laminating a highly weather-resistant decorative board according to the present invention. FIG. 3 is a cross-sectional view showing another example of the printing resin film for laminating a highly weather-resistant decorative board according to the present invention. FIG. 4 is a cross-sectional view showing an example of the highly weather-resistant decorative board of the present invention. FIG. 5 is a cross-sectional view showing another example of the highly weather-resistant decorative board of the present invention.

Claims (11)

接着樹脂層、基材樹脂層、ベタ印刷層、絵柄印刷層、表面樹脂層が下から順次積層された樹脂フィルムであって、
接着樹脂層とポリブチレンテレフタレート樹脂からなる基材樹脂層とを積層したフィルムの基材樹脂層面に、ポリアクリレートフィルムからなる透明な表面樹脂層の下面に設けた絵柄印刷層とベタ印刷層からなる印刷層を重ね合わせ、熱ロール間に通して圧着するとともに熱融着して積層したことを特徴とする高耐候性化粧板積層用印刷樹脂フィルム。 An adhesive resin layer, a base resin layer, a solid printing layer, a pattern printing layer, and a surface resin layer are laminated in order from the bottom ,
It consists of a pattern printing layer and a solid printing layer provided on the bottom surface of a transparent surface resin layer made of a polyacrylate film on the base resin layer surface of a film in which an adhesive resin layer and a base resin layer made of polybutylene terephthalate resin are laminated. A printed resin film for laminating a highly weather-resistant decorative board, characterized in that the printed layers are superposed, pressure-bonded through heat rolls and heat-sealed and laminated. 接着樹脂層、着色樹脂層、絵柄印刷層、基材樹脂層、表面樹脂層が下から順次積層された樹脂フィルムであって、
接着樹脂層と着色樹脂層との積層したフィルムの着色樹脂層面に、絵柄印刷層を施し、
その上にポリブチレンテレフタレート樹脂からなる基材樹脂層を重ね合わせ、
熱ロール間に通して圧着するとともに熱融着して積層し、
さらに前記基材樹脂層の上に接着剤層を介してポリアクリレートフィルムからなる透明な表面樹脂層を積層してなる高耐候性化粧板積層用印刷樹脂フィルム。 An adhesive resin layer, a colored resin layer, a pattern printing layer, a base resin layer, and a surface resin layer are laminated in order from the bottom ,
On the colored resin layer surface of the laminated film of the adhesive resin layer and the colored resin layer, a pattern printing layer is applied,
A base resin layer made of polybutylene terephthalate resin is overlaid thereon,
Passing between the heat rolls and crimping, heat-sealing and laminating,
Furthermore, the printing resin film for highly weather-resistant decorative board lamination formed by laminating | stacking the transparent surface resin layer which consists of a polyacrylate film on the said base resin layer through an adhesive bond layer. 接着樹脂層、着色樹脂層、ベタ印刷層、絵柄印刷層、基材樹脂層、表面樹脂層が下から順次積層された樹脂フィルムであって、
接着樹脂層と着色樹脂層との積層したフィルムの着色樹脂層面にベタ印刷層を設け、その上に絵柄印刷層を施し、
その上にポリブチレンテレフタレート樹脂からなる基材樹脂層を重ね合わせ、
熱ロール間に通して圧着するとともに熱融着して積層し、
さらに前記基材樹脂層の上に接着剤層を介してポリアクリレートフィルムからなる透明な表面樹脂層を積層してなる高耐候性化粧板積層用印刷樹脂フィルム。 An adhesive resin layer, a colored resin layer, a solid print layer, a pattern print layer, a base resin layer, and a surface resin layer are sequentially laminated from the bottom ,
A solid printing layer is provided on the colored resin layer surface of the laminated film of the adhesive resin layer and the colored resin layer, and a pattern printing layer is applied thereon,
A base resin layer made of polybutylene terephthalate resin is overlaid thereon,
Passing between the heat rolls and crimping, heat-sealing and laminating,
Furthermore, the printing resin film for highly weather-resistant decorative board lamination formed by laminating | stacking the transparent surface resin layer which consists of a polyacrylate film on the said base resin layer through an adhesive bond layer. エンボスロールを用いて前記基材樹脂層の表面にエンボス加工を施し、
該エンボス加工により形成されたエンボス凹部にインキが充填されてなるワイピング印刷層を有する、請求項２または３に記載の高耐候性化粧板積層用印刷樹脂フィルム。 Embossing the surface of the base resin layer using an embossing roll,
The printed resin film for laminating highly weather-resistant decorative board according to claim 2 or 3, further comprising a wiping printing layer in which ink is filled in an embossed recess formed by the embossing. 前記表面樹脂層の表面がエンボス加工によるエンボス凹部を有する、請求項１〜４のいずれかに記載の高耐候性化粧板積層用印刷樹脂フィルム。 The printed resin film for laminating highly weather-resistant decorative plates according to any one of claims 1 to 4, wherein the surface of the surface resin layer has an embossed recess formed by embossing. 樹脂フィルムを積層する基板の少なくとも片面に、請求項１〜５のいずれかに記載の高耐候性化粧板積層用印刷樹脂フィルムを積層した高耐候性化粧板。A high weather resistant decorative board in which the printed resin film for high weather resistant decorative board lamination according to any one of claims 1 to 5 is laminated on at least one surface of a substrate on which the resin film is laminated. 前記基板と前記高耐候性化粧板積層用印刷樹脂フィルムの間に接着剤層を介して積層した、請求項６に記載の高耐候性化粧板。The high weather-resistant decorative board according to claim 6 , which is laminated via an adhesive layer between the substrate and the printed resin film for laminating the high weather-resistant decorative board. 前記基板が金属板である、請求項６または７に記載の高耐候性化粧板。The highly weather-resistant decorative board according to claim 6 or 7 , wherein the substrate is a metal plate. 前記基板が木質板である、請求項６または７に記載の高耐候性化粧板。The highly weather-resistant decorative board according to claim 6 or 7 , wherein the substrate is a wood board. 前記基板がボードである、請求項６または７に記載の高耐候性化粧板。The highly weather-resistant decorative board according to claim 6 or 7 , wherein the substrate is a board. 請求項８に記載の高耐候性化粧板を用いて成形した物置。 The storeroom shape | molded using the highly weather-resistant decorative board of Claim 8 .
JP2000600841A 1999-02-26 2000-02-25 Printing resin film for laminating highly weather-resistant decorative board, high weather-resistant decorative board and storage for laminating the resin film Expired - Fee Related JP3839258B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11051707A JP2000246833A (en) 1999-02-26 1999-02-26 Print resin film for high weather resistant decorative plate laminate, high weather resistant decorative plate to which the resin film is laminated, and warehouse
PCT/JP2000/001122 WO2000050242A1 (en) 1999-02-26 2000-02-25 Printed resin film for highly weatherized decorative sheet lamination, highly weatherized decorative sheet laminated with the resin film and storeroom

Publications (1)

Publication Number Publication Date
JP3839258B2 true JP3839258B2 (en) 2006-11-01

Family

ID=12894380

Family Applications (2)

Application Number Title Priority Date Filing Date
JP11051707A Pending JP2000246833A (en) 1999-02-26 1999-02-26 Print resin film for high weather resistant decorative plate laminate, high weather resistant decorative plate to which the resin film is laminated, and warehouse
JP2000600841A Expired - Fee Related JP3839258B2 (en) 1999-02-26 2000-02-25 Printing resin film for laminating highly weather-resistant decorative board, high weather-resistant decorative board and storage for laminating the resin film

Family Applications Before (1)

Application Number Title Priority Date Filing Date
JP11051707A Pending JP2000246833A (en) 1999-02-26 1999-02-26 Print resin film for high weather resistant decorative plate laminate, high weather resistant decorative plate to which the resin film is laminated, and warehouse

Country Status (5)

Country Link
JP (2) JP2000246833A (en)
AU (1) AU2694000A (en)
MY (1) MY136381A (en)
TW (1) TW555648B (en)
WO (1) WO2000050242A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4068810B2 (en) * 2001-02-02 2008-03-26 東洋鋼鈑株式会社 Resin film laminated metal plate
JP4242081B2 (en) * 2001-03-30 2009-03-18 東洋鋼鈑株式会社 Resin coated metal plate
JP6905277B2 (en) * 2019-09-26 2021-07-21 フジ産業株式会社 How to form a wood grain pattern in an assembly shed

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07232415A (en) * 1994-02-24 1995-09-05 Dainippon Printing Co Ltd Decorative sheet
JPH0970939A (en) * 1995-09-07 1997-03-18 Dainippon Printing Co Ltd Decorative sheet

Also Published As

Publication number Publication date
WO2000050242A1 (en) 2000-08-31
AU2694000A (en) 2000-09-14
MY136381A (en) 2008-09-30
JP2000246833A (en) 2000-09-12
TW555648B (en) 2003-10-01

Similar Documents

Publication Publication Date Title
JP3705482B2 (en) Printed resin film for decorative board lamination and decorative board laminated with the resin film
JP4245284B2 (en) Decorative film material, decorative film, manufacturing method thereof, and decorative plate laminated with decorative film
JP4176088B2 (en) High-definition decorative film laminated metal plate
JP4068810B2 (en) Resin film laminated metal plate
JP3839258B2 (en) Printing resin film for laminating highly weather-resistant decorative board, high weather-resistant decorative board and storage for laminating the resin film
JP3913060B2 (en) Printed resin film for laminating high-definition decorative board excellent in processability and high-definition decorative board laminated with the resin film
JP3839257B2 (en) Printing resin film for laminating high-definition decorative board and high-definition decorative board laminated with the resin film
JP4107606B2 (en) Printed resin film for decorative plate lamination and decorative plate laminated therewith
JP3913061B2 (en) Printed resin film for decorative plate lamination, decorative plate laminated with the resin film, unit bath using the decorative plate, refrigerator door
JP4297858B2 (en) Decorative plate laminated resin film, decorative plate laminated with the resin film, and unit bath using the decorative plate
JP3945737B2 (en) Method for producing resin film for decorative laminate and method for producing decorative plate
JP3905316B2 (en) Decorative film and decorative board laminated with the decorative film
JP3712617B2 (en) Decorative plate manufacturing method
JP4792175B2 (en) Decorative film and decorative board laminated with the film
JP2002059512A (en) Resin film for laminating highly weatherable decorative sheet and highly weatherable decorative sheet having resin film laminated thereto
JP3678339B2 (en) Print resin film for laminating decorative plates excellent in alkali resistance, a decorative plate laminated with the resin film, and a unit bath using the decorative plate
JP3958936B2 (en) Unit bath decorative board and unit bath
JP3672870B2 (en) Printed resin film for decorative board lamination and decorative board laminated with the resin film
JP2002059518A (en) Resin film for laminating decorative plate excellent in antistatic property and decorative plate laminated with the film
JP6515561B2 (en) Aluminum decorative member
JP5582939B2 (en) Printed resin film for decorative plate lamination, decorative plate laminated with the film, and unit bath using the decorative plate
JP4615944B2 (en) Print resin film for laminating decorative plates excellent in alkali resistance, a decorative plate laminated with the resin film, and a unit bath using the decorative plate
JPH0717005A (en) Decorative sheet
JP3694460B2 (en) Printed resin film, decorative plate laminated with the printed resin film, and unit bath using the decorative plate
JP2005059538A (en) Resin film to be laminated on decorative board, decorative board formed by laminating resin film, unit bath using the board

Legal Events

Date Code Title Description
A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20050823

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20051024

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20060801

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20060802

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

Ref document number: 3839258

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20090811

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20100811

Year of fee payment: 4

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20100811

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110811

Year of fee payment: 5

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120811

Year of fee payment: 6

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130811

Year of fee payment: 7

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

LAPS Cancellation because of no payment of annual fees