JP4710385B2 - Decorative sheet for metal decorative board - Google Patents

Decorative sheet for metal decorative board Download PDF

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JP4710385B2
JP4710385B2 JP2005107197A JP2005107197A JP4710385B2 JP 4710385 B2 JP4710385 B2 JP 4710385B2 JP 2005107197 A JP2005107197 A JP 2005107197A JP 2005107197 A JP2005107197 A JP 2005107197A JP 4710385 B2 JP4710385 B2 JP 4710385B2
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decorative sheet
decorative
styrene
metal
sheet
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JP2006281687A (en
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誠治 佐野
浩一 佐川
勝之 新名
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Toppan Inc
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Description

本発明は住宅建材や自動車内装などに用いる化粧シートに関するものであり、特に金属に貼り合わせて曲げ加工を行うのに適した化粧シートに関する。   The present invention relates to a decorative sheet used for housing building materials, automobile interiors, and the like, and more particularly, to a decorative sheet suitable for bending by bonding to metal.

金属表面に意匠を付与する方法として、樹脂塗装を行う事により意匠性を保たせた塗装鋼板などが存在していたが、高い意匠性やエンボス表現などが塗装では得られない為、塩化ビニル製化粧シートを金属板用の化粧シートとして仕様する事が行われてきた。   As a method of imparting a design to a metal surface, there was a coated steel sheet that maintained its design by resin coating, but since high design properties and embossed expression cannot be obtained by painting, it is made of vinyl chloride. The decorative sheet has been specified as a decorative sheet for metal plates.

しかし、近年の塩化ビニルによる環境問題、特に燃焼時の塩素、ダイオキシン発生等の懸念により塩化ビニル以外での化粧シートへの要求が高まってきた。このような情勢のなかでアクリル樹脂を使用した化粧シートや完全非結晶性ポリエステル樹脂を使用した化粧シート等が現れてきた。ところがこれら塩化ビニル代替化粧シートは塩化ビニル樹脂と比較すると高価な樹脂を使用しており完全な代替品といえるものではなかった。   However, demands for decorative sheets other than vinyl chloride have increased due to environmental problems caused by vinyl chloride in recent years, particularly concerns regarding the generation of chlorine and dioxins during combustion. Under such circumstances, a decorative sheet using an acrylic resin, a decorative sheet using a completely non-crystalline polyester resin, and the like have appeared. However, these vinyl chloride substitute decorative sheets use expensive resins as compared with vinyl chloride resins, and are not perfect substitutes.

また、安価なポリオレフィン系樹脂系化粧シートを使用する例もあるが、曲げ加工時に白化、割れを生じる等の問題があり使用出来る部位に制限が出来ていた。最近ではリアクタータイプのオレフィン系熱可塑性エラストマーやゴム成分等の軟質成分を添加したオレフィン系熱可塑性エラストマーを使用する物もでてきたがこれらのシートは曲げ加工性は良い物の、表面硬度が低く傷が付きやすいという欠点もあった。   In addition, there is an example of using an inexpensive polyolefin-based resin decorative sheet, but there are problems such as whitening and cracking at the time of bending, and the usable parts are limited. Recently, there have been some products that use olefinic thermoplastic elastomers to which soft components such as reactor-type olefinic thermoplastic elastomers and rubber components are added, but these sheets have good bending workability but low surface hardness. There was also the fault of being easily scratched.

本発明は以上のような問題点を解決するものであり、その課題とすることは、従来の塩化ビニル樹脂以外の非塩素系樹脂を用いた化粧シートで、かつ曲げ加工の適正に優れかつ表面硬度の高い化粧シートを提供することにある。   The present invention solves the problems as described above, and the problem is that it is a decorative sheet using a non-chlorine resin other than the conventional vinyl chloride resin, and has an excellent bending process and a surface. The object is to provide a decorative sheet having high hardness.

本発明はこの課題を決するものであり、すなわちその請求項1記載の発明は、ポリプロピレン系樹脂からなる透明または半透明の表面樹脂層を有する金属化粧板用化粧シートにおいて、前記表面樹脂層が、5%以下のエチレン濃度を有するランダムポリプロピレンと、アイソタクチック指数96のアイソタチックポリプロピレンとに、スチレン含有量が15重量%であるスチレンブタジエンラバーを20重量部添加してなる混合体からなることを特徴とする金属化粧板用化粧シートである。 The present invention determines this problem, that is, the invention according to claim 1 is a decorative sheet for a metal decorative board having a transparent or translucent surface resin layer made of a polypropylene resin, wherein the surface resin layer comprises: It consists of a mixture obtained by adding 20 parts by weight of a styrene butadiene rubber having a styrene content of 15 % by weight to a random polypropylene having an ethylene concentration of 5% or less and an isotactic polypropylene having an isotactic index of 96. A decorative sheet for a metal decorative board.

本発明は以上の構成により、白化、割れに対して良好な耐性を示し、該化粧シートを貼り合わせた金属化粧板は良好な折り曲げ加工適性を示し、折り曲げ加工適性の高い化粧シートとする事ができる。   The present invention has a good resistance to whitening and cracking, and the metal decorative board to which the decorative sheet is bonded exhibits good folding processability and can be made into a decorative sheet having high folding processability. it can.

以下、本発明の実施の形態を図面を用いて詳細に説明する。図1に本発明の化粧シートの一実施例の断面の構造を示す。基材シート1に絵柄層2が施され、その上に接着層3を介して表面樹脂層4が積層されてなる。これを適宜金属板5に貼り合わせて用いる。
本発明における基材シート1、絵柄層2、接着層3、金属板5は適宜従来公知のものが使用可能である。接着層は特には2液硬化型ウレタン系のものが好適であるが、特にこれに限定するものではない。
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 shows a cross-sectional structure of one embodiment of the decorative sheet of the present invention. A pattern layer 2 is applied to the base material sheet 1, and a surface resin layer 4 is laminated thereon via an adhesive layer 3. This is used by appropriately bonding to the metal plate 5.
As the substrate sheet 1, the pattern layer 2, the adhesive layer 3, and the metal plate 5 in the present invention, conventionally known materials can be used as appropriate. The adhesive layer is particularly preferably a two-component curable urethane type, but is not particularly limited thereto.

本発明の表面樹脂層4で使用される樹脂は、5%以下のエチレン濃度を有するランダムポリプロピレンと、アイソタクチック指数96以上のアイソタチックポリプロピレンとに、スチレン含有量が5〜60重量%であるスチレンブタジエンラバーを5〜40重量部添加してなる混合体を用いる。ここでいうアイソタクチック指数は沸騰ヘプタン抽出後の不溶成分の割合である。   The resin used in the surface resin layer 4 of the present invention is a random polypropylene having an ethylene concentration of 5% or less and an isotactic polypropylene having an isotactic index of 96 or more and a styrene content of 5 to 60% by weight. A mixture obtained by adding 5 to 40 parts by weight of a certain styrene butadiene rubber is used. The isotactic index here is the ratio of insoluble components after extraction with boiling heptane.

スチレンブタジエンラバーのスチレン含有量が5未満もしくは60重量部を越えている場合、ポリプロピレン中でのスチレンブタジエンラバー界面でのクレーズ発生が起こりやすくなり曲げ白化の原因となりうる。   When the styrene content of the styrene butadiene rubber is less than 5 or exceeds 60 parts by weight, craze generation is likely to occur at the styrene butadiene rubber interface in polypropylene, which may cause bending whitening.

スチレンブタジエンラバーの配合が5重量%以下であると表面樹脂層の柔軟性が十分でなく曲げたときに割れ、白化が起きやすく又配合比が40重量%を越えると柔軟性は向上するものの、表面硬度が低くなり傷がつきやすいといった問題が現れてくる。   If the blend of styrene butadiene rubber is 5% by weight or less, the flexibility of the surface resin layer is not sufficient and cracking and whitening easily occur when bent, and if the blending ratio exceeds 40% by weight, the flexibility is improved. The problem that surface hardness becomes low and is easy to be damaged appears.

又、スチレンブタジエンラバーはブタジエンブロックに二重結合を持ち紫外線により黄変する可能性がある為水素添加して二重結合を飽和させた水素添加スチレンブタジエンラバーを使用するとより耐候性を向上させることが出来る。   Also, since styrene butadiene rubber has a double bond in the butadiene block and may turn yellow due to ultraviolet rays, the use of hydrogenated styrene butadiene rubber with hydrogen to saturate the double bond can improve weather resistance. I can do it.

また、スチレンブタジエンとしては、スチレン−ブタジエン−スチレン(SBS)、スチレン−イソプレン−スチレン(SIS)、スチレン−エチレン/ブチレン−スチレン(SEBS)、スチレン−エチレン/プロピレン−スチレン(SEPS)、スチレン−ブタジエン(SB)、スチレン−エチレン/プロピレン(SEP)、スチレン−エチレン/ブチレン(SEB)および水添スチレン−ブタジエン(HSB)、スチレン−エチレン−ブタジエン/オレフィン結晶(SEBC)、オレフィン結晶/エチレン−ブタジエン/オレフィン結晶(CEBC)等が挙げられる。   As styrene butadiene, styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene / butylene-styrene (SEBS), styrene-ethylene / propylene-styrene (SEPS), styrene-butadiene. (SB), styrene-ethylene / propylene (SEP), styrene-ethylene / butylene (SEB) and hydrogenated styrene-butadiene (HSB), styrene-ethylene-butadiene / olefin crystals (SEBC), olefin crystals / ethylene-butadiene / Examples thereof include olefin crystals (CEBC).

また、スチレンブタジエンラバーのMFRが2g/10min以下であると押し出し加工における樹脂圧力が高く生産性が低い。20g/10min以上の場合、最適な微分散形態を得るのにポリプロピレン樹脂の選定において制約を受けることが多い。   Further, if the MFR of the styrene butadiene rubber is 2 g / 10 min or less, the resin pressure in the extrusion process is high and the productivity is low. In the case of 20 g / 10 min or more, selection of a polypropylene resin is often restricted in order to obtain an optimal fine dispersion form.

さらに表面樹脂層4としてフィルム状に押し出す際及び得られた製品の熱酸化を防止するために酸化防止剤を、紫外線による劣化を防止するために光安定剤をそれぞれ適宜添加してもよい。これら添加剤の種類、添加量は特に規定しないが、オレフィン系樹脂に一般的に使用されているものの組み合わせで十分である。   Further, an antioxidant may be added as appropriate when the surface resin layer 4 is extruded as a film, and an antioxidant is added to prevent thermal oxidation of the resulting product, and a light stabilizer is added to prevent deterioration due to ultraviolet rays. The type and amount of these additives are not particularly limited, but a combination of those commonly used for olefin resins is sufficient.

なお基材シート1上に表面樹脂層4を積層する方法としては熱ラミネート法またはドライラミネート法、押し出しラミネート法、ニーラム法等があり用途に合わせて適宜選択すればよく、公知の方法により貼り合わせれば良い。   In addition, as a method of laminating the surface resin layer 4 on the base sheet 1, there are a heat laminating method, a dry laminating method, an extrusion laminating method, a knee laminating method, etc. It ’s fine.

化粧シートと金属板5との接着は、接着剤によるものであるが特に規定するものでは無く、一般的な物で十分であり、化粧シートの裏面にはプライマー層を設けても良い。   Adhesion between the decorative sheet and the metal plate 5 is based on an adhesive, but is not particularly defined, and a general object is sufficient, and a primer layer may be provided on the back surface of the decorative sheet.

基材シート1としてポリエチレン樹脂フィルムを用い、その上にウレタン系インキを用いて木目柄をグラビア印刷により印刷して絵柄層2とした。   A polyethylene resin film was used as the base sheet 1, and a wood grain pattern was printed thereon by gravure printing using urethane-based ink to form a picture layer 2.

上記で得られた絵柄層2の上に、グラビア印刷法によりウレタン系の接着剤3を厚さ約5μmになるように塗布した。その後フェノール系酸化防止剤を0.2重量%、ヒンダードアミン系光安定剤を0.3重量%、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、5%以下のエチレン濃度を有するランダムポリプロピレン、アイソタクチック指数96のアイソタチックポリプロピレン、更にスチレン含有量が15重量%であるスチレンブタジエンラバーを20重量部添加した混合樹脂を溶融押出し法により表面樹脂層4とし、前記接着剤3を設けた面に二液硬化型ウレタン系接着剤を用いてドライラミネートして化粧シートを得た。   On the pattern layer 2 obtained above, a urethane-based adhesive 3 was applied to a thickness of about 5 μm by a gravure printing method. Thereafter, 0.2% by weight of a phenolic antioxidant, 0.3% by weight of a hindered amine light stabilizer, and 0.5% by weight of a benzotriazole ultraviolet absorber are added, and a random polypropylene having an ethylene concentration of 5% or less. A surface resin layer 4 is formed by melt extrusion using a mixed resin to which 20 parts by weight of isotactic polypropylene having an isotactic index of 96 and styrene content rubber having a styrene content of 15% by weight is added, and the adhesive 3 is provided. The laminated surface was dry laminated using a two-component curable urethane adhesive to obtain a decorative sheet.

その後、溶融亜鉛メッキを施した鋼板5にウレタン変成ポリエステルポリオール/ポリイソシアネート系接着剤をロールコートで乾燥後の塗布厚が5g/m2となるように塗布して、該鋼板を200℃で3分加熱し、これと前記化粧シートの基材シート1側と貼り合わせゴムロールで圧着後水槽で急冷して金属化粧板を得た。   Thereafter, a urethane-modified polyester polyol / polyisocyanate adhesive was applied to the hot-dip galvanized steel plate 5 by roll coating so that the coating thickness after drying was 5 g / m 2, and the steel plate was applied at 200 ° C. for 3 minutes. This was heated and bonded to the base sheet 1 side of the decorative sheet and bonded with a rubber roll, and then rapidly cooled in a water tank to obtain a metal decorative board.

<比較例1>
上記実施例1において、ランダムポリプロピレンのエチレン含有量を30%とした以外は実施例1と同様にして化粧シートを得、金属化粧板を得た。
<Comparative Example 1>
In Example 1, a decorative sheet was obtained in the same manner as in Example 1 except that the ethylene content of random polypropylene was changed to 30% to obtain a metal decorative board.

上記実施例1及び比較例1で得られた金属化粧板に曲げ加工を2種類行い加工部の白化の有無を目視評価した。更にJISK5600の鉛筆硬度試験で表面硬度を評価した。最後にサンシャインウエザオメーターで紫外線を照射し、1000h後での外観変化を目視評価した。結果を表1に示す。   Two types of bending processing were performed on the metal decorative plates obtained in Example 1 and Comparative Example 1 above, and the presence or absence of whitening of the processed portion was visually evaluated. Furthermore, the surface hardness was evaluated by the pencil hardness test of JISK5600. Finally, ultraviolet rays were irradiated with a sunshine weatherometer, and the appearance change after 1000 hours was visually evaluated. The results are shown in Table 1.

Figure 0004710385
Figure 0004710385

実施例1で得られた化粧シート及び金属化粧板は非塩化ビニル系樹脂であることは言うまでもなく、表1からも明らかなように、折り曲げ加工性、鉛筆硬度に優れた金属化粧板であった。   Needless to say, the decorative sheet and the metal decorative board obtained in Example 1 are non-vinyl chloride resins, and as is apparent from Table 1, the decorative metal sheet and the metal decorative board were excellent in bending workability and pencil hardness. .

比較例1で得られた化粧シート1及び金属化粧板は曲げ白化性は良好だが、耐傷付き性が悪かった。   The decorative sheet 1 and the metal decorative board obtained in Comparative Example 1 had good bending whitening properties but poor scratch resistance.

本発明の化粧シートの一実施例の断面の構造を示した説明図である。It is explanatory drawing which showed the structure of the cross section of one Example of the decorative sheet of this invention.

符号の説明Explanation of symbols

1…基材シート
2…絵柄層
3…接着層
4…表面樹脂層
5…金属板
DESCRIPTION OF SYMBOLS 1 ... Base material sheet 2 ... Picture layer 3 ... Adhesive layer 4 ... Surface resin layer 5 ... Metal plate

Claims (1)

ポリプロピレン系樹脂からなる透明または半透明の表面樹脂層を有する金属化粧板用化粧シートにおいて、前記表面樹脂層が、5%以下のエチレン濃度を有するランダムポリプロピレンと、アイソタクチック指数96のアイソタチックポリプロピレンとに、スチレン含有量が15重量%であるスチレンブタジエンラバーを20重量部添加してなる混合体からなることを特徴とする金属化粧板用化粧シート。
In a decorative sheet for a metal decorative board having a transparent or translucent surface resin layer made of a polypropylene resin, the surface resin layer has a random polypropylene having an ethylene concentration of 5% or less, and an isotactic index of 96 . A decorative sheet for a metal decorative board, comprising a mixture obtained by adding 20 parts by weight of styrene butadiene rubber having a styrene content of 15 % by weight to polypropylene.
JP2005107197A 2005-04-04 2005-04-04 Decorative sheet for metal decorative board Expired - Fee Related JP4710385B2 (en)

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Publication number Priority date Publication date Assignee Title
JP5439714B2 (en) * 2007-08-29 2014-03-12 凸版印刷株式会社 Decorative sheet
JP5067118B2 (en) * 2007-10-26 2012-11-07 凸版印刷株式会社 Decorative sheet

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61139441A (en) * 1984-12-11 1986-06-26 チッソ株式会社 Polypropylene group sheet and workpiece using said sheet
JPS62256848A (en) * 1986-04-30 1987-11-09 Idemitsu Petrochem Co Ltd Propylene polymer composition and production thereof
JPH08291233A (en) * 1995-04-21 1996-11-05 Tonen Chem Corp Polypropylene resin composition for drawn film
JPH0985824A (en) * 1995-09-22 1997-03-31 Toppan Printing Co Ltd Embossed sheet, laminate using the same and production thereof
JPH1067080A (en) * 1996-08-28 1998-03-10 Mitsubishi Chem Mkv Co Decorative sheet
JP2003062955A (en) * 2001-08-24 2003-03-05 Toppan Printing Co Ltd Decorative sheet
JP2003535178A (en) * 2000-05-31 2003-11-25 バセル テクノロジー カンパニー ビー.ブイ. Propylene polymer composition having improved impact strength and excellent optical properties
JP2003340993A (en) * 2002-05-29 2003-12-02 Toppan Printing Co Ltd Decorative sheet
JP2005041174A (en) * 2003-07-25 2005-02-17 Toppan Printing Co Ltd Decorative sheet and decorative material

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61139441A (en) * 1984-12-11 1986-06-26 チッソ株式会社 Polypropylene group sheet and workpiece using said sheet
JPS62256848A (en) * 1986-04-30 1987-11-09 Idemitsu Petrochem Co Ltd Propylene polymer composition and production thereof
JPH08291233A (en) * 1995-04-21 1996-11-05 Tonen Chem Corp Polypropylene resin composition for drawn film
JPH0985824A (en) * 1995-09-22 1997-03-31 Toppan Printing Co Ltd Embossed sheet, laminate using the same and production thereof
JPH1067080A (en) * 1996-08-28 1998-03-10 Mitsubishi Chem Mkv Co Decorative sheet
JP2003535178A (en) * 2000-05-31 2003-11-25 バセル テクノロジー カンパニー ビー.ブイ. Propylene polymer composition having improved impact strength and excellent optical properties
JP2003062955A (en) * 2001-08-24 2003-03-05 Toppan Printing Co Ltd Decorative sheet
JP2003340993A (en) * 2002-05-29 2003-12-02 Toppan Printing Co Ltd Decorative sheet
JP2005041174A (en) * 2003-07-25 2005-02-17 Toppan Printing Co Ltd Decorative sheet and decorative material

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