JP2004314498A - Decorative sheet - Google Patents
Decorative sheet Download PDFInfo
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- JP2004314498A JP2004314498A JP2003113207A JP2003113207A JP2004314498A JP 2004314498 A JP2004314498 A JP 2004314498A JP 2003113207 A JP2003113207 A JP 2003113207A JP 2003113207 A JP2003113207 A JP 2003113207A JP 2004314498 A JP2004314498 A JP 2004314498A
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- JP
- Japan
- Prior art keywords
- resin
- decorative sheet
- ionizing radiation
- layer
- thermosetting resin
- 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.)
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、木質系基材、無機質系基材、金属系基材等々の基材へ貼り合わせるオレフィン系化粧シートおよびポリエステル系化粧シートに関することである。
【0002】
【従来の技術】
弊社で製造している化粧シートのうちポリオレフィン樹脂を主としている場合は特に、基材フィルムへの十分な接着は得られていない。最表層に電離放射線硬化型樹脂を含有している場合、その硬化収縮で常態での密着や、耐候、耐湿熱での密着、ハンドリング、耐衝撃性、後加工性等に影響したりする場合が多い。
【0003】
さらに、表面硬度等を得ようとすると電離放射線硬化型塗膜のみで最表層を形成しようとしてしまうが、前述の問題も残る。そこで、熱硬化型樹脂等を混合する手法が取られることが多いが、表面硬度を落とすことが多かった。
【0004】
【特許文献1】
特開2000−117925号公報
【特許文献2】
特開2002−028904号公報
【0005】
【発明が解決しようとする課題】
電離放射線硬化型樹脂と熱硬化型樹脂を混合した最表層の耐衝撃性や密着性を維持しつつ、表面硬度や耐汚染性も保持し、トータル的な塗膜物性を向上させた化粧シート。
【0006】
【課題を解決するための手段】
本発明は、(1)基材フィルム上に1層以上の層を具備し、その最表層が電離放射線硬化型樹脂と熱硬化型樹脂の混合体であり、その電離放射線硬化型樹脂のTgが90℃以上、熱硬化させた樹脂のTgが90℃以上であるものが混合されていることを特徴とする化粧シートであり、さらに、(2)2層以上存在する場合、下層のTgが上層の硬化塗膜のTgよりも低いことを特徴とする化粧シートであり、(3)2層以上存在する場合、下層の25℃での硬化塗膜伸度が、上層のそれよりも大きいことを特徴とする化粧シートであり、(4)前述した電離放射線硬化型樹脂と熱硬化性樹脂の混合比において、熱硬化性樹脂の存在比が10部以上(重量比)であることを特徴とする化粧シートである。
【0007】
【発明の実施の形態】
印刷の施された基材に対しオレフィン樹脂あるいはポリエステル樹脂等が積層されたシートに対して、塗工等によりオーバーコートする場合、その組成中に電離放射線硬化型樹脂を存在させ架橋密度を向上させ表面性能を得る場合があるが、特に硬化収縮等の問題から初期密着を始めとした、耐候密着、耐湿熱密着や樹脂設計によってはハンドリング、後加工性や耐衝撃性にも悪影響が出る場合があった。逆にその点を考慮した樹脂処方にすると上記の表面性能が損なわれる場合が多い。そこで、フィルム基材とトップコート層に緩衝層いわゆるリコート層を設けることにより、硬化収縮を緩和することができる。かつ、そこで、混合する硬化樹脂のTgや塗膜積層をコントロールすることにより、表面性能等を維持しつつ、塗膜密着やハンドリング等にも耐えうることができ、最終的に強靱な化粧シートを形成することができた。具体的には、基材フィルムと最表層の電離放射線硬化型樹脂と熱硬化樹脂の混合物を使用して1層以上の層を形成するが、混合される各樹脂のTgが90℃以上とすること、さらに複層化の場合は、下層樹脂のTgが表層のそれより低くすることにより前述の問題点を克服することが出来た。
【0008】
本発明は、電離放射線硬化型塗膜に熱硬化型樹脂を混合する手法において、そのTgを選択することによって、表面硬度や耐汚染性等の表面物性を低下させることなく、耐衝撃性等も維持させることができ、上記の問題点を克服することができた。
【0009】
また、基材フィルムや電離放射線硬化型樹脂と熱硬化型樹脂の混合比によっては、常態密着に優れない場合は、基材フィルムと最表層のトップコート層の間に1層以上の積層しさせることにより密着を向上させることができた。その際、その塗膜のTgをコントロールすることにより、他の諸物性に影響を与えることなく問題点を克服することができた。
【0010】
【実施例】
以下に、本発明の化粧シートに関する具体的な実施例及び比較例を挙げ、本発明をより詳細に説明する。
【0011】
<実施例1>
木目印刷(D)の施されたオレフィン系のシート(O)の裏面にプライマー樹脂(P)層を設け、アンカー樹脂層上にさらに、クリヤ樹脂(C)をラミネートした化粧シートにおいて、最表層トップコート(T)として、紫外線硬化型樹脂/アクリルポリオール/イソシアネート硬化剤を混合し、希釈溶剤で適切な粘度に希釈し、ナチュラルグラビア方式、グラビアリバース方式のコート方式によって、トータルで10g/m2塗布した。
【0012】
硬化方法は、UVランプ(フュージョン製:Dバルブ)にて硬化させた後、40℃の温乾養生を3日以上行い、化粧シートを得た。
【0013】
<実施例2>
木目の施されたオレフィン系のシート上の裏面にプライマー樹脂層を設け、アンカー樹脂層上にさらに、樹脂をラミネートした化粧シートにおいて、アクリルポリオールとHDI系硬化剤を当量の1.5倍混合したTg78℃の樹脂を希釈溶剤で適切な粘度に希釈した後、さらに、Tg95℃となるアクリルポリオールとイソシアネート硬化剤を同方法により塗布した後、40℃での温乾養生にて硬化させた。
【0014】
その後、最表層トップコートとして、実施例1のトップコート樹脂を希釈溶剤で適切な粘度に希釈し、ナチュラルグラビア方式、グラビアリバース方式のコート方式によって、トータルで10g/m2塗布した。
【0015】
硬化方法は、UVランプ(フュージョン製:Dバルブ)にて硬化させた後、40℃の温乾養生を3日以上行い、化粧シートを得た。
【0016】
<比較例1>
実施例1の方法と同様に化粧シートを作製する際に、最表層をして使用するトップコート樹脂の配合時、混合する熱硬化性樹脂(Tg:55℃)を使用し、化粧シートを得た。
【0017】
<比較例2>
実施例2と同様に化粧シートを作製する際、最表層よりもTgが高く、塗膜伸度の小さい樹脂を設定し、比較の為、同様の塗布量で2層に渡って塗布、硬化させた。最表層には、実施例2と同様のトップコートを具備させ、化粧シートを得た。
【0018】
<比較例3>
実施例1と同様に化粧シートを作製する際、最表層として使用するトップコート樹脂の配合時、熱硬化性樹脂の配合をゼロとし、電離放射線硬化型樹脂のみとして化粧シートを得た。
【0019】
<比較例4>
実施例1と同様に化粧シートを作製する際、Tgの70℃程度と低い電離放射線硬化型樹脂処方を用い、更に、同様に熱硬化樹脂も70℃程度のTgのモノを使用し、混合比は実施例1の通りで化粧シートを得た。
【0020】
<結果>
【表1】
但し、表中の「セロテープ」はニチバン株式会社の登録商標である。
【0021】
【発明の効果】
本発明は、最表層に電離放射線硬化型樹脂を用いた場合、表面硬度や耐汚染性等の表面物性に関しては良好であるが、密着性や耐衝撃性を満たすことができない。
【0022】
そこで、熱硬化性樹脂を混合する手段を用い、密着や耐衝撃性を向上させる場合が多いが、この時混合する熱硬化性樹脂のTgを考慮しないと前述の物性が両立できない場合が多い。そこで、本発明では、その電離放射線硬化樹脂、熱硬化樹脂各々のTgを90℃以上にすることにより前述の耐衝撃性や密着を維持しつつ、表面硬度や耐汚染性も保持することができ、トータル的な塗膜物性を向上させることが出来た。
【図面の簡単な説明】
【図1】本発明におけるシート構成。
【符号の説明】
P・・プライマー層
O・・オレフィン系シート
D・・印刷
C・・クリヤ樹脂
T・・トップコート層[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an olefin-based decorative sheet and a polyester-based decorative sheet to be bonded to substrates such as a wood-based substrate, an inorganic-based substrate, and a metal-based substrate.
[0002]
[Prior art]
Especially when the decorative sheet mainly manufactured by our company mainly uses polyolefin resin, sufficient adhesion to the base film has not been obtained. When the outermost layer contains an ionizing radiation-curable resin, its cure shrinkage may affect normal adhesion, weather resistance, adhesion under wet heat, handling, impact resistance, post-processability, etc. Many.
[0003]
Further, when the surface hardness and the like are to be obtained, the outermost layer is formed only with the ionizing radiation-curable coating film, but the above-mentioned problem remains. Therefore, a method of mixing a thermosetting resin or the like is often used, but the surface hardness is often reduced.
[0004]
[Patent Document 1]
JP 2000-117925 A [Patent Document 2]
JP-A-2002-28904 [0005]
[Problems to be solved by the invention]
A decorative sheet that maintains the impact resistance and adhesion of the outermost layer of a mixture of ionizing radiation-curable resin and thermosetting resin, while maintaining surface hardness and stain resistance, and improving the overall physical properties of the coating film.
[0006]
[Means for Solving the Problems]
The present invention provides (1) one or more layers on a base film, the outermost layer of which is a mixture of an ionizing radiation-curable resin and a thermosetting resin, and the Tg of the ionizing radiation-curable resin is A decorative sheet characterized by being mixed with a resin having a Tg of 90 ° C. or higher and a thermosetting resin of 90 ° C. or higher. (2) When two or more layers are present, the lower layer has an upper layer Tg. (3) When two or more layers are present, the lower layer has a cured film elongation at 25 ° C. greater than that of the upper layer. (4) The mixing ratio of the ionizing radiation-curable resin and the thermosetting resin, wherein the mixing ratio of the thermosetting resin is 10 parts or more (weight ratio). It is a decorative sheet.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
When a sheet on which an olefin resin or polyester resin is laminated on a printed substrate is overcoated by coating or the like, an ionizing radiation-curable resin is present in the composition to improve the crosslinking density. Although surface performance may be obtained, there are cases where handling, post-processability and impact resistance may be adversely affected depending on weather resistance, wet heat resistance, or resin design, especially initial adhesion due to problems such as curing shrinkage. there were. Conversely, when the resin formulation is made in consideration of this point, the above-mentioned surface performance is often impaired. Therefore, by providing a buffer layer, a so-called recoat layer, on the film substrate and the top coat layer, cure shrinkage can be reduced. In addition, by controlling the Tg of the cured resin to be mixed and the lamination of the coating film, it is possible to withstand the adhesion and handling of the coating film while maintaining the surface performance and the like. Could be formed. Specifically, one or more layers are formed using a mixture of the base film and the outermost layer of the ionizing radiation-curable resin and the thermosetting resin, and the Tg of each resin to be mixed is 90 ° C. or higher. In the case of a multilayer structure, the above-mentioned problems could be overcome by lowering the Tg of the lower resin to that of the surface layer.
[0008]
The present invention relates to a method of mixing a thermosetting resin with an ionizing radiation-curable coating film, by selecting the Tg thereof, without deteriorating the surface physical properties such as surface hardness and stain resistance, and also improving impact resistance and the like. The above problems could be overcome.
[0009]
In addition, depending on the mixing ratio of the base film or the ionizing radiation-curable resin and the thermosetting resin, if the normal state adhesion is not excellent, one or more layers are laminated between the base film and the outermost top coat layer. As a result, the adhesion could be improved. At that time, by controlling the Tg of the coating film, the problems could be overcome without affecting other physical properties.
[0010]
【Example】
Hereinafter, the present invention will be described in more detail with reference to specific examples and comparative examples relating to the decorative sheet of the present invention.
[0011]
<Example 1>
In the decorative sheet in which a primer resin (P) layer is provided on the back surface of the olefin-based sheet (O) on which the grain print (D) has been applied, and a clear resin (C) is further laminated on the anchor resin layer, As the coat (T), an ultraviolet curing resin / acrylic polyol / isocyanate curing agent is mixed, diluted to an appropriate viscosity with a diluting solvent, and applied in a total amount of 10 g / m 2 by a natural gravure method or a gravure reverse method. did.
[0012]
The curing method was such that after curing with a UV lamp (manufactured by Fusion: D-bulb), warm drying at 40 ° C. was performed for 3 days or more to obtain a decorative sheet.
[0013]
<Example 2>
A primer resin layer was provided on the back surface of the olefin-based sheet provided with the wood grain, and further, on a decorative sheet in which a resin was laminated on the anchor resin layer, an acrylic polyol and an HDI-based curing agent were mixed at 1.5 times the equivalent weight. After diluting the resin having a Tg of 78 ° C. to an appropriate viscosity with a diluting solvent, an acrylic polyol and an isocyanate curing agent having a Tg of 95 ° C. were further applied by the same method, and then cured by warm drying at 40 ° C.
[0014]
Thereafter, as a top coat on the outermost layer, the top coat resin of Example 1 was diluted to an appropriate viscosity with a diluting solvent, and a total of 10 g / m 2 was applied by a natural gravure method or a gravure reverse method.
[0015]
The curing method was such that after curing with a UV lamp (manufactured by Fusion: D-bulb), warm drying at 40 ° C. was performed for 3 days or more to obtain a decorative sheet.
[0016]
<Comparative Example 1>
When preparing a decorative sheet in the same manner as in Example 1, a thermosetting resin (Tg: 55 ° C.) to be mixed with the top coat resin used as the outermost layer is used to obtain a decorative sheet. Was.
[0017]
<Comparative Example 2>
When preparing a decorative sheet in the same manner as in Example 2, a resin having a higher Tg than the outermost layer and a small coating film elongation was set, and for comparison, applied and cured over two layers with the same application amount. Was. The outermost layer was provided with the same top coat as in Example 2 to obtain a decorative sheet.
[0018]
<Comparative Example 3>
When preparing a decorative sheet in the same manner as in Example 1, the mixing of the thermosetting resin was zero when the top coat resin used as the outermost layer was mixed, and a decorative sheet was obtained using only the ionizing radiation-curable resin.
[0019]
<Comparative Example 4>
When preparing a decorative sheet in the same manner as in Example 1, an ionizing radiation-curable resin formulation having a low Tg of about 70 ° C. was used. Was obtained as in Example 1.
[0020]
<Result>
[Table 1]
However, "cellotape" in the table is a registered trademark of Nichiban Corporation.
[0021]
【The invention's effect】
In the present invention, when an ionizing radiation-curable resin is used for the outermost layer, surface properties such as surface hardness and stain resistance are good, but adhesion and impact resistance cannot be satisfied.
[0022]
Therefore, a method of mixing a thermosetting resin is often used to improve adhesion and impact resistance. However, in many cases, the above-mentioned physical properties cannot be achieved without considering the Tg of the thermosetting resin to be mixed. Therefore, in the present invention, by setting the Tg of each of the ionizing radiation-curable resin and the thermosetting resin to 90 ° C. or more, the above-described impact resistance and adhesion can be maintained, and the surface hardness and stain resistance can be maintained. Thus, the overall properties of the coating film could be improved.
[Brief description of the drawings]
FIG. 1 is a sheet configuration according to the present invention.
[Explanation of symbols]
P ・ ・ Primer layer O ・ ・ Olefin-based sheet D ・ ・ Printing C ・ ・ Clear resin T ・ ・ Top coat layer
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP2003113207A JP2004314498A (en) | 2003-04-17 | 2003-04-17 | Decorative sheet |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003113207A JP2004314498A (en) | 2003-04-17 | 2003-04-17 | Decorative sheet |
Publications (1)
Publication Number | Publication Date |
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JP2004314498A true JP2004314498A (en) | 2004-11-11 |
Family
ID=33473206
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP2003113207A Pending JP2004314498A (en) | 2003-04-17 | 2003-04-17 | Decorative sheet |
Country Status (1)
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JP (1) | JP2004314498A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013067099A (en) * | 2011-09-22 | 2013-04-18 | Dainippon Printing Co Ltd | Decorative board and method of manufacturing the same |
JP2016093968A (en) * | 2014-11-17 | 2016-05-26 | 株式会社トッパン・コスモ | Decorative sheet |
JP2017019113A (en) * | 2015-07-07 | 2017-01-26 | 凸版印刷株式会社 | Decorative sheet and decorative plate |
JP2017024201A (en) * | 2015-07-16 | 2017-02-02 | 凸版印刷株式会社 | Decorative sheet and decorative panel |
JP2017024202A (en) * | 2015-07-16 | 2017-02-02 | 凸版印刷株式会社 | Decorative sheet and decorative panel |
-
2003
- 2003-04-17 JP JP2003113207A patent/JP2004314498A/en active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013067099A (en) * | 2011-09-22 | 2013-04-18 | Dainippon Printing Co Ltd | Decorative board and method of manufacturing the same |
JP2016093968A (en) * | 2014-11-17 | 2016-05-26 | 株式会社トッパン・コスモ | Decorative sheet |
JP2017019113A (en) * | 2015-07-07 | 2017-01-26 | 凸版印刷株式会社 | Decorative sheet and decorative plate |
JP2017024201A (en) * | 2015-07-16 | 2017-02-02 | 凸版印刷株式会社 | Decorative sheet and decorative panel |
JP2017024202A (en) * | 2015-07-16 | 2017-02-02 | 凸版印刷株式会社 | Decorative sheet and decorative panel |
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