JP3923332B2 - Decorative sheet - Google Patents
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- JP3923332B2 JP3923332B2 JP2002036375A JP2002036375A JP3923332B2 JP 3923332 B2 JP3923332 B2 JP 3923332B2 JP 2002036375 A JP2002036375 A JP 2002036375A JP 2002036375 A JP2002036375 A JP 2002036375A JP 3923332 B2 JP3923332 B2 JP 3923332B2
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Description
【0001】
【発明の属する技術分野】
この発明は、装飾用シートに関し、更に詳しくは、従来にない柔軟な風合いと耐候性と耐衝撃性とを有し、その表面於ける耐スクラッチ性、耐薬品性に優れ、後加工に於ける折り曲げ時に白化せず、その柔軟性の故に3次元曲面への追従性に優れ、PVCの代替としての使用が可能であって、しかも着色性、印刷性、接着性に優れ、可塑剤等のブリードもない装飾用シートに関するものである。
【0002】
【従来の技術】
近年、塩化ビニル(PVC)は環境保護の観点から好ましくないため、非塩素化材料への代替が求められるようになってきている。非塩素化材料としては、特に経済性や安全性を考慮して、ポリエチレン、ポリプロピレン、熱可塑性オレフィン(TPO)等のポリオレフィン系樹脂が有力視されている。しかしながら、フィルムの柔軟性、透明性、耐候性等の性能に於いてPVCには及ばないのが実状である。特に、ポリオレフィンフィルムの三次曲面追従性は、PVCと比較すると、延伸時に白化が生じ、延伸後の回復性が悪く、ネッキングが生じ易いなど、現時点ではPVCの代替材料として満足なものはない。
【0003】
装飾用シートとしては、オレフィンフィルムを用いたものが多数製品化され、例えば耐候性及び耐薬品性を改良するためにフッ化ビニリデン樹脂とアクリル樹脂のブレンドフィルムの表面保護層にポリプロピレン又はABS樹脂からなる基材層を積層したシート(特開2001−71428号公報)がある。しかし、この積層シートは柔軟性という点では不十分であり、後加工方法も平張りに近いものであり、3次元曲面張等の特殊な用途には使用できない。この3次元曲面へフィルムをラミネートする場合は、80℃前後の熱をかけた状態でフィルムを引っ張りながら行う。しかし、従来のオレフィン、ABS基材では、熱量が不十分な場合には伸び難く、逆に局所的に加熱された場合には一部分だけがネッキング又は伸びてフィルムが薄くなったりする等、問題が多かった。
【0004】
そこで、基材フィルムとして、非常に加工性に優れた配合からなるアクリルフィルムを使用することが考えられる。アクリル樹脂は優れた機械的特性及び化学的性質を有し、透明性、耐候性、硬度の点で優れることから有機ガラスとして従来より使用され、照明カバー、屋外用の看板等、様々な分野に使用されている。また、人体に悪影響を及ぼす物質を含まないことから、医療器具としても広く使用されている。近年、特に焼却時にダイオキシン発生の虞がある塩化ビニル系樹脂が避けられる傾向があることから、PVCに代わる材料として注目を集めている。
【0005】
【発明が解決しようとする課題】
しかしながら、アクリル樹脂そのものでは非常に硬く、フィルム又はシート状に加工すると割れ易く、延伸性にも劣る。一部の製品には、厚物シート用としてゴム成分を含むアクリル樹脂を使用したものもあったが、200μm以下のフィルム状又はシート状に加工すると白化するか、柔軟性に乏しいために軟質PVCのような風合いは得られず、強度、加工性の点に於いても満足なものは存在しなかった。また、アクリル樹脂は耐薬品性及び耐スクラッチ性にやや劣ることも欠点としてあげられる。このように、PVCの風合いに似た柔軟なフィルム又はシートはこれまで存在せず、硬さ、割れ、白化等の点から3次元曲面への満足な加工性を有するものも存在しないのが実状である。
【0006】
本発明は、上記の問題を解決するために為されたものであり、本発明の目的は、非PVCでありながらPVCのような柔軟な風合いを有し、耐スクラッチ性、耐候性、耐薬品性等の点で優れ、後加工で折り曲げ時に白化せず、3次元曲面への追従性に優れた柔軟な加工適性を有する装飾用シートを提供することである。
【0007】
【課題を解決するための手段】
上記の問題を解決するために、本発明は、基材層として柔軟性に富むアクリル系樹脂を使用し、硬度、耐スクラッチ性、耐磨耗性、耐薬品性等に優れるポリフッ化ビニリデン樹脂とアクリル樹脂のブレンドからなる表面保護層を基材層上に積層することにより、優れた装飾用シートが得られることを見出し、完成するに至ったものである。
【0008】
即ち、本発明の装飾用シートは、アクリル系樹脂を含有する基材層に、フッ化ビニリデン樹脂及びアクリル系樹脂を含有する表面保護層を積層したことを特徴とする。
【0009】
なお、本明細書に於いて、「シート」とは「フィルム」をも含む概念をいう。
【0010】
また、本発明の装飾用シートは、上記構成に於いて、前記基材層と前記表面保護層との間に、必要に応じて、着色層、印刷層、接着剤層及び粘着剤層からなる群から選択される機能層を設けることもできる。
【0011】
また、前記基材層が、メタクリル酸メチル−アクリル酸アルキル共重合体Aと、メタクリル酸メチル−アクリル酸アルキル−スチレン共重合体Bとを含有している構成を採用することが可能である。
【0012】
上記の場合に於いて、前記基材層には、前記共重合体Aと前記共重合体Bとの合計100重量部に対して50重量部以下の可塑剤を配合することができる。
【0013】
前記可塑剤としては、ポリエステル系可塑剤、具体的には、化2の一般式(I)で示されるアジピン酸系ポリエステル(化2に於いて、Rは、n−オクチル基、イソノニル基、2−エチルキシル基及びこれらの基を混合したものからなる群から選択される基である。)を用いることができる。
【0014】
【化2】
【0015】
前記可塑剤として、アクリル系可塑剤を用いることもできる。
【0016】
【発明の実施の形態】
以下、本発明の実施の形態について説明する。
【0017】
本発明に於ける基材層としては、耐候性に優れるアクリル系樹脂が使用される。アクリル系樹脂としては、例えば、メタクリル酸メチル−アクリル酸アルキル共重合体Aとメタクリル酸メチル−アクリル酸アルキル−スチレン共重合体Bとをブレンドしたものが好適に用いられる。
【0018】
メタクリル酸メチル−アクリル酸アルキル共重合体A単体では硬度が高すぎ、シート状に加工しても延伸性が低いため非常に割れ易いが、アクリル系のゴム成分であるメタクリル酸メチル−アクリル酸アルキル−スチレン共重合体Bを配合することにより、シートの柔軟性が増し、折り曲げ時の白化が抑制される。また、本発明に於ける基材層は、押し出し成型又はカレンダー成型が可能となっている。
【0019】
上記の成分を含有する基材層のみでも柔軟な装飾用シートを得ることができるが、更に柔軟性を向上させ、PVCのような風合いを発現させるためには、可塑剤を基材層の構成成分として添加することが好ましい。
【0020】
柔軟性、風合い(ドレープ性)、延伸性等の物性を発現させるためには、上記の共重合体Aと共重合体Bとの合計100重量部に対して、50重量部以下の可塑剤を配合することが好ましい。これにより、PVCの風合いを備えながら、PVC以上の耐候性等の性能を有する装飾用シートを得ることができる。また、このようにして得られる基材層は、ポリオレフィンやアクリロニトリル−ブタジエン−スチレン共重合体(ABS)よりも柔軟性優れているため、従来の装飾用シートよりも3次元曲面への追従性に優れたものとなる。
【0021】
可塑剤としては、内分泌撹乱物質(環境ホルモン)等としての疑いのないポリエステル系のものが望ましい。更にポリエステル系可塑剤のうち、化2の一般式(I)に示すようなアジピン酸系ポリエステルが、シートからのブリードの少ない優れた可塑化性能を発揮するという点で好ましい。中でも、化2に於いて、Rがn−オクチル、イソノニル基、2−エチルヘキシル基及びこれらの基を混合したものからなる群から選択される基であるものが好適に使用される。また、上記可塑剤は、同様に内分泌撹乱物質(環境ホルモン)等の疑いのないアクリル系可塑剤から選んでもよい。
【0022】
本発明に於ける表面保護層は、フッ化ビニリデン樹脂とアクリル樹脂とを含有している。耐薬品性及び耐スクラッチ性に優れたフッ化ビニリデン樹脂と、基材層に積層する際の接着性を発現するアクリル樹脂とをブレンドすることにより、耐薬品性及び耐スクラッチ性と接着性とを両立させた表面保護層を得ることができる。本発明に於いては、基材層がアクリル系樹脂であるため、ポリオレフィンやABSを基材層として用いたシートよりも、基材層と表面保護層との接着性は優れたものとなる。
【0023】
また、本発明に於いては、基材層の表面保護層を積層する側に、必要に応じて、着色層、印刷層、接着剤層、粘着剤層等の機能層を設けることが可能であり、種々の意匠を付加したり、種々の機能を付加することが可能となる。
【0024】
本発明の基材層には、上記アクリル系樹脂、可塑剤の他に、酸化防止剤、紫外線吸収剤、滑剤、顔料等の一般に樹脂に添加される公知の添加剤を適量添加することができる。
【0025】
【実施例】
(実施例)
メタクリル酸メチル−アクリル酸アルキル共重合体A(商品名:パラペットHR−A、クラレ株式会社製)を50重量部と、メタクリル酸メチル−アクリル酸アルキル−スチレン共重合体B(商品名:メタブレンW341、三菱レイヨン株式会社製)を50重量部(メルトフローレート(MFR)=1)と、酸化防止剤としてアンチオクス10(日本油脂社製)を1重量部と、安定剤としてステアリン酸カルシウムを0.2重量部及びステアリン酸亜鉛を0.2重量部と、滑剤としてLS−5(旭電化製)を1重量部と、紫外線吸収剤としてバイオソープ583(住友化学製)を0.5重量部とを、バンバリーミキサーで溶融混錬後、カレンダー本体の各ロールに通し、厚みが0.08mmのフィルムを作製した。このフィルムに、フッ化ビニリデン樹脂とアクリル樹脂のブレンドからなるフィルム(電気化学工業株式会社製)のラミネート面にホットメルト接着剤を塗布したものをドライラミネートすることにより、本実施例の装飾用シートを作製した。
【0026】
(比較例1)
メタクリル酸メチル−アクリル酸アルキル共重合体(商品名:パラペットHR−A、クラレ株式会社製)を50重量部と、メタクリル酸メチル−アクリル酸アルキル−スチレン共重合体B(商品名:メタブレンW341、三菱レイヨン株式会社製)を50重量部(メルトフローレート(MFR)=1)と、酸化防止剤としてアンチオクス10(日本油脂社製)を1重量部と、安定剤としてステアリン酸カルシウムを0.2重量部及びステアリン酸亜鉛を0.2重量部と、滑剤としてLS−5(旭電化製)を1重量部と、紫外線吸収剤としてバイオソープ583(住友化学製)を0.5重量部とを、バンバリーミキサーで溶融混錬後、カレンダー本体の各ロールを通して厚みが0.08mmのフィルム単層を作製し、これを比較例1の装飾用シートとした。
【0027】
(比較例2)
ランダムポリプロピレン樹脂(商品名:ジェイアロマーPM620A、日本ポリオレフィン株式会社製)を100重量部と、安定剤としてアデカスタブ2112(旭電化工業株式会社製)を0.3重量部と、酸化防止剤としてアンチオクス10(日本油脂製)を0.2重量部と、滑剤としてEW−K8391(Henkel社製)0.1重量部とを、バンバリーミキサーで混錬後、カレンダーにて0.08mmのフィルムを作製した。このフィルムに、フッ化ビニリデン樹脂とアクリル樹脂のブレンドからなるフィルム(電気化学工業株式会社製)のラミネート面にホットメルト接着剤を塗布したものをドライラミネートすることにより、比較例2の装飾用シートを作製した。
【0028】
(比較例3(PVC))
内部可塑軟質ウレタン/塩化ビニル系共重合樹脂(バンドー化学製)100重量部に対して、Ba−Zn系安定剤を1.5重量部と、酸化チタンを15重量部とを混合したコンパウンドを作製した。このコンパウンドをカレンダーに通して、厚み80μmのフィルムを得た。これとは別に、塩化ビニル樹脂100重量部に対してDOP可塑剤を30重量部と、Ba−Zn系安定剤を1.5重量部と、ガラス繊維を5重量部と、加工助剤を1.5重量部とを混合したコンパウンドを作製した。このコンパウンドをカレンダーにて80μmのフィルムを作製した。次に、上記2種類のフィルムを熱融着して、比較例3の装飾用シートを作製した。
【0029】
上記の実施例及び各比較例の装飾用シートについて、耐スクラッチ性、温度依存性及び貼り施工性について試験を行いその結果を表1に示した。また、貼り加工時に生じる問題点を表1に併せて示した。
【0030】
耐スクラッチ性の試験は、1mmのアルミ板に各装飾用シートを貼り付けたものを使用し、JIS K5400による鉛筆引っかき試験により行った。温度依存性試験は、各フィルムを低温(5℃)から常温23℃までのシートの硬さを評価することにより行った。また、貼り施工性試験は、80℃のドライヤーを使用して貼り加工を行った場合の張りやすさを評価した。
【0031】
【表1】
【0032】
上記試験の結果、フッ化ビニリデン樹脂とアクリル樹脂のブレンドからなるフィルムを貼り合わせていない比較例1の装飾用シートでは、耐スクラッチ性が極端に低かった。また、基材層にポリプロピレン樹脂を用いた比較例2の装飾用シートでは、シート自体が低温で硬くなり、貼り加工時に白化及びネッキングを生じるという問題点があった。これに対して、実施例の装飾用シートは低温で硬くなったり、貼り加工時に白化及びネッキングを生じることもなく、従来のPVCからなる比較例3の装飾用シートよりも高い耐スクラッチ性を示すことが分かる。
【0033】
【発明の効果】
本発明の装飾用シートは、高温から低温に亘って従来にない柔軟な風合いを示し、耐候性と耐衝撃性に優れている。また、その表面は耐スクラッチ性、耐薬品性に優れ、後加工に於ける折り曲げ時にも白化しない。また、その柔軟性の故に3次元曲面への追従性に優れ、PVCの代替としての使用が可能である。しかも、着色性、印刷性、接着性に優れ、可塑剤等のブリードも生じない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative sheet, and more specifically, has an unprecedented soft texture, weather resistance and impact resistance, and has excellent scratch resistance and chemical resistance on the surface thereof, and in post-processing. It does not whiten when bent, and because of its flexibility, it has excellent followability to 3D curved surfaces, can be used as an alternative to PVC, and has excellent colorability, printability, and adhesiveness, and bleed such as plasticizers. The present invention relates to a decorative sheet.
[0002]
[Prior art]
In recent years, since vinyl chloride (PVC) is not preferable from the viewpoint of environmental protection, an alternative to a non-chlorinated material has been demanded. As non-chlorinated materials, polyolefin resins such as polyethylene, polypropylene, and thermoplastic olefin (TPO) are considered to be prominent particularly in consideration of economy and safety. However, in reality, the film performance is not as good as that of PVC in terms of performance such as flexibility, transparency, and weather resistance. In particular, the third-order curved surface followability of a polyolefin film is not satisfactory as a substitute material for PVC at present, such as whitening occurs during stretching, recovery after stretching is poor, and necking is likely to occur.
[0003]
Many decorative sheets using olefin films have been commercialized. For example, in order to improve weather resistance and chemical resistance, polypropylene or ABS resin is used as the surface protective layer of the blend film of vinylidene fluoride resin and acrylic resin. There is a sheet (Japanese Patent Laid-Open No. 2001-71428) on which a base material layer is laminated. However, this laminated sheet is insufficient in terms of flexibility, and the post-processing method is close to flat tension, and cannot be used for special applications such as three-dimensional curved surface tension. When laminating a film on this three-dimensional curved surface, it is carried out while pulling the film in a state where heat of about 80 ° C. is applied. However, with conventional olefin and ABS base materials, it is difficult to stretch when the amount of heat is insufficient, and conversely, when locally heated, only a part of the material is necked or stretched, resulting in a thin film. There were many.
[0004]
Therefore, it is conceivable to use an acrylic film having a composition with very excellent processability as the base film. Acrylic resin has excellent mechanical properties and chemical properties, and has been used as an organic glass from the viewpoint of transparency, weather resistance, and hardness, and has been used in various fields such as lighting covers and outdoor signboards. in use. In addition, since it does not contain substances that adversely affect the human body, it is also widely used as a medical instrument. In recent years, vinyl chloride-based resins that may cause dioxin generation during incineration tend to be avoided, and thus has attracted attention as a substitute for PVC.
[0005]
[Problems to be solved by the invention]
However, the acrylic resin itself is very hard, is easily broken when processed into a film or sheet, and has poor stretchability. Some products used an acrylic resin containing a rubber component for thick sheets, but when processed into a film or sheet of 200 μm or less, it was whitened or soft PVC due to lack of flexibility. Such a texture was not obtained, and no satisfactory one was found in terms of strength and workability. Another disadvantage is that acrylic resins are slightly inferior in chemical resistance and scratch resistance. Thus, there has been no flexible film or sheet that resembles the texture of PVC, and there is no film or sheet that has satisfactory processability to a three-dimensional curved surface in terms of hardness, cracking, whitening, and the like. It is.
[0006]
The present invention has been made to solve the above-mentioned problems, and the object of the present invention is to have a soft texture like PVC while being non-PVC, and to have scratch resistance, weather resistance, and chemical resistance. It is an object of the present invention to provide a decorative sheet having excellent flexibility and suitability to follow a three-dimensional curved surface, which is excellent in terms of properties and the like, does not whiten when bent in post-processing.
[0007]
[Means for Solving the Problems]
In order to solve the above problems, the present invention uses a polyvinylidene fluoride resin excellent in hardness, scratch resistance, abrasion resistance, chemical resistance, and the like, using a flexible acrylic resin as a base material layer. It has been found that an excellent decorative sheet can be obtained by laminating a surface protective layer made of an acrylic resin blend on a base material layer, and has been completed.
[0008]
That is, the decorative sheet of the present invention is characterized in that a surface protective layer containing a vinylidene fluoride resin and an acrylic resin is laminated on a base material layer containing an acrylic resin.
[0009]
In this specification, “sheet” refers to a concept including “film”.
[0010]
Moreover, the decorative sheet of the present invention has a colored layer, a printed layer, an adhesive layer, and an adhesive layer between the base material layer and the surface protective layer, if necessary, in the above configuration. A functional layer selected from the group can also be provided.
[0011]
Moreover, it is possible to employ | adopt the structure in which the said base material layer contains the methyl methacrylate-alkyl acrylate copolymer A and the methyl methacrylate-alkyl acrylate-styrene copolymer B.
[0012]
In the above case, the base material layer may contain 50 parts by weight or less of a plasticizer with respect to a total of 100 parts by weight of the copolymer A and the copolymer B.
[0013]
Examples of the plasticizer include polyester-based plasticizers, specifically, adipic acid-based polyester represented by the general formula (I) of Chemical Formula 2 (in Chemical Formula 2, R is an n-octyl group, isononyl group, 2 -A group selected from the group consisting of an ethylxyl group and a mixture of these groups).
[0014]
[Chemical 2]
[0015]
An acrylic plasticizer can also be used as the plasticizer.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
[0017]
As the base material layer in the present invention, an acrylic resin having excellent weather resistance is used. As the acrylic resin, for example, a blend of methyl methacrylate-alkyl acrylate copolymer A and methyl methacrylate-alkyl acrylate-styrene copolymer B is suitably used.
[0018]
The methyl methacrylate-alkyl acrylate copolymer A alone is too high in hardness, and even if processed into a sheet, it is very easy to break because of its low stretchability. However, methyl methacrylate-alkyl acrylate is an acrylic rubber component. -By mix | blending the styrene copolymer B, the softness | flexibility of a sheet | seat increases and whitening at the time of bending is suppressed. Further, the base material layer in the present invention can be extruded or calendered.
[0019]
A flexible decorative sheet can be obtained with only the base material layer containing the above components. However, in order to further improve the flexibility and develop a texture like PVC, a plasticizer is used as the base material layer. It is preferable to add it as a component.
[0020]
In order to express physical properties such as flexibility, texture (drapability) and stretchability, a plasticizer of 50 parts by weight or less is added to 100 parts by weight of the total of copolymer A and copolymer B described above. It is preferable to mix. Thereby, it is possible to obtain a decorative sheet having performance such as weather resistance higher than that of PVC while having a PVC texture. Moreover, since the base material layer obtained in this way is superior in flexibility to polyolefin and acrylonitrile-butadiene-styrene copolymer (ABS), it can follow a three-dimensional curved surface more than a conventional decorative sheet. It will be excellent.
[0021]
As the plasticizer, a polyester-based one that is not suspected as an endocrine disrupting substance (environmental hormone) is desirable. Further, among the polyester plasticizers, adipic acid polyesters represented by the general formula (I) of Chemical Formula 2 are preferable in that they exhibit excellent plasticizing performance with little bleeding from the sheet. Among them, in Chemical Formula 2, those in which R is a group selected from the group consisting of n-octyl, isononyl group, 2-ethylhexyl group and a mixture of these groups are preferably used. Similarly, the plasticizer may be selected from acrylic plasticizers that are not suspected of endocrine disrupting substances (environmental hormones).
[0022]
The surface protective layer in the present invention contains a vinylidene fluoride resin and an acrylic resin. By blending vinylidene fluoride resin with excellent chemical resistance and scratch resistance and acrylic resin that exhibits adhesiveness when laminated on the base material layer, chemical resistance, scratch resistance and adhesiveness are achieved. A compatible surface protective layer can be obtained. In the present invention, since the base material layer is an acrylic resin, the adhesion between the base material layer and the surface protective layer is superior to a sheet using polyolefin or ABS as the base material layer.
[0023]
In the present invention, a functional layer such as a colored layer, a printing layer, an adhesive layer, or a pressure-sensitive adhesive layer can be provided on the side of the base material layer on which the surface protective layer is laminated, if necessary. Yes, various designs can be added and various functions can be added.
[0024]
In addition to the acrylic resin and plasticizer, an appropriate amount of known additives generally added to the resin, such as antioxidants, ultraviolet absorbers, lubricants, and pigments, can be added to the base material layer of the present invention. .
[0025]
【Example】
(Example)
50 parts by weight of methyl methacrylate-alkyl acrylate copolymer A (trade name: Parapet HR-A, manufactured by Kuraray Co., Ltd.) and methyl methacrylate-alkyl acrylate-styrene copolymer B (trade name: methabrene W341) 50 parts by weight (manufactured by Mitsubishi Rayon Co., Ltd.) (melt flow rate (MFR) = 1), 1 part by weight of ANTIOX 10 (manufactured by NOF Corporation) as an antioxidant, and 0.2 parts of calcium stearate as a stabilizer. 0.2 parts by weight of zinc stearate, 1 part by weight of LS-5 (Asahi Denka) as a lubricant, and 0.5 parts by weight of Biosoap 583 (Sumitomo Chemical) as an ultraviolet absorber After melt-kneading with a Banbury mixer, the film was passed through each roll of the calendar body to produce a film having a thickness of 0.08 mm. A decorative sheet of this embodiment is obtained by dry laminating a film made of a blend of vinylidene fluoride resin and acrylic resin (manufactured by Denki Kagaku Kogyo Co., Ltd.) with a hot melt adhesive applied to this film. Was made.
[0026]
(Comparative Example 1)
50 parts by weight of methyl methacrylate-alkyl acrylate copolymer (trade name: Parapet HR-A, manufactured by Kuraray Co., Ltd.) and methyl methacrylate-alkyl acrylate-styrene copolymer B (trade name: methabrene W341, 50 parts by weight (manufactured by Mitsubishi Rayon Co., Ltd.) (melt flow rate (MFR) = 1), 1 part by weight of ANTIOX 10 (manufactured by NOF Corporation) as an antioxidant, and 0.2 parts by weight of calcium stearate as a stabilizer 0.2 parts by weight of zinc stearate, 1 part by weight of LS-5 (manufactured by Asahi Denka) as a lubricant, and 0.5 parts by weight of biosoap 583 (manufactured by Sumitomo Chemical) as an ultraviolet absorber, After melt-kneading with a Banbury mixer, a film single layer having a thickness of 0.08 mm is produced through each roll of the calendar body, and this is used as a decorative sheet of Comparative Example 1. It was.
[0027]
(Comparative Example 2)
100 parts by weight of a random polypropylene resin (trade name: J-Aroma PM620A, manufactured by Nippon Polyolefin Co., Ltd.), 0.3 parts by weight of Adeka Stub 2112 (manufactured by Asahi Denka Kogyo Co., Ltd.) as a stabilizer, and ANTIOX 10 as an antioxidant After kneading 0.2 parts by weight (manufactured by NOF Corporation) and 0.1 parts by weight of EW-K8391 (manufactured by Henkel) as a lubricant with a Banbury mixer, a 0.08 mm film was produced with a calendar. A decorative sheet of Comparative Example 2 is obtained by dry laminating a film (made by Denki Kagaku Kogyo Co., Ltd.) on which a hot melt adhesive is applied to a laminate of a vinylidene fluoride resin and an acrylic resin. Was made.
[0028]
(Comparative Example 3 (PVC))
A compound is prepared by mixing 1.5 parts by weight of a Ba-Zn stabilizer and 15 parts by weight of titanium oxide with 100 parts by weight of an internal plastic soft urethane / vinyl chloride copolymer resin (manufactured by Bando Chemical). did. This compound was passed through a calendar to obtain a film having a thickness of 80 μm. Separately, 30 parts by weight of DOP plasticizer, 1.5 parts by weight of Ba-Zn stabilizer, 5 parts by weight of glass fiber, and 1 processing aid for 100 parts by weight of vinyl chloride resin. A compound was prepared by mixing 5 parts by weight. An 80 μm film was prepared from this compound using a calendar. Next, the two types of films were heat-sealed to produce a decorative sheet of Comparative Example 3.
[0029]
The decorative sheets of the above Examples and Comparative Examples were tested for scratch resistance, temperature dependency and pasting workability, and the results are shown in Table 1. In addition, Table 1 also shows problems that occur during pasting.
[0030]
The scratch resistance test was performed by a pencil scratch test according to JIS K5400 using a 1 mm aluminum plate with each decorative sheet attached. The temperature dependency test was performed by evaluating the hardness of the sheet from a low temperature (5 ° C.) to a normal temperature of 23 ° C. for each film. Moreover, the pasting workability test evaluated the ease of tension when pasting was performed using a dryer at 80 ° C.
[0031]
[Table 1]
[0032]
As a result of the above test, in the decorative sheet of Comparative Example 1 in which a film made of a blend of vinylidene fluoride resin and acrylic resin was not bonded, the scratch resistance was extremely low. Further, the decorative sheet of Comparative Example 2 using a polypropylene resin for the base material layer has a problem that the sheet itself becomes hard at a low temperature, and whitening and necking occur during the pasting process. On the other hand, the decorative sheet of the example does not become hard at low temperature and does not cause whitening and necking at the time of pasting, and exhibits higher scratch resistance than the decorative sheet of Comparative Example 3 made of conventional PVC. I understand that.
[0033]
【The invention's effect】
The decorative sheet of the present invention exhibits an unprecedented flexible texture from high temperature to low temperature and is excellent in weather resistance and impact resistance. In addition, its surface is excellent in scratch resistance and chemical resistance, and does not whiten when bent in post-processing. In addition, because of its flexibility, it has excellent followability to a three-dimensional curved surface and can be used as an alternative to PVC. And it is excellent in coloring property, printability, and adhesiveness, and bleeding such as plasticizer does not occur.
Claims (3)
前記基材層には、化1の一般式(I)で示されるアジピン酸系ポリエステル(化1に於いて、Rは、n−オクチル基、イソノニル基、2−エチルキシル基及びこれらの基を混合したものからなる群から選択される基である。)が可塑剤として配合されていることを特徴とする装飾用シート。
In the base material layer, an adipic acid-based polyester represented by the general formula (I) of Chemical Formula 1 (In Chemical Formula 1, R is an n-octyl group, an isononyl group, a 2-ethylxyl group, and a mixture thereof. Is a group selected from the group consisting of: a plasticizer and a decorative sheet.
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JP2005343003A (en) * | 2004-06-02 | 2005-12-15 | Bando Chem Ind Ltd | Decorative sheet and its manufacturing method |
US8034441B2 (en) * | 2005-07-08 | 2011-10-11 | Arkema France | Multilayer composition |
JP2007050590A (en) * | 2005-08-17 | 2007-03-01 | Sony Corp | Method for cleaning liquid jet head |
JP5987691B2 (en) * | 2011-09-12 | 2016-09-07 | 三菱レイヨン株式会社 | Laminated film and laminated molded product |
JP6361741B2 (en) | 2015-09-11 | 2018-07-25 | 三菱ケミカル株式会社 | Laminated film and laminated molded product |
CN110506090B (en) | 2017-04-13 | 2022-05-31 | 王子控股株式会社 | Adhesive sheet for decorative molding |
US11173693B2 (en) | 2017-11-28 | 2021-11-16 | Denka Company Limited | Vinylidene fluoride-based resin multi-layered film |
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JPH02166148A (en) * | 1988-12-20 | 1990-06-26 | Bando Chem Ind Ltd | Acrylic resin composition |
JPH06107814A (en) * | 1992-09-30 | 1994-04-19 | Okamoto Ind Inc | Agricultural synthetic resin film |
US5538770A (en) * | 1994-11-18 | 1996-07-23 | W. R. Grace & Co. -Conn. | Vinylidene chloride film with controlled gas permeability |
JP2000102950A (en) * | 1998-09-30 | 2000-04-11 | Kansai Paint Co Ltd | Decorative film for molding plastic and injection-molded article obtained by using the film |
JP4197205B2 (en) * | 1998-12-17 | 2008-12-17 | 旭化成ケミカルズ株式会社 | Methacrylic resin composition using acrylic multilayer polymer |
JP4580066B2 (en) * | 2000-07-10 | 2010-11-10 | 株式会社クレハ | Fluororesin laminate and molded body comprising the same |
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