JPH0550566A - Production of vinylidene fluoride resin type composite film - Google Patents
Production of vinylidene fluoride resin type composite filmInfo
- Publication number
- JPH0550566A JPH0550566A JP3206145A JP20614591A JPH0550566A JP H0550566 A JPH0550566 A JP H0550566A JP 3206145 A JP3206145 A JP 3206145A JP 20614591 A JP20614591 A JP 20614591A JP H0550566 A JPH0550566 A JP H0550566A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- vinylidene fluoride
- film
- fluoride resin
- 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.)
- Granted
Links
Landscapes
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、耐候性、耐汚染性及び
耐溶剤性に優れ、かつ、プラスチック、ゴムその他の基
材との接着性の改良されたフッ化ビニリデン樹脂とメタ
クリル酸エステル系樹脂とを主成分とするフッ化ビニリ
デン樹脂系複合フィルムの製造方法に関するものであ
る。FIELD OF THE INVENTION The present invention relates to a vinylidene fluoride resin and a methacrylic acid ester-based resin having excellent weather resistance, stain resistance and solvent resistance, and improved adhesion to plastics, rubber and other substrates. The present invention relates to a method for producing a vinylidene fluoride resin-based composite film containing a resin as a main component.
【0002】[0002]
【従来の技術】近年屋内外装用部材の表面保護フィルム
としてポリ塩化ビニル系、ポリメタクリル酸エステル
系、およびポリフッ素系フィルム等が各種塗料とともに
使用されている。これら保護フィルムの用途は、壁紙や
エレベーター、車輌等の内装用のほか屋根材、壁材、雨
どい、ガレージの屋根、サンルーム、農業用資材、看
板、標識、ラベル、窓ガラス用等その優れた耐候性等を
生かして多岐にわたっている。ところで前記した3種類
の素材をベースとした保護フィルムは、それぞれの価
格、特性等によって、いろいろな用途に使いわけされて
いるが、価格面では前者ほど安価であり、一方特性面で
は後者ほど耐候性が優れている。2. Description of the Related Art In recent years, polyvinyl chloride-based films, polymethacrylic acid ester-based films, polyfluorine-based films and the like have been used as a surface protective film for interior and exterior members together with various coating materials. These protective films are used for wallpaper, elevators, interiors such as vehicles, roof materials, wall materials, rain gutters, garage roofs, solariums, agricultural materials, signs, signs, labels, window glass, etc. It has a wide range of properties, making the most of its weather resistance. By the way, the above-mentioned protective films based on three types of materials are used for various purposes depending on their prices, characteristics, etc., but in terms of price, the former is cheaper, while the latter is weatherproof. It has excellent properties.
【0003】またこれら保護フィルムの貼り合わせの対
象基材は、ポリ塩化ビニル、ポリカーボネート、ポリメ
タクリル酸メチル、アクリロニトリル−ブタジエン−ス
チレン共重合体、FRP 等のプラスチック基材の他、EPD
M、CSM その他のゴム基材、アルミニウム箔、鋼板等の
金属のほか、合板、ガラス等と幅広い。Substrates to which these protective films are attached are not only plastic substrates such as polyvinyl chloride, polycarbonate, polymethylmethacrylate, acrylonitrile-butadiene-styrene copolymer and FRP but also EPD.
In addition to M, CSM and other rubber substrates, metals such as aluminum foil and steel plates, it also has a wide range of plywood and glass.
【0004】[0004]
【発明が解決しようとする課題】しかしこれら3種類の
素材フィルムの中で、ポリフッ素系フィルムは、前記耐
候性のほか耐汚染性、強度面で他の2者よりもはるかに
優れた性能を有する反面、基材との接着性に劣るという
欠点を有する。However, among these three kinds of material films, the polyfluorine-based film has much higher performance than the other two in terms of weather resistance, stain resistance and strength. On the other hand, it has the drawback of being poor in adhesiveness to the substrate.
【0005】従って、ポリ塩化ビニル系およびポリメタ
クリル酸エステル系フィルムでは、用途によって熱接着
方式を採用しているのに対して、ポリフッ素系フィルム
では、すべて接着剤を使用した接着方式となり、この点
でも価格的に高価となり、そのすぐれた耐候性や耐汚染
性を十分生かしきれず、この熱接着性の付与が強く要望
されているのが現状である。Therefore, the polyvinyl chloride-based film and the polymethacrylic acid ester-based film adopt the heat-bonding method depending on the application, while the polyfluorine-based film uses the adhesive method in which the adhesive method is used. Also in terms of price, the price is high, and the excellent weather resistance and stain resistance cannot be fully utilized, and there is a strong demand for the provision of this thermal adhesiveness.
【0006】本発明は、フッ化ビニリデン樹脂からなる
フィルムの接着性を改良したものであり、フッ化ビニリ
デン樹脂とメタクリル酸エステル系樹脂との複合フィル
ム又は混合比を異にする2種類のフィルムを用いること
により耐候性、耐汚染性及び耐溶剤性に優れ、被接着基
材との接着性も良好なフッ化ビニリデン樹脂系複合フィ
ルムの製造方法を提供するものである。The present invention is to improve the adhesiveness of a film made of vinylidene fluoride resin, and to form a composite film of vinylidene fluoride resin and methacrylic acid ester resin or two kinds of films having different mixing ratios. It is intended to provide a method for producing a vinylidene fluoride resin-based composite film which is excellent in weather resistance, stain resistance and solvent resistance by using, and also has good adhesiveness to a substrate to be adhered.
【0007】[0007]
【課題を解決するための手段】すなわち本発明は、フッ
化ビニリデン樹脂 100〜50重量部とメタクリル酸エステ
ル系樹脂0〜50重量部とを成分とするA層と、フッ化ビ
ニリデン樹脂0〜65重量部とメタクリル酸エステル系樹
脂 100〜35重量部とを成分とするB層とから構成される
複合フィルムを溶融押出して一体に結合してなる事を特
徴とするフッ化ビニリデン樹脂系複合フィルムの製造方
法である。Means for Solving the Problems That is, the present invention provides an A layer containing 100 to 50 parts by weight of a vinylidene fluoride resin and 0 to 50 parts by weight of a methacrylic acid ester resin, and a vinylidene fluoride resin of 0 to 65 parts by weight. A vinylidene fluoride resin-based composite film, characterized in that a composite film comprising a B layer containing 100 parts by weight of methacrylic acid ester resin and 100 to 35 parts by weight of a methacrylic acid ester resin is melt-extruded and integrally bonded. It is a manufacturing method.
【0008】本発明で使用するフッ化ビニリデン樹脂と
は、フッ化ビニリデンのホモポリマー、又はフッ化ビニ
リデンと共重合可能な単量体との共重合体をいう。共重
合可能な単量体としては、例えばフッ化ビニル、四フッ
化エチレン、三フッ化塩化エチレンなどがある。The vinylidene fluoride resin used in the present invention is a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride and a copolymerizable monomer. Examples of the copolymerizable monomer include vinyl fluoride, tetrafluoroethylene, and trifluorochloroethylene.
【0009】次にメタクリル酸エステル系樹脂とは、メ
タクリル酸メチルのホモポリマーの他のメタクリル酸メ
チルと共重合可能な単量体との共重合体をいう。共重合
可能な単量体としては、メタクリル酸ブチル、メタクリ
ル酸エチルの他アクリル酸エステル類等がある。The methacrylic acid ester-based resin is a copolymer of a homopolymer of methyl methacrylate and another monomer copolymerizable with methyl methacrylate. Examples of the copolymerizable monomer include butyl methacrylate, ethyl methacrylate, and acrylic acid esters.
【0010】複合フィルムA層(以下A層という)に使
用するフッ化ビニリデン樹脂とメタクリル酸エステル系
樹脂の混合比は、 100〜50重量部/0〜50重量部、好ま
しくは95〜60重量部/ 5〜40重量部であり、これはフッ
化ビニリデン樹脂が50重量部以上存在しないと、その優
れた耐候性と耐汚染性及び耐溶剤性が発揮できない理由
による。The mixing ratio of the vinylidene fluoride resin and the methacrylic acid ester resin used for the composite film A layer (hereinafter referred to as A layer) is 100 to 50 parts by weight / 0 to 50 parts by weight, preferably 95 to 60 parts by weight. / 5 to 40 parts by weight, which is because the excellent weather resistance, stain resistance and solvent resistance cannot be exhibited unless the vinylidene fluoride resin is present in an amount of 50 parts by weight or more.
【0011】一方複合フィルムB層(以下B層という)
に使用するフッ化ビニリデン樹脂とメタクリル酸エステ
ル系樹脂の混合比は、0〜65重量部/ 100〜35重量部、
好ましくは20〜50重量部/80〜50重量部であり、これは
フッ化ビニリデン樹脂が65重量部を超えるとメタクリル
酸エステル系樹脂の優れた接着性が疎外されるためであ
る。On the other hand, layer B of composite film (hereinafter referred to as layer B)
The mixing ratio of vinylidene fluoride resin and methacrylic acid ester resin used for is 0 to 65 parts by weight / 100 to 35 parts by weight,
It is preferably 20 to 50 parts by weight / 80 to 50 parts by weight, because when the vinylidene fluoride resin exceeds 65 parts by weight, the excellent adhesiveness of the methacrylic acid ester resin is excluded.
【0012】さらにA層がフッ化ビニリデン樹脂単独、
B層がメタクリル酸エステル樹脂単独からなるフィルム
構成の場合には、中間層にフッ化ビニリデン樹脂とメタ
クリル酸エステル系樹脂とを混合したフィルムを介在さ
せると、A層とB層との接着性が向上する。なおA層、
B層および層全体のフィルム厚さは特に規定されない
が、保護フィルムとして使用する場合には、A層は3〜
100 μ、B層は5〜200μ、層全体としては10〜300 μ
程度が好ましい。しかし耐溶剤性を必要とする用途等で
は、この限りではなく数mmの厚さでも使用出来る。Further, the A layer is a vinylidene fluoride resin alone,
In the case where the B layer has a film structure composed of a methacrylic acid ester resin alone, when a film obtained by mixing a vinylidene fluoride resin and a methacrylic acid ester resin is interposed in the intermediate layer, the adhesiveness between the A layer and the B layer is increased. improves. Layer A,
The film thicknesses of the B layer and the entire layer are not particularly specified, but when used as a protective film, the A layer has a thickness of 3 to
100 μ, B layer is 5 to 200 μ, and the entire layer is 10 to 300 μ
A degree is preferable. However, it is not limited to this and can be used with a thickness of several mm in applications requiring solvent resistance.
【0013】一方A層およびB層の少なくとも一方の層
に遮光性を付与し基材の耐候性を向上させる目的で使用
する際、その遮光性付与の方法は、少なくとも一方の層
に酸化チタン、タルク、炭酸カルシウム、カーボンブラ
ック、ベンガラの他調合された無機顔料を含む充填剤、
着色剤を練り込む事により達成出来る。しかもいずれか
一方の層を、2層構造とし、その上に他層が積層された
3層構成にして前記2層構造の中間層に当たる層を遮光
層とすることもできる。On the other hand, when it is used for the purpose of imparting a light-shielding property to at least one of the A layer and the B layer to improve the weather resistance of the base material, the method of imparting the light-shielding property is as follows. Fillers containing talc, calcium carbonate, carbon black, red iron oxide and other formulated inorganic pigments,
It can be achieved by kneading a colorant. Moreover, either one of the layers may have a two-layer structure, and the other layer may be laminated thereon to form a three-layer structure, and the layer corresponding to the intermediate layer of the two-layer structure may be used as the light-shielding layer.
【0014】また透明フィルムの状態で基材の耐候性を
さらに向上(特に紫外線の遮断が目的)させる方法とし
ては、A層およびB層の少なくとも一方の層にベンゾト
リアゾール系、ベンゾフェノン系、サリチル酸誘導体等
の紫外線吸収剤を練り込む方法が採用される。この際ラ
ジカル補捉剤や酸化防止剤を併用すると更に効果があ
る。Further, as a method for further improving the weather resistance of the substrate in the state of the transparent film (particularly for the purpose of blocking ultraviolet rays), benzotriazole type, benzophenone type, salicylic acid derivative in at least one of the A layer and the B layer is used. A method of kneading an ultraviolet absorber such as At this time, it is more effective to use a radical scavenger and an antioxidant together.
【0015】次に製造方法について述べる。本発明によ
る複合フィルムは、A層とB層の2層より構成され、溶
融押出成形して一体に結合する事を特徴とする。Next, the manufacturing method will be described. The composite film according to the present invention is characterized in that it is composed of two layers, A layer and B layer, and is melt-extruded and integrally bonded.
【0016】溶融押出成形には、一般の単軸押出機のほ
か2軸押出機も使用されるが、複数の層を一体に結合す
る方法としては次の方法がある。For the melt extrusion molding, a general single-screw extruder as well as a twin-screw extruder is used, and the following method is available as a method for integrally bonding a plurality of layers.
【0017】まず複数の押出成形機を利用して樹脂を溶
融状態で接着せしめて多層とするT−ダイ使用共押出成
形法には、マルチマニホールドダイと称し、複数の樹脂
層をシートの状態にした後接触接着する方法と、フィー
ドブロックダイと称し、複数の樹脂を接着後シート状に
拡げる方法とがある。またインフレーション成形法と称
し、丸型ダイを使用する方法でも多層フィルムが成形出
来る。First, a co-extrusion molding method using a T-die in which a plurality of extruders are used to bond resins in a molten state to form a multilayer structure is called a multi-manifold die, and a plurality of resin layers are formed into sheets. After that, there is a method of contact bonding and a method called a feed block die, and a method of spreading a plurality of resins into a sheet after bonding. A multilayer film can also be formed by a method called an inflation molding method, which uses a round die.
【0018】次に、A層またはB層の少なくともいづれ
か一方に遮光性を付与するためには、2〜30重量%程度
の顔料の添加が必要であり、押出機等を使用して樹脂と
顔料を溶融混練する方法でもよいが、一般には顔料の分
散が十分でなく、高速回転かつ高せん断混練機例えば神
戸製鋼所のFCM 型混練機を使用すると顔料の分散が非常
によくなり、表面状態の優れた遮光層用の原料を提供す
る事が出来る。Next, in order to impart a light-shielding property to at least one of the A layer and the B layer, it is necessary to add a pigment in an amount of about 2 to 30% by weight. Although the method of melt kneading may be used, in general, the pigment is not sufficiently dispersed, and when a high-speed rotation and high-shear kneading machine such as FCM type kneading machine of Kobe Steel is used, the dispersion of the pigment becomes very good and the surface condition It is possible to provide excellent raw materials for the light shielding layer.
【0019】[0019]
【実施例】なおこれからフッ化ビニリデン樹脂をPVDF、
メタクリル酸メチル樹脂をPMMAと略して説明する。フッ
化ビニリデン系樹脂は、ペンウォルト社製、商品名カイ
ナー740 (以下K-740 と略す)一方メタクリル酸エステ
ル系樹脂は、三菱レイヨン(株)社製、商品名アクリペ
ットMD(PMMAで以下MDと略す)および同社製、商品名ハ
イペットHBE (アクリル系ゴムを含むメタクリル酸メチ
ル樹脂で以下HBEと略す)を使用した。なおK-740 とMD
又はHBE の混合品は、これらを一定比率でブレンドし、
あらかじめ30mmφ異方向回転2軸押出機で溶融、再ペレ
ット化して用いた。[Example] In addition, vinylidene fluoride resin was changed to PVDF,
The methyl methacrylate resin will be abbreviated as PMMA. Vinylidene fluoride resin is a product of Pen Walt, trade name Kainer 740 (hereinafter abbreviated as K-740), and methacrylate ester resin is a product of Mitsubishi Rayon Co., Ltd., trade name Acrypet MD (hereinafter referred to as PMMA MD Abbreviated) and the company's trade name HiPET HBE (methyl methacrylate resin containing acrylic rubber, abbreviated as HBE below). K-740 and MD
Or, for HBE mixture, blend these in a fixed ratio,
The product was melted and re-pelletized with a 30 mmφ counter-rotating twin-screw extruder in advance.
【0020】実施例1 A層用原料としてK-740 とMDより得たPVDF/PMMA=80/20
品を、一方B層用原料としてK-740 とMDより得たPVDF/P
MMA=50/50 品を用い、40mmφ押出機2台と幅300 mm、ス
リット0.5mmのマルチマニホールドダイを使用して2層
共押出成形を行った。なお引取装置のダイに最も近い冷
却ロールは水冷した。得られた複合フィルムの各特性を
測定した結果は、表1に示す様にA層15μ、B層35μ、
合計50μの厚さであり、耐汚染性、耐候性に優れ、かつ
熱接着性にも優れていた。Example 1 PVDF / PMMA = 80/20 obtained from K-740 and MD as raw materials for layer A
On the other hand, PVDF / P obtained from K-740 and MD as raw material for layer B
Using MMA = 50/50, two-layer coextrusion molding was performed using two 40 mmφ extruders and a multi-manifold die having a width of 300 mm and a slit of 0.5 mm. The cooling roll closest to the die of the take-up device was water-cooled. The results of measuring the respective properties of the obtained composite film are as shown in Table 1, A layer 15μ, B layer 35μ,
With a total thickness of 50μ, it was excellent in stain resistance, weather resistance, and thermal adhesion.
【0021】実施例2 A層用原料としてK-740 とMDより得たPVDF/PMMA=70/30
品を、一方B層用原料として同じくK-740 とMDより得た
PVDF/PMMA=30/70 品を用い、それぞれ40mmφ押出機、65
mmφ押出機およびフィードブロックダイ、450mm幅、ス
リット0.3mmのT-ダイを使用して、2層フィルムの共押
出成形を行った。なおこの際にもT-ダイに近接する引取
ロールは水冷した。得られた2層フィルムは、A層5
μ、B層20μ、合計25μの厚さであった。各特性は、表
1の様な結果を示した。Example 2 PVDF / PMMA = 70/30 obtained from K-740 and MD as a raw material for layer A
Was obtained from K-740 and MD as raw material for layer B
PVDF / PMMA = 30/70, 40mmφ extruder, 65
A two-layer film was coextruded using a mmφ extruder and a feed block die, a T-die having a width of 450 mm and a slit of 0.3 mm. Also at this time, the take-up roll near the T-die was water-cooled. The obtained two-layer film is A layer 5
μ, B layer 20 μ, total thickness 25 μ. Each property shows the results as shown in Table 1.
【0022】実施例3 A層用原料としてK-740 とMDより得たPVDF/PMMA=60/40
品を、一方B層用原料として同じくK-740 とMDより得た
PVDF/PMMA=20/80 品を用い、それぞれ40mmφ押出機、65
mmφ押出機およびフィードブロックダイ、450mm幅、ス
リット0.3mmのT-ダイを使用して、2層フィルムの共押
出成形を行った。なおこの際にもT-ダイに近接する引取
ロールは水冷した。得られた2層フィルムは、A層10
μ、B層30μ、合計40μの厚さであった。各特性は、表
1の様な結果を示した。Example 3 PVDF / PMMA = 60/40 obtained from K-740 and MD as a raw material for layer A
Was obtained from K-740 and MD as raw material for layer B
PVDF / PMMA = 20/80 product, 40mmφ extruder, 65
A two-layer film was coextruded using a mmφ extruder and a feed block die, a T-die having a width of 450 mm and a slit of 0.3 mm. Also at this time, the take-up roll near the T-die was water-cooled. The obtained two-layer film is A layer 10
μ, B layer 30 μ, total thickness 40 μ. Each property shows the results as shown in Table 1.
【0023】実施例4 K-740 とMDより得たPVDF/PMMA=80/20 品100 重量部にル
チル型酸化チタン20重量部を神戸製鋼所製FCM 型混練機
を使用して溶融混練ペレット化した原料をA層用とし、
一方、K-740 とMDより得たPVDF/PMMA=40/60 品をB層用
として40mmφ押出機2台とスパイラル型2層インフレー
ションダイ(ダイ径 100mmφ)を使用して、フィルム成
形を行った。得られた2層フィルムの特性は、表1の様
な結果を示した。Example 4 100 parts by weight of PVDF / PMMA = 80/20 obtained from K-740 and MD and 20 parts by weight of rutile type titanium oxide were melt-kneaded into pellets using an FCM type kneader manufactured by Kobe Steel. Made raw material for A layer,
On the other hand, PVDF / PMMA = 40/60 obtained from K-740 and MD was used as a layer B for film formation using two 40 mmφ extruders and a spiral type two-layer inflation die (die diameter 100 mmφ). .. The characteristics of the obtained two-layer film showed the results shown in Table 1.
【0024】実施例5 A層用原料としてK-740 とMDより得たPVDF/PMMA=80/20
品を、一方B層用原料としてK-740 のPVDF/ ゴム入りPM
MA(HBE)=40/60 品を用い、それぞれ40mmφ押出機、65mm
φ押出機およびフィードブロックダイ、450 mm幅、スリ
ット0.3mmのT-ダイを使用して2層フィルムの共押出成
形を行った。この際、T-ダイに最も近接する引取ロール
は水冷した。得られた2層フィルムの特性と厚さとを表
1に示す。Example 5 PVDF / PMMA = 80/20 obtained from K-740 and MD as raw materials for layer A
On the other hand, as a raw material for layer B, K-740 PVDF / rubber PM
MA (HBE) = 40/60 product, 40mmφ extruder, 65mm
A two-layer film was coextruded using a φ extruder and a feed block die, a T-die having a width of 450 mm and a slit of 0.3 mm. At this time, the take-up roll closest to the T-die was water-cooled. Table 1 shows the properties and thickness of the obtained two-layer film.
【0025】比較例1 K-740 とMDより得たPVDF/PMMA=80/20 品の単層フィルム
をインフレーション成形を得た。厚さ50μのフィルムで
耐汚染性と、耐候性は良好であったが、熱接着性は、満
足すべき結果が得られなかった。特性は表2に示す。Comparative Example 1 A PVDF / PMMA = 80/20 monolayer film obtained from K-740 and MD was subjected to inflation molding. The 50 μm-thick film had good stain resistance and weather resistance, but did not give satisfactory results with respect to thermal adhesion. The characteristics are shown in Table 2.
【0026】比較例2 K-740 とMDより得たPVDF/PMMA=30/70 の単層フィルムを
T-ダイ成形で得た。得られたフィルムの特性は、表2の
様な結果であった。Comparative Example 2 A single layer film of PVDF / PMMA = 30/70 obtained from K-740 and MD was used.
Obtained by T-die molding. The characteristics of the obtained film were as shown in Table 2.
【0027】比較例3 厚さ30μの市販メタクリル酸エステル樹脂系フィルムの
特性を測定した結果は、第2表のとおりの値を得た。Comparative Example 3 As a result of measuring the characteristics of a commercially available methacrylic acid ester resin film having a thickness of 30 μ, the values shown in Table 2 were obtained.
【0028】比較例4 厚さ25μの市販フッ素フィルムの特性を測定した結果
は、表2のとおりの値を得た。Comparative Example 4 As a result of measuring the characteristics of a commercially available fluorine film having a thickness of 25 μ, the values shown in Table 2 were obtained.
【0029】[0029]
【表1】 [Table 1]
【0030】[0030]
【表2】 [Table 2]
【0031】表1および表2の特性測定は、次の通りに
行なった。 (1) フィルム厚さ:1/1000mm目盛のピーコック厚さ計
を使用して測定。なお2層のうちのAおよびB層の厚さ
は各押出機の押出量比より計算した。The characteristics of Tables 1 and 2 were measured as follows. (1) Film thickness: Measured using a Peacock thickness gauge with a scale of 1/1000 mm. The thicknesses of the A and B layers of the two layers were calculated from the extrusion rate ratio of each extruder.
【0032】(2) 引張強度:JIS K-6732に準拠引張速度
100mm/分、MDは押出機と平行方向、TDは押出機と直角
方向を示す。(2) Tensile strength: tensile speed according to JIS K-6732
100 mm / min, MD is parallel to the extruder, TD is perpendicular to the extruder.
【0033】(3) 光線透過率:JIS K-6714に準拠 (4) 耐候性 (イ) 耐候性促進試験JIS A-1415 (ロ) 黄色度測定 JIS K-7103 黄変指数=暴露後の黄色度/初期黄色度(3) Light transmittance: In accordance with JIS K-6714 (4) Weather resistance (a) Weather resistance accelerated test JIS A-1415 (b) Yellowness measurement JIS K-7103 Yellowing index = yellow after exposure Degree / initial yellowness
【0034】(5) 耐汚染性(A層側) 1.試験方法 1各フィルムに約1cm2 程度マジックでマークする。 2乾燥後ガーゼで30回こすり落す。 3残ったインキを肉眼で評価する。 2.評価基準 1:完全に落ちる。 2:落ちるがこすったあとが薄く残る。 3:落ちるがこすったあとが濃く残る。 4:一部落ちるが残るところもある(落ちたところもあ
とが残る)。 5:ほとんど落ちない。(5) Contamination resistance (A layer side) 1. Test method 1 Mark each film with a marker of about 1 cm 2 . 2 After drying, scrape with gauze 30 times. 3 Visually evaluate the remaining ink. 2. Evaluation criteria 1: Completely falls. 2: Drops but remains thin after rubbing. 3: It drops, but remains thick after rubbing. 4: A part falls, but there is a place (the place where it falls still remains). 5: Almost does not fall.
【0035】(5) 耐溶剤性(A層側のみを浸漬) 1.試験方法:室温にて各溶剤に2日間浸漬後肉眼で評価
した。 2.評価基準◎:変化なし ○: わずかながらフィルム収縮 △:フィルム収縮 △〜×:フィルム収縮・膨潤 ×:フィルム溶解(5) Solvent resistance (only the layer A side is immersed) 1. Test method: Immersed in each solvent for 2 days at room temperature and evaluated visually. 2. Evaluation criteria ◎: No change ○: Slight film shrinkage △: Film shrinkage △ to ×: Film shrinkage / swelling ×: Film dissolution
【0036】(7) 熱接着性(B層側) 1.試験方法基材:テーブルクロス用軟質塩ビシート 2
00μ 接着ロールと条件: 鏡面/シリコンゴム 100φ× 350
mmリットル速度1m /分 2.評価方法 25mm幅積層シートを20mm/分の速度で180
°剥離し強度を測定。(7) Thermal Adhesiveness (B Layer Side) 1. Test Method Base Material: Soft PVC Sheet for Tablecloth 2
00μ Bonding roll and conditions: mirror surface / silicone rubber 100φ × 350
mm liter speed 1 m / min 2. Evaluation method 180 mm of 25 mm width laminated sheet at 20 mm / min
° Peel and measure strength.
【0037】[0037]
【発明の効果】本発明の製造方法で得られたフッ化ビニ
リデン樹脂系複合フィルムは、高い強・伸度を有し、か
つフッ化ビニリデン樹脂の有する優れた長期耐候性を有
するばかりでなく、水性、油性インキ類や塵埃が付着し
ても簡単に除去出来る耐汚染性や耐溶剤性にすぐれてい
る。しかもメタクリル酸エステル系樹脂が混合されて接
着性に富んでいるので、壁紙やエレベーター及び車輌等
の内装用、屋根材、壁材、雨どい等の用途に適用するこ
とができる。The vinylidene fluoride resin-based composite film obtained by the production method of the present invention has high strength and elongation, and not only has excellent long-term weather resistance of the vinylidene fluoride resin, It has excellent stain resistance and solvent resistance that can be easily removed even if water-based or oil-based inks and dust adhere. Moreover, since it is mixed with a methacrylic acid ester-based resin and has excellent adhesiveness, it can be applied to applications such as wallpaper, interiors of elevators and vehicles, roofing materials, wall materials, rain gutters, and the like.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 // B29K 27:12 B29L 7:00 4F 9:00 4F ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location // B29K 27:12 B29L 7:00 4F 9:00 4F
Claims (1)
メタクリル酸エステル系樹脂0〜50重量部とを成分とす
るA層と、フッ化ビニリデン樹脂0〜65重量部とメタク
リル酸エステル系樹脂 100〜35重量部とを成分とするB
層とから構成される複合フィルムを溶融押出して一体に
結合させる事を特徴とするフッ化ビニリデン樹脂系複合
フィルムの製造方法。1. A layer comprising 100 to 50 parts by weight of vinylidene fluoride resin and 0 to 50 parts by weight of methacrylic ester resin, 0 to 65 parts by weight of vinylidene fluoride resin and 100 of methacrylic acid ester resin. ~ 35 parts by weight of B
A method for producing a vinylidene fluoride resin-based composite film, which comprises melt-extruding a composite film composed of a layer and bonding them together.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3206145A JPH0671785B2 (en) | 1984-06-23 | 1991-07-24 | Method for producing vinylidene fluoride resin-based composite film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59129782A JPH0611536B2 (en) | 1984-06-23 | 1984-06-23 | Vinylidene fluoride resin-based composite film |
JP3206145A JPH0671785B2 (en) | 1984-06-23 | 1991-07-24 | Method for producing vinylidene fluoride resin-based composite film |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59129782A Division JPH0611536B2 (en) | 1984-06-23 | 1984-06-23 | Vinylidene fluoride resin-based composite film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0550566A true JPH0550566A (en) | 1993-03-02 |
JPH0671785B2 JPH0671785B2 (en) | 1994-09-14 |
Family
ID=26465069
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3206145A Expired - Lifetime JPH0671785B2 (en) | 1984-06-23 | 1991-07-24 | Method for producing vinylidene fluoride resin-based composite film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0671785B2 (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000094577A (en) * | 1998-09-22 | 2000-04-04 | Mitsubishi Plastics Ind Ltd | Weather resistant resin-coated metal plate |
WO2006016618A1 (en) * | 2004-08-11 | 2006-02-16 | Kaneka Corporation | Vinylidene fluoride resin film |
JP2007524532A (en) * | 2004-02-20 | 2007-08-30 | サン−ゴバン パフォーマンス プラスティックス コーポレイション | Take-up resonance resistance multilayer film |
JP2008028294A (en) * | 2006-07-25 | 2008-02-07 | Toppan Printing Co Ltd | Sheet for sealing rear surface of solar battery |
JP2009013418A (en) * | 2004-02-20 | 2009-01-22 | Arkema France | Composition coextrudable with pvdf and having no stress-whitening effect |
JP2009035695A (en) * | 2007-08-03 | 2009-02-19 | Nippon Shokubai Co Ltd | Thermoplastic resin composition and film |
JP2009078393A (en) * | 2007-09-25 | 2009-04-16 | Toppan Cosmo Inc | Decorative sheet |
JP2009522134A (en) * | 2005-12-29 | 2009-06-11 | アーケマ・インコーポレイテッド | Multilayer fluoropolymer film |
WO2009151071A1 (en) | 2008-06-10 | 2009-12-17 | 株式会社カネカ | Fluororesin film and fluororesin-laminated acrylic resin film |
JP2010120386A (en) * | 2002-04-18 | 2010-06-03 | Three M Innovative Properties Co | Fluoropolymer article |
US10294342B2 (en) | 2014-05-15 | 2019-05-21 | Kaneka Corporation | Film obtained by laminating coating layer made of fluorine-containing acrylic resin on base film |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5544898A (en) * | 1978-09-25 | 1980-03-29 | Ugine Kuhlmann | Compound material containing polyfluovinylidene and its preparation |
JPS57187248A (en) * | 1981-05-12 | 1982-11-17 | Kureha Chemical Ind Co Ltd | Laminate |
-
1991
- 1991-07-24 JP JP3206145A patent/JPH0671785B2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5544898A (en) * | 1978-09-25 | 1980-03-29 | Ugine Kuhlmann | Compound material containing polyfluovinylidene and its preparation |
JPS57187248A (en) * | 1981-05-12 | 1982-11-17 | Kureha Chemical Ind Co Ltd | Laminate |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000094577A (en) * | 1998-09-22 | 2000-04-04 | Mitsubishi Plastics Ind Ltd | Weather resistant resin-coated metal plate |
JP2010120386A (en) * | 2002-04-18 | 2010-06-03 | Three M Innovative Properties Co | Fluoropolymer article |
JP2009013418A (en) * | 2004-02-20 | 2009-01-22 | Arkema France | Composition coextrudable with pvdf and having no stress-whitening effect |
JP2007524532A (en) * | 2004-02-20 | 2007-08-30 | サン−ゴバン パフォーマンス プラスティックス コーポレイション | Take-up resonance resistance multilayer film |
US8303875B2 (en) | 2004-08-11 | 2012-11-06 | Kaneka Corporation | Method for producing vinylidene fluoride resin transparent film |
US7452602B2 (en) | 2004-08-11 | 2008-11-18 | Kaneka Corporation | Vinylidene fluoride-based resin film |
WO2006016618A1 (en) * | 2004-08-11 | 2006-02-16 | Kaneka Corporation | Vinylidene fluoride resin film |
JP2009522134A (en) * | 2005-12-29 | 2009-06-11 | アーケマ・インコーポレイテッド | Multilayer fluoropolymer film |
JP2008028294A (en) * | 2006-07-25 | 2008-02-07 | Toppan Printing Co Ltd | Sheet for sealing rear surface of solar battery |
JP2009035695A (en) * | 2007-08-03 | 2009-02-19 | Nippon Shokubai Co Ltd | Thermoplastic resin composition and film |
JP2009078393A (en) * | 2007-09-25 | 2009-04-16 | Toppan Cosmo Inc | Decorative sheet |
WO2009151071A1 (en) | 2008-06-10 | 2009-12-17 | 株式会社カネカ | Fluororesin film and fluororesin-laminated acrylic resin film |
EP2325005A2 (en) | 2008-06-10 | 2011-05-25 | Kaneka Corporation | Fluororesin-laminated acrylic resin film |
US9074058B2 (en) | 2008-06-10 | 2015-07-07 | Kaneka Corporation | Fluororesin film and fluororesin-laminated acrylic resin film |
US10253143B2 (en) | 2008-06-10 | 2019-04-09 | Kaneka Corporation | Fluororesin film and fluororesin-laminated acrylic resin film |
US10294342B2 (en) | 2014-05-15 | 2019-05-21 | Kaneka Corporation | Film obtained by laminating coating layer made of fluorine-containing acrylic resin on base film |
Also Published As
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---|---|
JPH0671785B2 (en) | 1994-09-14 |
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