JP2788756B2 - Fluororesin-based colored film and method for producing the same - Google Patents

Fluororesin-based colored film and method for producing the same

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Publication number
JP2788756B2
JP2788756B2 JP1150616A JP15061689A JP2788756B2 JP 2788756 B2 JP2788756 B2 JP 2788756B2 JP 1150616 A JP1150616 A JP 1150616A JP 15061689 A JP15061689 A JP 15061689A JP 2788756 B2 JP2788756 B2 JP 2788756B2
Authority
JP
Japan
Prior art keywords
weight
parts
resin
layer
composition
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
JP1150616A
Other languages
Japanese (ja)
Other versions
JPH0316730A (en
Inventor
吉久 森谷
美基雄 清水
政太郎 佐塚
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.)
Denka Co Ltd
Original Assignee
Denki Kagaku Kogyo KK
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Filing date
Publication date
Application filed by Denki Kagaku Kogyo KK filed Critical Denki Kagaku Kogyo KK
Priority to JP1150616A priority Critical patent/JP2788756B2/en
Publication of JPH0316730A publication Critical patent/JPH0316730A/en
Application granted granted Critical
Publication of JP2788756B2 publication Critical patent/JP2788756B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Description

【発明の詳細な説明】 (産業上の利用分野) 本発明はプラスチツク、ゴム、金属板、ガラス、木
板、スレート、その他の基材表面に、表面保護、装飾等
の目的で永久もしくは半永久的に貼合せる表面保護着色
フイルムに関するものであり、耐候性、装飾性、耐汚染
性、耐薬品性等の堅牢度及び各種基材との接着性に優
れ、特に基材と貼合せた後の接着耐久性に優れたフツ素
樹脂系着色フイルムに関するものである。
DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention is applied to a surface of plastic, rubber, metal plate, glass, wood plate, slate, or other base material permanently or semi-permanently for the purpose of surface protection and decoration. It relates to a surface protective colored film that can be pasted, and has excellent durability such as weather resistance, decorative properties, stain resistance, and chemical resistance, and excellent adhesion to various substrates, especially adhesion durability after pasting to the substrate. The present invention relates to a fluororesin-based colored film having excellent properties.

(従来の技術) 従来建築物の内外装等に使用されるプラスチツク板や
金属板、その他の各種基材は耐久性の向上や装飾を目的
として、その表面を塗装したり、耐久性フイルム(印刷
等加工したものも含めて)をラミネートしたりして使用
されている。
(Prior Art) Conventionally, plastic plates, metal plates, and various other base materials used for interior and exterior of buildings and the like are coated with a surface or a durable film (printing) for the purpose of improving durability and decoration. (Including those that have undergone equal processing).

表面処理される基材にはポリ塩化ビニル、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等プラスチツク基
材の他、各種ゴム基材、アルミニウム−ステンレス−亜
鉛鋼板等金属基材、その他木板、ガラス、スレート等が
あり、その用途は壁紙やエレベーター、車輛等の内装用
の他、屋根材、壁材、雨どい、デツキ材、ガレージ、ア
ーケード、サンルーム、テント地、農業用資材、看板、
標識、防音壁、ラベル、窓ガラス、家具、家電製品等多
岐にわたり実用面の美観等を考えて着色フイルムを使用
することが望まれている。
Substrates to be surface-treated include polyvinyl chloride, polycarbonate, polymethyl methacrylate, acrylonitrile
In addition to plastic base materials such as butadiene-styrene copolymer and FRP, there are various rubber base materials, metal base materials such as aluminum-stainless steel-zinc steel plate, other wood plates, glass, slate, etc. Roofing materials, roofing materials, wall materials, gutters, decking materials, garages, arcades, solariums, tents, agricultural materials, signs,
It is desired to use colored films in consideration of aesthetics of practical use in a wide variety of signs, soundproof walls, labels, window glasses, furniture, home appliances, and the like.

(発明が解決しようとする課題) 従来耐候性および接着性を有するフツ素系着色フイル
ムとしては、特開昭64−90733号公報にフツ化ビニリデ
ン系樹脂およびメタクリル酸エステル系樹脂からなる樹
脂成分に無機顔料を添加したフイルムが知られている。
しかし、無機顔料を使用した場合は、顔料の色調等が限
定されるため、(1)あざやかな色調のフイルムが得ら
れない(2)透明および半透明フイルムが得られない等
欠点があつた。また耐久性着色フイルムと各種基材との
貼り合わせは、各種接着剤もしくは熱加工により接着を
行うが、前記した接着界面でのはがれ、浮き、ふくれ等
の問題がある。したがつて接着界面に位置する有機物の
光による劣化を防止する方法が考えられているが、フイ
ルムの物理的強度性能バランスの優れたフイルムの製造
が困難である。
(Problems to be Solved by the Invention) Conventional fluorine-based colored films having weather resistance and adhesiveness include a resin component comprising a vinylidene fluoride resin and a methacrylate ester resin described in JP-A-64-90733. A film to which an inorganic pigment is added is known.
However, when an inorganic pigment is used, since the color tone and the like of the pigment are limited, there are disadvantages such as (1) a film having a vivid color tone cannot be obtained, and (2) a transparent and translucent film cannot be obtained. In addition, when the durable colored film and various substrates are bonded together by various adhesives or heat processing, there are problems such as peeling, floating and blistering at the bonding interface described above. Therefore, a method of preventing the deterioration of the organic substance located at the bonding interface due to light has been considered, but it is difficult to produce a film having an excellent balance of physical strength performance of the film.

本発明の目的は耐候性、装飾性、耐汚染性、耐薬品性
等の堅牢度及び各種基材との接着性に優れた耐久性表面
保護着色フイルムを提供する事にある。
SUMMARY OF THE INVENTION It is an object of the present invention to provide a durable surface protective colored film which is excellent in fastness such as weather resistance, decorative property, stain resistance, chemical resistance and the like and adhesion to various substrates.

本発明のもう1つの目的は各種基材と貼り合せた後の
接着耐久性に優れた表面保護用フイルムを提供する事に
ある。
Another object of the present invention is to provide a surface protection film having excellent adhesion durability after being bonded to various substrates.

本発明者らは上記の課題を解決すべく、従来使用され
ている素材、及びフイルムにとらわれる事なく研究を重
ねてきたところ、フツ化ビニリデン系樹脂及びメタクリ
ル酸エステル系樹脂成分とし(1)表面層、中間層およ
び裏面層の少なくとも1層を有機顔料で着色し(2)フ
イルムおよび該フイルムの下層に存在する樹脂又は接着
剤層の保護のため紫外線吸収剤を含有する層をもつ着色
フイルムを使用した際に、今まで知られている無機顔料
を使用したフイルムでは得られない、あざやかな色調を
もち、かつ透明および半透明フイルムも可能な耐候性着
色フイルムを見い出し、本発明を完成するに至つた。
In order to solve the above-mentioned problems, the present inventors have conducted research without being restricted to materials and films conventionally used. As a result, vinylidene fluoride resin and methacrylic acid ester resin component were used as (1) surface (2) A colored film having a layer containing an ultraviolet absorber for protecting the film and a resin or adhesive layer present under the film, wherein at least one of the layer, the intermediate layer and the back layer is colored with an organic pigment. When used, to find a weather-resistant colored film that has a vivid color tone, which is not possible with films using inorganic pigments known until now, and that can also be transparent and translucent, to complete the present invention. It has been reached.

(課題を解決するための手段) すなわち本発明は (1)フツ化ビニリデン系樹脂100〜50重量部及びメタ
クリル酸エステル系樹脂0〜50重量部及び紫外線吸収剤
0〜15重量部を主成分とする組成物(A)を表面層と
し、メタクリル酸エステル系樹脂95〜55重量部、フツ化
ビニリデン系樹脂5〜45重量部及び紫外線吸収剤0.1〜1
5重量部を主成分とする組成物(B)を裏面層とする少
なくとも1層が有機顔料で着色されたフツ素樹脂系着色
フイルム。
(Means for Solving the Problems) That is, the present invention comprises (1) 100 to 50 parts by weight of a vinylidene fluoride resin, 0 to 50 parts by weight of a methacrylate resin, and 0 to 15 parts by weight of an ultraviolet absorbent. The composition (A) to be used as a surface layer, 95 to 55 parts by weight of a methacrylate resin, 5-45 parts by weight of a vinylidene fluoride resin, and 0.1 to 1 parts of an ultraviolet absorber
A fluororesin-based colored film in which at least one layer having a back surface layer of the composition (B) containing 5 parts by weight as a main component is colored with an organic pigment.

(2)フツ化ビニリデン系樹脂100〜50重量部及びメタ
クリル酸エステル系樹脂0〜50重量部及び紫外線吸収剤
0〜15重量部を主成分とする組成物(A)を表面層及び
裏面層とし、メタクリル酸エステル系樹脂95〜55重量
部、フツ化ビニリデン系樹脂5〜45重量部及び紫外線吸
収剤0.1〜15重量部を主成分とする組成物(B)を中間
層とする少なくとも1層が有機顔料で着色されたフツ素
樹脂系着色フイルム。
(2) Composition (A) containing 100 to 50 parts by weight of vinylidene fluoride resin, 0 to 50 parts by weight of methacrylate ester resin and 0 to 15 parts by weight of ultraviolet absorber as a main surface layer and a rear surface layer At least one layer having a composition (B) containing 95 to 55 parts by weight of a methacrylate ester resin, 5 to 45 parts by weight of a vinylidene fluoride resin and 0.1 to 15 parts by weight of an ultraviolet absorber as an intermediate layer, Fluororesin-based colored film colored with organic pigments.

(3)フツ化ビニリデン系樹脂100〜50重量部及びメタ
クリル酸エステル系樹脂0〜50重量部及び紫外線吸収剤
0〜15重量部を主成分とする組成物(A)を表面層と
し、メタクリル酸エステル系樹脂95〜55重量部、フツ化
ビニリデン系樹脂5〜45重量部及び紫外線吸収剤0.1〜1
5重量部を主成分とする組成物(B)を裏面層とする少
なくとも1層が有機顔料で着色されたフツ素樹脂系着色
フイルムを共押出成形法又は熱ラミネーションで製造す
ることを特徴とするフツ素樹脂系着色フイルムの製造方
法。
(3) A composition comprising, as a main component, 100 to 50 parts by weight of vinylidene fluoride resin, 0 to 50 parts by weight of a methacrylate ester resin and 0 to 15 parts by weight of an ultraviolet absorber as a surface layer, and methacrylic acid Ester resin 95 to 55 parts by weight, vinylidene fluoride resin 5 to 45 parts by weight and ultraviolet absorber 0.1 to 1
A fluororesin-based colored film in which at least one layer having a composition (B) containing 5 parts by weight as a main component and a back layer is colored with an organic pigment is produced by a coextrusion molding method or thermal lamination. A method for producing a fluororesin-based colored film.

(4)フツ化ビニリデン系樹脂100〜50重量部及びメタ
クリル酸エステル系樹脂0〜50重量部及び紫外線吸収剤
0〜15重量部を主成分とする組成物(A)を表面層及び
裏面層とし、メタクリル酸エステル系樹脂95〜55重量
部、フツ化ビニリデン系樹脂5〜45重量部及び紫外線吸
収剤0.1〜15重量部を主成分とする組成物(B)を中間
層とする少なくとも1層が有機顔料で着色されたフツ素
樹脂系着色フイルムを共押出成形法又は熱ラミネーショ
ンで製造することを特徴とするフツ素樹脂系着色フイル
ムの製造方法。
(4) Composition (A) containing 100 to 50 parts by weight of vinylidene fluoride resin, 0 to 50 parts by weight of methacrylic acid ester resin and 0 to 15 parts by weight of ultraviolet absorber as a main surface layer and a rear surface layer At least one layer having a composition (B) containing 95 to 55 parts by weight of a methacrylate ester resin, 5 to 45 parts by weight of a vinylidene fluoride resin and 0.1 to 15 parts by weight of an ultraviolet absorber as an intermediate layer, A method for producing a fluororesin-based colored film, characterized by producing a fluororesin-based colored film colored with an organic pigment by coextrusion molding or thermal lamination.

本発明の組成物(A)及び組成物(B)で使用するフ
ツ化ビニリデン系樹脂(以下PVDFという)とは、フツ化
ビニリデンのホモポリマー、又はフツ化ビニリデンと共
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4フツ化エチレン、6フツ化プロピ
レン、3フツ化塩化エチレン、フツ化ビニルなどがあ
る。
The vinylidene fluoride resin (hereinafter referred to as PVDF) used in the compositions (A) and (B) of the present invention is a homopolymer of vinylidene fluoride or a monomer copolymerizable with vinylidene fluoride. Means a copolymer of Examples of the copolymerizable monomer include ethylene tetrafluoride, propylene hexafluoride, ethylene trifluoride chloride, and vinyl fluoride.

次にメタクリル酸エステル系樹脂(以下PMMAという)
とは、メタクリル酸メチルのホモポリマー又はメタクリ
ル酸メチルと共重合可能な単量体との共重合体及びポリ
メタクリル酸メチルとアクリル系ゴムとのブレンド物等
をいう。共重合可能な単量体としては、炭素数2〜4の
メタクリル酸エステル、アクリル酸ブチルをはじめとす
る炭素数1〜8のアクリル酸エステル、エチレン、α−
メチルスチレン、アクリロニトリル、アクリル酸、他の
エチレン性不飽和モノマー等がある。
Next, methacrylate resin (hereinafter referred to as PMMA)
The term "methyl methacrylate" refers to a homopolymer of methyl methacrylate, a copolymer of a monomer copolymerizable with methyl methacrylate, and a blend of polymethyl methacrylate and an acrylic rubber. Examples of the copolymerizable monomer include methacrylates having 2 to 4 carbon atoms, acrylates having 1 to 8 carbon atoms such as butyl acrylate, ethylene, α-
Examples include methylstyrene, acrylonitrile, acrylic acid, and other ethylenically unsaturated monomers.

本発明の組成物(A)及び(B)に用いる紫外線吸収
剤としては、組成物(A)及び(B)に使用する樹脂と
相溶性のあるものであればよく、揮散を防ぐためには、
高分子量の紫外線吸収剤が好ましい。前記吸収剤の例と
しては、ベンゾトリアゾール系、オキザリツクアツシド
系、ベンゾフエノン系、ヒンダードアミン系及びその他
多くの種類の公知のものが使用できる。更に具体的に
は、2−〔3,5−ジ−(アロフアージメチルベンジル−
2−ヒドロキシフエニル〕ベンゾトリアゾール、2−
(3,5−ジ−t−ブチル−2−ヒドロキシフエニル)ペ
ンゾトリアゾール、2−(3−t−ブチル−5−メチル
−2ヒドロキシフエニル)−5−クロロベンゾトリアゾ
ール、2−(3,5−ジ−t−ブチル−2−ヒドロキシフ
エニル)−5−クロロベンゾトリアゾール、2−(3,5
−ジ−t−アミル−2−ヒドロキシフエニル)ベンゾト
リアゾール、2−エトキシ−2′−エチルオキザツクア
シツドビスアニリド、2−エトキシ−5−t−ブチル−
2′エチルオキザツクアシツドビスアニリド、2−ヒド
ロキシ−4−n−オクトオキシベンゾフエノン、ビス
(1,2,2,6,6−ペンチメチル−4−ピペリジル)セバケ
ート、ビス(1,2,2,6,6−テトラメチル−4−ピペリジ
ル)セバケート、ジメチル−2−(4−ヒドロキシ−2,
2,6,6−テトラメチル−1−ピペリジル)エタノール、
1−〔2−3−(3,5−ジ−t−ブチル−4−ヒドロキ
シフエニル)プロピオニルオキシ〕−2,2,6,6−T−テ
トラメチルピペリジン等がある。
The ultraviolet absorber used in the compositions (A) and (B) of the present invention may be any as long as it is compatible with the resin used in the compositions (A) and (B).
High molecular weight UV absorbers are preferred. Examples of the absorbent include benzotriazoles, oxalic quats, benzophenones, hindered amines, and many other types of known absorbents. More specifically, 2- [3,5-di- (allophenyldimethylbenzyl-
2-hydroxyphenyl] benzotriazole, 2-
(3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 , 5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5
-Di-t-amyl-2-hydroxyphenyl) benzotriazole, 2-ethoxy-2'-ethyloxacid bisanilide, 2-ethoxy-5-t-butyl-
2'-Ethyl oxalic acid bisanilide, 2-hydroxy-4-n-octoxybenzophenone, bis (1,2,2,6,6-pentymethyl-4-piperidyl) sebacate, bis (1,2, 2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-2- (4-hydroxy-2,
2,6,6-tetramethyl-1-piperidyl) ethanol,
1- [2-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-T-tetramethylpiperidine and the like.

本発明の組成物に用いる有機顔料としては、一般的に
プラスチツクに用いられる有機顔料が使用できる。用い
られる有機顔料としては、例えばアゾ顔料としてモノア
ゾ顔料、ジスアゾ顔料、縮合アゾ顔料があり、多環系顔
料としてキナクリドン、ジオキサジン、イソインドリノ
ン、バツト系、フタロシアニン、アントラキノなどがあ
り、化学構造的に耐候性のすぐれた有機顔料を用いるこ
とが好ましい。これらの有機顔料は単独で用いてもよい
し、2種以上混合して用いてもよい。また若干量の無機
顔料も併用して使用できる。
As the organic pigment used in the composition of the present invention, an organic pigment generally used for plastics can be used. The organic pigments used include, for example, monoazo pigments, disazo pigments, and condensed azo pigments as azo pigments, and quinacridone, dioxazine, isoindolinone, buttoyl, phthalocyanine, anthraquino, and the like as polycyclic pigments. It is preferable to use an organic pigment having excellent weather resistance. These organic pigments may be used alone or in combination of two or more. Also, a small amount of inorganic pigments can be used in combination.

これらの顔料の具体例を表1に示すが本発明に使用し
うる有機顔料は、これらの例に限定されるものではな
い。
Specific examples of these pigments are shown in Table 1, but the organic pigments that can be used in the present invention are not limited to these examples.

本発明の顔料含有量は、PVDFおよびPMMAの合計量100
重量部に対して0.01〜20重量部である。
The pigment content of the present invention is a total amount of PVDF and PMMA of 100
It is 0.01 to 20 parts by weight based on parts by weight.

有機顔料での着色は、本発明フイルムの、少くとも1
層にて実施される。また2層以上を着色する場合は、同
一色にて着色しても異なつた色にて着色してもよい。
The coloring with the organic pigment is at least 1% of the film of the present invention.
Implemented in layers. When two or more layers are colored, they may be colored in the same color or different colors.

本発明の表面層及び裏面層となる組成物(A)の主成
分には、PVDF及びPMMAが用いられ、それぞれの含有量PV
DF100〜50重量部とPMMA0〜50重量部である。
PVDF and PMMA are used as the main components of the composition (A) to be the surface layer and the back layer according to the present invention.
100 to 50 parts by weight of DF and 0 to 50 parts by weight of PMMA.

PVDFの含有量が50重量部未満では、耐候性が低下する
ので好ましくない。
If the content of PVDF is less than 50 parts by weight, the weather resistance is undesirably reduced.

次に本発明の裏面層及び中間層となる組成物(B)の
主成分には、PVDF、PMMA及び紫外線吸収剤とが用いら
れ、PMMAは100〜50重量部、好ましくは95〜55重量部で
あり、PVDFは0〜50重量部、好ましくは5〜45重量部で
ある。PMMAの含有量が50重量部未満では、紫外線吸収剤
の分散が不十分となり好ましくない。
Next, PVDF, PMMA and an ultraviolet absorber are used as the main components of the composition (B) to be the back layer and the intermediate layer of the present invention, and PMMA is 100 to 50 parts by weight, preferably 95 to 55 parts by weight. And PVDF is 0 to 50 parts by weight, preferably 5 to 45 parts by weight. If the content of PMMA is less than 50 parts by weight, the dispersion of the ultraviolet absorber is insufficient, which is not preferable.

さらに紫外線吸収剤の含有量は、PMMA及びPVDF合計量
100重量部に対して0.1〜15重量部、好ましくは0.5〜5
重量部である。添加量が0.1重量部未満では、紫外線吸
収量が少ないので保護膜層としての性能が不十分とな
り、また15重量部を越えても効果は変わらなく、しかも
コストが高くなる。
Furthermore, the content of the UV absorber is the total amount of PMMA and PVDF.
0.1 to 15 parts by weight, preferably 0.5 to 5 parts by weight per 100 parts by weight
Parts by weight. If the addition amount is less than 0.1 part by weight, the performance as a protective film layer becomes insufficient due to a small amount of ultraviolet absorption, and if the addition amount exceeds 15 parts by weight, the effect remains unchanged and the cost increases.

本発明の組成物(A)及び組成物(B)には、酸化防
止剤、分散剤等を使用することもできる。本発明の着色
フイルムの厚さは、全体で200μm以下、好ましくは、1
0〜150μmの範囲である。さらに保護膜層としての性能
を発揮させるうえから、組成物(B)から作られたフイ
ルムがフイルム全体の20%以上を占めることが望まし
い。着色フイルムと貼り合せる基材のうち表面処理され
る基材の形状は特に制限はないが、ポリ塩化ビニル等の
プラスチツクの場合は一般的にフイルム、シート、及び
板状のものにラミネートして使用され、基材の厚み等に
制限はない。
In the composition (A) and the composition (B) of the present invention, an antioxidant, a dispersant and the like can be used. The thickness of the colored film of the present invention is 200 μm or less in total, preferably 1 μm.
The range is from 0 to 150 μm. Further, from the viewpoint of exhibiting the performance as a protective film layer, it is desirable that the film made of the composition (B) accounts for 20% or more of the entire film. There is no particular limitation on the shape of the substrate to be surface-treated among the substrates to be bonded to the colored film, but in the case of a plastic such as polyvinyl chloride, it is generally used by laminating it on a film, sheet, or plate. The thickness of the substrate is not limited.

さらに本発明の着色フイルムは、表面層に印刷処理等
をほどこして各種用途に使用出来る事はいうまでもな
い。また、本発明における着色フイルムと各種基材との
接着には、エポキシ樹脂系、アクリル樹脂系、ウレタン
樹脂系等の一般的接着剤を使用できるし、天然ゴム、ア
クリル樹脂系等を使用した感圧性接着剤をあらかじめ着
色フイルムの接着面に塗布しておいて使用できる他、基
材の種類によつては熱加工のみによつても接着する事が
できる。
Further, needless to say, the colored film of the present invention can be used for various applications by subjecting the surface layer to printing treatment or the like. In addition, a general adhesive such as an epoxy resin, an acrylic resin, or a urethane resin can be used for adhesion between the colored film and various substrates in the present invention, and a natural rubber, an acrylic resin, or the like can be used. The pressure-sensitive adhesive can be used by applying it to the adhesive surface of the colored film in advance, or it can be bonded only by heat processing depending on the type of the base material.

次に本発明のフツ素樹脂系着色フイルムは、通常複数
の層を一体に結合する共押出成形法を用いて押出するこ
とができる。
Next, the fluororesin-based colored film of the present invention can be usually extruded using a coextrusion molding method in which a plurality of layers are integrally bonded.

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、接触させて接着する方法と、複数の樹脂
を接着後、シート状に拡げる方法がある。またインフレ
ーシヨン成形法と称し、丸型ダイを使用する方法でも多
層フイルムが成形できる。
Using a T-die to bond the resin in a molten state using multiple extruders to form a multilayer. The co-extrusion molding method is called a multi-manifold die. There is a method of bonding by bonding, and a method of bonding a plurality of resins and then spreading them in a sheet shape. Also, a multilayer film can be formed by a method using a round die, which is called an inflation molding method.

また別な方法としては、単層フイルム成形機を使用
し、組成物(A)及び(B)を用いてそれぞれの単相フ
イルムを作成後、熱ラミネーシヨンによつて組成物
(A)及び(B)からなる着色フイルム積層体を作成し
てもよい。
As another method, a single-layer film forming machine is used to form each single-phase film using the compositions (A) and (B), and then the compositions (A) and ( A colored film laminate comprising B) may be prepared.

PVDFとPMMAを樹脂成分とする層に有機系顔料、及び紫
外線吸収剤等の添加剤を混入する方法としては、樹脂と
添加剤をあらかじめ混合しておき一般に使用される単軸
押出機を使用して溶融混練する方法でもよいが、一般に
は添加剤の樹脂中への分散が十分でなく、高混練タイプ
の2軸押出機を使用すると表面状態の優れた原料を提供
する事が出来る。
As a method of mixing additives such as an organic pigment and an ultraviolet absorber into a layer containing PVDF and PMMA as a resin component, a resin and additives are mixed in advance, and a commonly used single screw extruder is used. Although the method of melt-kneading may be used, the dispersing of the additive in the resin is generally insufficient, and a high-kneading type twin-screw extruder can provide a raw material having an excellent surface state.

(実施例) 本発明を実施例及び比較例にてさらに詳しく説明する
が、本発明はこれらに限定されるものではない。
(Examples) The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

実施例1 〔表面層フイルム原料組成物(A)の調整〕 ソルベイ社ポリフツ化ビニリデン商品名「ソーレフ10
10」70重量部、三菱レイヨン(株)社メタクリル酸エス
テル系樹脂商品名「アクリペツトMD」15重量部、旭化成
工業(株)社メタクリル酸エステル系樹脂商品名「デル
ペツトSR−6500」15重量部をミキシングした後、2軸混
練押出機で混練し、コンパウンドとした。
Example 1 [Preparation of Surface Layer Film Raw Material Composition (A)] Solef 10 (vinylidene fluoride trade name, Solef 10)
10 "70 parts by weight, Mitsubishi Rayon Co., Ltd. methacrylate ester resin trade name" Acrypet MD "15 parts by weight, Asahi Chemical Industry Co., Ltd. methacrylate ester resin trade name" Delpet SR-6500 "15 parts by weight. After mixing, the mixture was kneaded with a twin-screw kneading extruder to obtain a compound.

〔裏面層フイルム原料組成物(B)の調整〕[Preparation of back layer film raw material composition (B)]

ソルベイ社ポリフツ化ビニリデン商品名「ソーレフ10
10」30重量部、三菱レイヨン(株)社メタクリル酸エス
テル系樹脂商品名「アクリペツトMD」35重量部、旭化成
工業(株)社メタクリル酸エステル系樹脂商品名「デル
ペツトSR−6500」35重量部、紫外線吸収剤として2−ヒ
ドロキシ−4−オクトオキシベンゾフエノン3重量部及
び縮合アゾ系顔料(C.I.ピグメントナンバーイエロー9
3)1重量部をミキシングした後、2軸混練押出機で混
練し、コンパウンドとした。
Solvay polyvinylidene fluoride
10 "30 parts by weight, Mitsubishi Rayon Co., Ltd. methacrylate ester resin trade name" Acrypet MD "35 parts by weight, Asahi Kasei Kogyo Co., Ltd. methacrylate ester resin trade name" Delpet SR-6500 "35 parts by weight, As an ultraviolet absorber, 3 parts by weight of 2-hydroxy-4-octoxybenzophenone and a condensed azo pigment (CI Pigment Number Yellow 9)
3) After mixing 1 part by weight, the mixture was kneaded with a twin-screw kneading extruder to obtain a compound.

次に調整した2種類のコンパウンドを原料とし、40mm
φ押出機2台、フイードブロツクダイ、スリツト幅0.4m
m、幅450mmのコートハンガーダイを備えた装置を使用し
て共押出成形し、表2に示す2層構成フイルムを得た。
得られたフイルムの試験結果を表2に示した。
Next, use the adjusted two kinds of compounds as raw materials, 40mm
φ2 extruders, feed block die, slit width 0.4m
Co-extrusion was performed using an apparatus equipped with a coat hanger die having a width of 450 mm and a width of 450 mm to obtain a two-layer film shown in Table 2.
Table 2 shows the test results of the obtained films.

実施例2 実施例1のフイルム原料組成物(B)の紫外線吸収剤
を2−(3,5−ジ−t−ブチル−2−ヒドロキシフエニ
ル)−5−クロロベンゾトリアゾールに変え、ベンジジ
ンレツド顔料(C.I.ピグメントナンバーレツド38)2重
量部を用いた以外は実施例1と同様に行つた。結果を表
2に示す。
Example 2 The UV absorber of the film raw material composition (B) of Example 1 was changed to 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, and a benzidine red was used. The procedure was performed in the same manner as in Example 1 except that 2 parts by weight of a pigment (CI Pigment Number Red 38) was used. Table 2 shows the results.

実施例3 実施例1のフイルム原料組成物(B)においてベンズ
イミダゾロン顔料(C.I.ピグメントナンバーオレンジ3
6)2重量部を用いた以外は実施例1と同様に行つた。
結果を表2に示す。
Example 3 In the film raw material composition (B) of Example 1, a benzimidazolone pigment (CI Pigment Number Orange 3) was used.
6) The procedure was performed in the same manner as in Example 1 except that 2 parts by weight was used.
Table 2 shows the results.

実施例4 実施例1のフイルム原料(A)において紫外線吸収剤
として2−ヒドロキシ−4−n−オクトオキシベンゾフ
エノン3重量部及びジオキサジン顔料(C.I.ピグメント
ナンバーバイオレツト23)1重量部を用い、フイルム原
料(B)において前記ジオキサジン顔料1重量部を用い
た以外は実施例1と同様に行つた。結果を表2に示す。
Example 4 In the film raw material (A) of Example 1, 3 parts by weight of 2-hydroxy-4-n-octoxybenzophenone and 1 part by weight of a dioxazine pigment (CI Pigment Number Violet 23) were used as an ultraviolet absorber. Example 1 was repeated except that 1 part by weight of the dioxazine pigment was used in the film raw material (B). Table 2 shows the results.

実施例5 〔表面層及び裏面層フイルム原料組成物(A)の調整〕 ソルベイ社ポリフツ化ビニリデン商品名「ソーレフ10
10」80重量部、三菱レイヨン(株)社メタクリル酸エス
テル系樹脂商品名「アクリペツトMD」10重量部、旭化成
工業(株)社メタクリル酸エステル系樹脂商品名「デル
ペツトSR−6500」10重量部をミキシングした後、2軸混
練押出機で混練し、コンパウンドとした。
Example 5 [Preparation of raw material composition (A) for front layer and back layer film] Solef 10 polyvinylidene fluoride trade name "SOLEF 10
10 "80 parts by weight, Mitsubishi Rayon Co., Ltd. methacrylate ester resin trade name" Acrypet MD "10 parts by weight, Asahi Kasei Kogyo Co., Ltd. methacrylate ester resin trade name" Delpet SR-6500 "10 parts by weight. After mixing, the mixture was kneaded with a twin-screw kneading extruder to obtain a compound.

〔中間層フイルム原料組成物(B)の調整〕[Preparation of intermediate layer film raw material composition (B)]

ソルベイ社ポリフツ化ビニリデン商品名「ソーレフ10
10」50重量部、三菱レイヨン(株)社メタクリル酸エス
テル系樹脂商品名「アクリペツトMD」25重量部、旭化成
工業(株)社メタクリル酸エステル系樹脂商品名「デル
ペツトSR−6500」25重量部、紫外線吸収剤として2−ヒ
ドロキシ−4−n−オクトオキシベンゾフエノン3重量
部及びフタロシアニン顔料(C.I.ピグメントナンバーブ
ルー15)2重量部をミキシングした後、2軸混練押出機
で混練しコンパウンドとした。
Solvay polyvinylidene fluoride
10 "50 parts by weight, Mitsubishi Rayon Co., Ltd. methacrylate ester resin trade name" Acrypet MD "25 parts by weight, Asahi Kasei Kogyo Co., Ltd. methacrylate ester resin trade name" Delpet SR-6500 "25 parts by weight, After mixing 3 parts by weight of 2-hydroxy-4-n-octoxybenzophenone as an ultraviolet absorber and 2 parts by weight of a phthalocyanine pigment (CI Pigment Number Blue 15), the mixture was kneaded with a twin-screw kneading extruder to obtain a compound.

次に40mmφ押出機3台およびフイードブロツクダイ、
更に幅450mmスリツト幅0.3mmのコートハンガータイプを
使用して3層共押出成形を行なつた。結果を表2に示
す。
Next, three 40mmφ extruders and a feed block die,
Further, three-layer coextrusion molding was performed using a coat hanger type having a width of 450 mm and a slit width of 0.3 mm. Table 2 shows the results.

比較例1 表面層として実施例1のフイルム原料組成物(A)
を、裏面層として紫外線吸収剤を含有しない実施例1の
フイルム原料組成物(B)を用いた以外は、実施例1と
同様な操作を行つた。結果を表2に示す。
Comparative Example 1 The film raw material composition of Example 1 (A) was used as a surface layer.
Was performed in the same manner as in Example 1 except that the film raw material composition (B) of Example 1 containing no ultraviolet absorber was used as the back layer. Table 2 shows the results.

比較例2 表面層及び裏面層として実施例4のフイルム原料組成
物(A)を中間層として紫外線吸収剤を含有しない実施
例4のフイルム原料組成物(B)を用いた以外は、実施
例4と同様な操作を行つた。結果を表2に示す。
Comparative Example 2 Example 4 was repeated except that the film raw material composition (A) of Example 4 was used as the intermediate layer, and the film raw material composition (B) of Example 4 containing no ultraviolet absorber was used as the intermediate layer. The same operation was performed. Table 2 shows the results.

応用例 実施例1〜5を比較例1〜2の耐候フイルムを用いて
該耐候フイルム裏面層と白色塩化ビニル樹脂板(以下PV
C板という)、Zn鋼板とをそれぞれ接着し、物性を測定
した。結果を表2に示す。
Application Examples Examples 1 to 5 were prepared using the weatherproof films of Comparative Examples 1 and 2 and the backside layer of the weatherproof film and a white vinyl chloride resin plate (hereinafter referred to as PV).
C plate) and a Zn steel plate, respectively, and their physical properties were measured. Table 2 shows the results.

試験方法 1)フイルム厚さ:1/1000mm目盛のピーコツク厚さ計を
使用して測定した。なお2層構成の場合の上層と下層の
厚さは各押出機の押出量比より計算した。
Test method 1) Film thickness: Measured using a Peacock thickness gauge with a scale of 1/1000 mm. In addition, the thickness of the upper layer and the lower layer in the case of a two-layer configuration was calculated from the extrusion rate of each extruder.

2)耐薬品性 :フイルム上層に滴定し、室温(23
℃)24時間後の外観を肉眼で判定した。使用薬品:10%H
Cl、10%H2SO410%CaCl2、10%N2OH 全く変化ないもの:○ 軽微な変化 :△ 3)耐 候 性: サンシヤインウエザーメーター法に
よる促進試験 ブラツクパネル63℃、スプレー有 1000時間経過時にブランクサンプルと比較し、色差
(ΔE)及び光沢保持率(GR)を測定した。色差及び光
沢はJIS K7105に準じた。
2) Chemical resistance: Titration on the film upper layer, room temperature (23
° C) The appearance after 24 hours was visually judged. Chemicals used: 10% H
Cl, 10% H 2 SO 4 10% CaCl 2 , 10% N 2 OH No change: ○ Minor change: △ 3) Weather resistance: Acceleration test by sunshine weather meter method Black panel 63 ° C, spray After 1000 hours, color difference (ΔE) and gloss retention (GR) were measured by comparing with blank sample. The color difference and gloss conformed to JIS K7105.

4)接着耐久性 :基材と接着したフイルム側にゴバン
目を入れサンシヤインウエザーメーター法で試験し、10
00時間経過後、ゴバン目、セロテープ剥離試験した。
4) Adhesive durability: A test was conducted with a sunshine weather meter method by inserting a gobang on the side of the film adhered to the substrate,
After a lapse of 00 hours, a peeling test was performed on a scotch tape and a cellophane tape.

剥離が全くないもの:100/100 全部剥離したもの:0/100 5)基材との接着:基材が0.5mm PVC板の場合は熱接
着、温度140−180℃、基材が金属板の場合ウレタン系接
着剤使用し、いずれもロールラミネーターで熱接着し
た。
No peeling: 100/100 Fully peeled: 0/100 5) Adhesion to base material: When the base material is 0.5 mm PVC plate, heat bonding, temperature 140-180 ° C, base material is metal plate In each case, a urethane-based adhesive was used, and all were thermally bonded with a roll laminator.

(発明の効果) 以上の説明からも明らかな様に、本発明によつて得ら
れるフツ素樹脂系着色フイルムは、装飾性や耐薬品性に
すぐれ、しかもフツ化ビニリデン樹脂の有する優れた長
期耐候性をそなえ、加えて基材との接着性が長期にわた
り低下しない特徴を有している。したがつて建築物の内
外装、とりわけ直照日光の影響が厳しい外装用途に有効
に使用できる。
(Effects of the Invention) As is clear from the above description, the fluororesin-based colored film obtained by the present invention has excellent decorative properties and chemical resistance, and also has excellent long-term weather resistance of vinylidene fluoride resin. In addition, it has the characteristic that the adhesiveness with the base material does not decrease for a long time. Therefore, it can be effectively used for the interior and exterior of buildings, especially exterior applications where the influence of direct sunlight is severe.

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6,DB名) B32B 1/00 - 35/00──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. 6 , DB name) B32B 1/00-35/00

Claims (4)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】フツ化ビニリデン系樹脂100〜50重量部及
びメタクリル酸エステル系樹脂0〜50重量部及び紫外線
吸収剤0〜15重量部を主成分とする組成物(A)を表面
層とし、メタクリル酸エステル系樹脂95〜55重量部、フ
ツ化ビニリデン系樹脂5〜45重量部及び紫外線吸収剤0.
1〜15重量部を主成分とする組成物(B)を裏面層とす
る少なくとも1層が有機顔料で着色されたフツ素樹脂系
着色フイルム。
1. A surface layer comprising a composition (A) comprising 100 to 50 parts by weight of a vinylidene fluoride resin, 0 to 50 parts by weight of a methacrylate resin and 0 to 15 parts by weight of an ultraviolet absorber as main components, 95 to 55 parts by weight of a methacrylate resin, 5-45 parts by weight of a vinylidene fluoride resin and an ultraviolet absorber
A fluororesin-based colored film having at least one layer colored with an organic pigment, the composition having a composition (B) containing 1 to 15 parts by weight as a main component.
【請求項2】フツ化ビニリデン系樹脂100〜50重量部及
びメタクリル酸エステル系樹脂0〜50重量部及び紫外線
吸収剤0〜15重量部を主成分とする組成物(A)を表面
層及び裏面層とし、メタクリル酸エステル系樹脂95〜55
重量部、フツ化ビニリデン系樹脂5〜45重量部及び紫外
線吸収剤0.1〜15重量部を主成分とする組成物(B)を
中間層とする少なくとも1層が有機顔料で着色されたフ
ツ素樹脂系着色フイルム。
2. A composition comprising a composition (A) containing 100 to 50 parts by weight of a vinylidene fluoride resin, 0 to 50 parts by weight of a methacrylate ester resin and 0 to 15 parts by weight of an ultraviolet absorber as a main component. Layer, methacrylate resin 95-55
Fluorine resin in which at least one layer having a composition (B) as an intermediate layer, which is mainly composed of 5 parts by weight, 5 to 45 parts by weight of vinylidene fluoride resin and 0.1 to 15 parts by weight of an ultraviolet absorber, is colored with an organic pigment System colored film.
【請求項3】フツ化ビニリデン系樹脂100〜50重量部及
びメタクリル酸エステル系樹脂0〜50重量部及び紫外線
吸収剤0〜15重量部を主成分とする組成物(A)を表面
層とし、メタクリル酸エステル系樹脂95〜55重量部、フ
ツ化ビニリデン系樹脂5〜45重量部及び紫外線吸収剤0.
1〜15重量部を主成分とする組成物(B)を裏面層とす
る少なくとも1層が有機顔料で着色されたフツ素樹脂系
着色フイルムを共押出成形法又は熱ラミネーションで製
造することを特徴とするフツ素樹脂系着色フイルムの製
造方法。
3. A surface layer comprising a composition (A) comprising 100 to 50 parts by weight of a vinylidene fluoride resin, 0 to 50 parts by weight of a methacrylate resin and 0 to 15 parts by weight of an ultraviolet absorber as main components. 95 to 55 parts by weight of a methacrylate resin, 5-45 parts by weight of a vinylidene fluoride resin and an ultraviolet absorber
It is characterized in that a fluororesin-based colored film in which at least one layer having a composition (B) containing 1 to 15 parts by weight as a main component and a back layer is colored with an organic pigment is produced by a coextrusion molding method or thermal lamination. Of producing a fluororesin-based colored film.
【請求項4】フツ化ビニリデン系樹脂100〜50重量部及
びメタクリル酸エステル系樹脂0〜50重量部及び紫外線
吸収剤0〜15重量部を主成分とする組成物(A)を表面
層及び裏面層とし、メタクリル酸エステル系樹脂95〜55
重量部、フツ化ビニリデン系樹脂5〜45重量部及び紫外
線吸収剤0.1〜15重量部を主成分とする組成物(B)を
中間層とする少なくとも1層が有機顔料で着色されたフ
ツ素樹脂系着色フイルムを共押出成形法又は熱ラミネー
ションで製造することを特徴とするフツ素樹脂系着色フ
イルムの製造方法。
4. A composition comprising a composition (A) comprising 100 to 50 parts by weight of a vinylidene fluoride resin, 0 to 50 parts by weight of a methacrylate ester resin and 0 to 15 parts by weight of an ultraviolet absorber as a main component. Layer, methacrylate resin 95-55
Fluorine resin in which at least one layer having a composition (B) as an intermediate layer, which is mainly composed of 5 parts by weight, 5 to 45 parts by weight of vinylidene fluoride resin and 0.1 to 15 parts by weight of an ultraviolet absorber, is colored with an organic pigment A method for producing a fluororesin-based colored film, wherein the colored film is produced by a coextrusion molding method or thermal lamination.
JP1150616A 1989-06-15 1989-06-15 Fluororesin-based colored film and method for producing the same Expired - Fee Related JP2788756B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1150616A JP2788756B2 (en) 1989-06-15 1989-06-15 Fluororesin-based colored film and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1150616A JP2788756B2 (en) 1989-06-15 1989-06-15 Fluororesin-based colored film and method for producing the same

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Publication Number Publication Date
JPH0316730A JPH0316730A (en) 1991-01-24
JP2788756B2 true JP2788756B2 (en) 1998-08-20

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Country Link
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010120386A (en) * 2002-04-18 2010-06-03 Three M Innovative Properties Co Fluoropolymer article

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