JPH05117416A - Vinyl chloride resin film excellent in heat resistance and flame retardancy - Google Patents
Vinyl chloride resin film excellent in heat resistance and flame retardancyInfo
- Publication number
- JPH05117416A JPH05117416A JP28133791A JP28133791A JPH05117416A JP H05117416 A JPH05117416 A JP H05117416A JP 28133791 A JP28133791 A JP 28133791A JP 28133791 A JP28133791 A JP 28133791A JP H05117416 A JPH05117416 A JP H05117416A
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- vinyl chloride
- resin film
- pts
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性及び難燃性にす
ぐれる塩化ビニル系樹脂フイルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin film having excellent heat resistance and flame retardancy.
【０００２】[0002]
【従来の技術】塩化ビニル系樹脂からなるフイルムは、
従来、産業分野に広く用いられており、特に、耐熱性を
有するそのようなフイルムは、電気用途に広く用いられ
ている。しかし、それらは、殆どが可塑剤を含む軟質塩
化ビニル系樹脂からなるので、耐熱性及び難燃性は不十
分である。2. Description of the Related Art Films made of vinyl chloride resin are
Heretofore, it has been widely used in the industrial field, and in particular, such a film having heat resistance is widely used for electric applications. However, since most of them consist of a soft vinyl chloride resin containing a plasticizer, their heat resistance and flame retardancy are insufficient.
【０００３】そこで、従来、耐熱老化性を与えるため
に、可塑剤として非移行性のトリメリツト酸トリオクチ
ルを配合したり、或いは難燃性を有せしめるために、三
酸化アンチモンを配合してなる塩化ビニル系樹脂フイル
ムが知られている。しかし、トリメリツト酸トリオクチ
ルを可塑剤として用いても、長期熱老化後には、可塑剤
が揮発し、硬度が増すので、実用性に欠けることとな
る。また、トリクレジルホスフエートのような液状難燃
剤も、長期熱老化によつて揮発し、同様の問題を生じ
る。Therefore, conventionally, non-migrating trioctyl trimellitate as a plasticizer has been blended in order to impart heat aging resistance, or antimony trioxide has been blended in order to impart flame retardance to vinyl chloride. A resin film is known. However, even if trioctyl trimellitate is used as a plasticizer, the plasticizer is volatilized and the hardness increases after long-term heat aging, so that it is not practical. Liquid flame retardants such as tricresyl phosphate also volatilize due to long term heat aging, causing similar problems.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記した問
題を解決するためになされたものであつて、耐熱性及び
難燃性にすぐれる塩化ビニル系樹脂フイルムを提供する
ことを目的とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a vinyl chloride resin film having excellent heat resistance and flame retardancy. ..
【０００５】[0005]
【課題を解決するための手段】本発明による耐熱性及び
難燃性にすぐれる塩化ビニル系樹脂フイルムは、ポリ塩
化ビニル−ポリウレタン共重合樹脂１００重量部につい
て、エチレン−酢酸ビニル共重合体１〜５０重量部と水
酸化アルミニウム２０〜２００重量部と三酸化アンチモ
ン１〜１５重量部とカツプリング剤0.１〜５重量部と三
塩基性硫酸鉛５〜１５重量部とを含む樹脂組成物からな
ることを特徴とする。A vinyl chloride resin film excellent in heat resistance and flame retardancy according to the present invention is obtained by using ethylene-vinyl acetate copolymer 1 to 100 parts by weight of polyvinyl chloride-polyurethane copolymer resin. A resin composition containing 50 parts by weight, 20 to 200 parts by weight of aluminum hydroxide, 1 to 15 parts by weight of antimony trioxide, 0.1 to 5 parts by weight of a coupling agent, and 5 to 15 parts by weight of tribasic lead sulfate. It is characterized by
【０００６】本発明による耐熱性及び難燃性にすぐれる
塩化ビニル系樹脂フイルムは、基材樹脂がポリ塩化ビニ
ル−ポリウレタン共重合樹脂からなる。ポリ塩化ビニル
−ポリウレタン共重合樹脂は、塩化ビニル単量体に熱可
塑性ポリウレタンを溶解させ、懸濁重合させて得られる
ポリ塩化ビニルグラフトポリウレタン共重合体（例え
ば、特開昭５８−４０３１２号公報、特開昭５８−４２
６１１号公報、特開昭５８−３７０１９号公報等に記載
されている。）、固体ポリ塩化ビニルにポリオールを含
浸させ、次いで、これにポリイソシアネートを加えて、
固体ポリ塩化ビニル中でポリウレタンを生成させてなる
共重合体（例えば、特公昭５９−３９４６４号公報等に
記載されている。）、ポリ塩化ビニル、ポリオール及び
ポリイソシアネートの混合物を加熱溶融して、ポリウレ
タンを生成させてなる共重合体（例えば、特開昭６２−
１７１５号公報、特開昭６３−２５１４１３号公報等に
記載されている。）等をいう。In the vinyl chloride resin film excellent in heat resistance and flame retardancy according to the present invention, the base resin is a polyvinyl chloride-polyurethane copolymer resin. The polyvinyl chloride-polyurethane copolymer resin is a polyvinyl chloride graft polyurethane copolymer obtained by dissolving thermoplastic polyurethane in a vinyl chloride monomer and subjecting it to suspension polymerization (for example, JP-A-58-40312, JP-A-58-42
No. 611, JP-A-58-37019 and the like. ), Impregnating solid polyvinyl chloride with a polyol, and then adding polyisocyanate thereto,
A copolymer obtained by forming polyurethane in solid polyvinyl chloride (for example, described in JP-B-59-39464), a mixture of polyvinyl chloride, a polyol and a polyisocyanate is melted by heating, Copolymers produced from polyurethane (see, for example, JP-A-62-
1715, JP-A-63-251413, and the like. ) Etc.
【０００７】例えば、特開昭６３−２５１４１３号公報
には、ポリ塩化ビニル粉末とヘキサメチレンジイソシア
ネートとを含む混合物にポリエステルポリオールを加
え、加熱溶融下に反応させて、ポリ塩化ビニル−ポリウ
レタン共重合樹脂を得る方法が記載されている。本発明
においては、特に、かかるポリウレタン−ポリ塩化ビニ
ルグラフト共重合体が好適に用いられる。For example, in Japanese Patent Laid-Open No. 63-251413, a polyester polyol is added to a mixture containing polyvinyl chloride powder and hexamethylene diisocyanate, and the mixture is reacted while heating and melting to give a polyvinyl chloride-polyurethane copolymer resin. A method of obtaining is described. In the present invention, such a polyurethane-polyvinyl chloride graft copolymer is particularly preferably used.
【０００８】また、このようなポリ塩化ビニル−ポリウ
レタン共重合樹脂は、市販品として入手することができ
る。例えば、東ソー（株）から「ドミナス」として市販
されているポリ塩化ビニル−ポリウレタン共重合樹脂
は、本発明において好適に用いることができる。本発明
による塩化ビニル系樹脂フイルムは、基材樹脂としてか
かるポリ塩化ビニル−ポリウレタン共重合樹脂を用いる
ものであつて、可塑剤を含まないながら、ポリウレタン
が可塑剤の役割を果たすので、半硬質の性質を有する。Further, such a polyvinyl chloride-polyurethane copolymer resin can be obtained as a commercial product. For example, a polyvinyl chloride-polyurethane copolymer resin commercially available from Tosoh Corporation as "Dominus" can be preferably used in the present invention. The vinyl chloride resin film according to the present invention uses such a polyvinyl chloride-polyurethane copolymer resin as a base resin, and since it does not contain a plasticizer, the polyurethane plays a role of a plasticizer, and thus is a semi-rigid resin. It has the property.
【０００９】本発明による塩化ビニル系樹脂フイルム
は、上記したようなポリ塩化ビニル−ポリウレタン共重
合樹脂１００重量部について、エチレン−酢酸ビニル共
重合体１〜５０重量部、好ましくは１０〜３０重量部を
含む。エチレン−酢酸ビニル共重合体は、常温で固体で
あるので、高温環境下にあつても、フイルムから揮発す
ることなく、フイルムの伸びを保持する。特に、本発明
においては、エチレン−酢酸ビニル共重合体は、酢酸ビ
ニル含量が５〜８５重量％の範囲にあるものが好適に用
いられる。The vinyl chloride resin film according to the present invention contains 1 to 50 parts by weight, preferably 10 to 30 parts by weight, of an ethylene-vinyl acetate copolymer based on 100 parts by weight of the above polyvinyl chloride-polyurethane copolymer resin. including. Since the ethylene-vinyl acetate copolymer is a solid at room temperature, it does not evaporate from the film even under a high temperature environment and retains the elongation of the film. In particular, in the present invention, the ethylene-vinyl acetate copolymer having a vinyl acetate content of 5 to 85% by weight is preferably used.
【００１０】本発明においては、難燃剤として、水酸化
アルミニウムと三酸化アンチモンとが用いられる。これ
らはいずれも粉末であつて、難燃効果にすぐれる。ポリ
塩化ビニル−ポリウレタン共重合樹脂１００重量部につ
いて、水酸化アルミニウム２０〜２００重量部、好まし
くは５０〜１００重量部と、三酸化アンチモン１〜１５
重量部、好ましくは５〜１５重量部とが用いられる。In the present invention, aluminum hydroxide and antimony trioxide are used as the flame retardant. All of them are powders and have excellent flame retardant effect. 20 to 200 parts by weight of aluminum hydroxide, preferably 50 to 100 parts by weight, and antimony trioxide 1 to 15 per 100 parts by weight of polyvinyl chloride-polyurethane copolymer resin.
Parts by weight, preferably 5 to 15 parts by weight are used.
【００１１】しかし、一般に、このような無機粉末を塩
化ビニル系樹脂に多量に配合するときは、樹脂における
分散が悪く、フイルムの物性にばらつきが大きい。そこ
で、本発明によれば、ポリ塩化ビニル−ポリウレタン共
重合樹脂１００重量部について、カツプリング剤0.１〜
５重量部を配合し、これによつて上記無機難燃剤粉末の
樹脂への高充填を実現することができる。即ち、カツプ
リング剤は、無機難燃剤粉末の分散性を高め、得られる
フイルムの伸びを低下させることなく、上述したような
難燃剤である水酸化アルミニウムと三酸化アンチモンの
粉末の高充填を可能とする。However, in general, when a large amount of such an inorganic powder is mixed with a vinyl chloride resin, the dispersion in the resin is poor and the physical properties of the film vary widely. Therefore, according to the present invention, the coupling agent 0.1 to 100 parts by weight of polyvinyl chloride-polyurethane copolymer resin is used.
By blending 5 parts by weight, the resin can be highly filled with the above inorganic flame retardant powder. That is, the coupling agent enhances the dispersibility of the inorganic flame retardant powder, and does not reduce the elongation of the obtained film, and enables high filling of the above-described flame retardant aluminum hydroxide and antimony trioxide powder. To do.
【００１２】上記カツプリング剤としては、アルミニウ
ムカツプリング剤又はチタネート系カツプリング剤が用
いられる。アルミニウムカツプリング剤としては、例え
ば、アセトアルコキシアルミニウムジイソプロピレート
を挙げることができ、また、チタネート系カツプリング
剤としては、例えば、イソプロピルトリステアロイルチ
タネート、イソプロピルトリス（ジオクチルパイロホス
フエート）チタネート等を挙げることができる。An aluminum coupling agent or a titanate coupling agent is used as the coupling agent. Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate, and examples of the titanate coupling agent include isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate and the like. You can
【００１３】また、前述したエチレン−酢酸ビニル共重
合体も、無機材料の高充填を高める作用を有し、カツプ
リング剤と共同して、無機難燃剤粉末の高充填を可能と
する。そのうえ、エチレン−酢酸ビニル共重合体は、原
料塩化ビニル系樹脂の配合物の混練性を高めるので、得
られるフイルムは、表面の平滑性にすぐれる。また、従
来は、無機粉末を前述したように高充填すれば、塩化ビ
ニル系樹脂フイルムの特有の表面の風合が失われるが、
本発明によれば、エチレン−酢酸ビニル共重合体が柔軟
性を保持させるので、得られる樹脂フイルムは、軟質塩
化ビニル系樹脂フイルムが有する風合と殆ど同じ風合を
有する。Further, the above-mentioned ethylene-vinyl acetate copolymer also has an effect of increasing the high filling of the inorganic material, and in cooperation with the coupling agent, enables the high filling of the inorganic flame retardant powder. In addition, the ethylene-vinyl acetate copolymer enhances the kneadability of the blend of the raw material vinyl chloride resin, so that the obtained film has excellent surface smoothness. Further, conventionally, if the inorganic powder is highly filled as described above, the texture of the surface peculiar to the vinyl chloride resin film is lost,
According to the present invention, since the ethylene-vinyl acetate copolymer retains flexibility, the obtained resin film has almost the same feeling as that of the soft vinyl chloride resin film.
【００１４】更に、本発明による塩化ビニル系樹脂フイ
ルムは、静的熱安定性を高めるために、ポリ塩化ビニル
−ポリウレタン共重合樹脂１００重量部について、三塩
基性硫酸鉛を５〜１５重量部含有する。また、本発明に
おいては、塩化ビニル系樹脂フイルムの耐候性を高めら
れるために紫外線吸収剤、耐衝撃性を改良するためにＭ
ＢＳ樹脂、加工性を改善するために加工助剤、安定剤、
滑剤や、顔料等を配合することができる。Further, the vinyl chloride resin film according to the present invention contains 5 to 15 parts by weight of tribasic lead sulfate per 100 parts by weight of polyvinyl chloride-polyurethane copolymer resin in order to enhance static thermal stability. To do. Further, in the present invention, the weather resistance of the vinyl chloride resin film can be increased, so that an ultraviolet absorber can be used, and in order to improve the impact resistance, M
BS resin, processing aids, stabilizers to improve processability,
Lubricants, pigments and the like can be added.
【００１５】本発明による塩化ビニル系樹脂フイルム
は、厚さにおいて特に限定されるものではないが、通
常、0.０５〜0.５mmの範囲が好適である。The thickness of the vinyl chloride resin film according to the present invention is not particularly limited, but a range of 0.05 to 0.5 mm is usually preferable.
【００１６】[0016]
【発明の効果】本発明による塩化ビニル系樹脂フイルム
は、以上のように、ポリ塩化ビニル−ポリウレタン共重
合樹脂を基材樹脂とし、これと共にエチレン−酢酸ビニ
ル共重合体を含むので、高温環境下においても柔軟性又
は弾性を保持しており、他方において、無機難燃剤粉末
の充填能力にすぐれるエチレン−酢酸ビニル共重合体と
共にカツプリング剤を含有するので、無機難燃剤粉末を
高充填しつつ、伸びを保持することができる。従つて、
本発明による塩化ビニル系樹脂フイルムは、耐熱老化性
及び難燃性にすぐれる。As described above, the vinyl chloride resin film according to the present invention has the polyvinyl chloride-polyurethane copolymer resin as the base resin and the ethylene-vinyl acetate copolymer together with the polyvinyl chloride-polyurethane copolymer resin. Also holds flexibility or elasticity, on the other hand, since it contains a coupling agent with an ethylene-vinyl acetate copolymer excellent in the filling ability of the inorganic flame retardant powder, while highly filling the inorganic flame retardant powder, Elongation can be maintained. Therefore,
The vinyl chloride resin film according to the present invention has excellent heat aging resistance and flame retardancy.
【００１７】[0017]
【実施例】以下に実施例及び比較例を挙げて本発明を説
明するが、本発明はこれら実施例により何ら限定される
ものではない。表１及び表２に示す組成を有し、厚み0.
１６mmの塩化ビニル系樹脂フイルムをカレンダー成形
し、熱老化前後の物性を調べた。結果を表１及び表２に
示す。ポリ塩化ビニル−ポリウレタン共重合樹脂として
は、東ソー（株）製ドミナスＫ−８００Ｃを、エチレン
−酢酸ビニル共重合体としては、大日本インキ化学工業
（株）製エバスレン４５０Ｐを、また、カツプリング剤
としては、アセトアルコキシアルミニウムジイソプロピ
レート（味の素（株）製ＡＬ−Ｍ）をそれぞれ用いた。The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. It has the composition shown in Table 1 and Table 2 and has a thickness of 0.
A 16 mm vinyl chloride resin film was calendered and the physical properties before and after heat aging were examined. The results are shown in Tables 1 and 2. As polyvinyl chloride-polyurethane copolymer resin, Dominus K-800C manufactured by Tosoh Corporation, as ethylene-vinyl acetate copolymer, Ebaslen 450P manufactured by Dainippon Ink and Chemicals, Inc., and as a coupling agent. Used acetoalkoxy aluminum diisopropylate (AL-M manufactured by Ajinomoto Co., Inc.).
【００１８】伸びは、幅１９mm、長さ１５０mmの試料フ
イルムをシヨツパー引張試験機にて３００mm／分の速度
で引張つて、破断に至る伸びを測定した。試料フイルム
をギヤーオーブン中で１２０℃で１６８時間加熱して、
熱老化後の測定を行なつた。酸素指数はJIS K 7201によ
つた。本発明によれば、熱老化後の伸び残存率９０％以
上、酸素指数３０以上を得ることができ、実用上、耐熱
老化性及び難燃性にすぐれる塩化ビニル系樹脂フイルム
を得ることができる。The elongation was measured by pulling a sample film having a width of 19 mm and a length of 150 mm at a rate of 300 mm / min with a Shipper super tensile tester to measure the elongation at break. Heat the sample film in a gear oven at 120 ° C for 168 hours,
The measurement was performed after heat aging. The oxygen index is according to JIS K 7201. According to the present invention, a residual elongation after heat aging of 90% or more and an oxygen index of 30 or more can be obtained, and a vinyl chloride resin film excellent in heat aging resistance and flame retardancy can be obtained in practical use. ..
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【表２】 [Table 2]
───────────────────────────────────────────────────── 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 Ｃ０８Ｌ 27/06 ＬＥＵ 9166−4Ｊ 51/08 ＬＬＴ 7142−4Ｊ 75/04 ＮＧＧ 8620−4Ｊ //(Ｃ０８Ｌ 27/06 23:08 31:04） 27:06 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C08L 27/06 LEU 9166-4J 51/08 LLT 7142-4J 75/04 NGG 8620-4J // ( C08L 27/06 23:08 31:04) 27:06
Claims (2)
１００重量部について、エチレン−酢酸ビニル共重合体
１〜５０重量部と水酸化アルミニウム２０〜２００重量
部と三酸化アンチモン１〜１５重量部とカツプリング剤
0.１〜５重量部と三塩基性硫酸鉛５〜１５重量部とを含
む樹脂組成物からなることを特徴とする耐熱性及び難燃
性にすぐれる塩化ビニル系樹脂フイルム。1. A polyvinyl chloride-polyurethane copolymer resin 100 parts by weight, ethylene-vinyl acetate copolymer 1-50 parts by weight, aluminum hydroxide 20-200 parts by weight, antimony trioxide 1-15 parts by weight and coupling. Agent
A vinyl chloride resin film having excellent heat resistance and flame retardancy, which comprises a resin composition containing 0.1 to 5 parts by weight and 5 to 15 parts by weight of tribasic lead sulfate.
グ剤又はチタネートカツプリング剤であることを特徴と
する請求項第１項記載の塩化ビニル系樹脂フイルム。2. The vinyl chloride resin film according to claim 1, wherein the coupling agent is an aluminum coupling agent or a titanate coupling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28133791A JPH05117416A (en) | 1991-10-28 | 1991-10-28 | Vinyl chloride resin film excellent in heat resistance and flame retardancy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28133791A JPH05117416A (en) | 1991-10-28 | 1991-10-28 | Vinyl chloride resin film excellent in heat resistance and flame retardancy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05117416A true JPH05117416A (en) | 1993-05-14 |
Family
ID=17637704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28133791A Pending JPH05117416A (en) | 1991-10-28 | 1991-10-28 | Vinyl chloride resin film excellent in heat resistance and flame retardancy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05117416A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4916555A (en) * | 1976-03-19 | 1990-04-10 | Ampex Corporation | Method and apparatus for producing time base altered effects in data recording and reproducing apparatus |
| US8129619B2 (en) | 2005-11-21 | 2012-03-06 | Sumitomo Electric Industries, Ltd. | Flame-retardant resin composition, and insulated wire, insulated shielded wire, insulated cable and insulation tube using the same |
| CN109280287A (en) * | 2018-08-08 | 2019-01-29 | 广东冠盛新材料有限公司 | A kind of fire-retardant electric heating blanket film and preparation method thereof |
| CN114656729A (en) * | 2022-03-18 | 2022-06-24 | 金发科技股份有限公司 | High-flame-retardant low-temperature-resistant polyvinyl chloride composition and preparation method and application thereof |
-
1991
- 1991-10-28 JP JP28133791A patent/JPH05117416A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4916555A (en) * | 1976-03-19 | 1990-04-10 | Ampex Corporation | Method and apparatus for producing time base altered effects in data recording and reproducing apparatus |
| US8129619B2 (en) | 2005-11-21 | 2012-03-06 | Sumitomo Electric Industries, Ltd. | Flame-retardant resin composition, and insulated wire, insulated shielded wire, insulated cable and insulation tube using the same |
| CN109280287A (en) * | 2018-08-08 | 2019-01-29 | 广东冠盛新材料有限公司 | A kind of fire-retardant electric heating blanket film and preparation method thereof |
| CN114656729A (en) * | 2022-03-18 | 2022-06-24 | 金发科技股份有限公司 | High-flame-retardant low-temperature-resistant polyvinyl chloride composition and preparation method and application thereof |
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