JPH06166764A - Flame-resistant thermoset polyester film - Google Patents
Flame-resistant thermoset polyester filmInfo
- Publication number
- JPH06166764A JPH06166764A JP34548792A JP34548792A JPH06166764A JP H06166764 A JPH06166764 A JP H06166764A JP 34548792 A JP34548792 A JP 34548792A JP 34548792 A JP34548792 A JP 34548792A JP H06166764 A JPH06166764 A JP H06166764A
- Authority
- JP
- Japan
- Prior art keywords
- film
- group
- flame
- curing agent
- polyester 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐炎性、可撓性、寸法
安定性、防融性、耐薬品性にすぐれたポリエステル系熱
硬化フィルムに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester thermosetting film which is excellent in flame resistance, flexibility, dimensional stability, antifussion property and chemical resistance.
【０００２】[0002]
【従来の技術】従来、モーター用絶縁フィルムやフレキ
シブルプリント基板等の耐炎性、可撓性、寸法安定性、
防融性、耐薬品性等を要求される分野では、一般の衣料
用、産業資材用ポリエステルやポリアミド等の熱可塑性
樹脂のフィルムではこれらの性能が十分でなく、使用条
件に制限があった。また、ポリエーテルエーテルケトン
やポリイミド等の高耐熱性樹脂ではコストが高かった
り、フィルム成形性がよくなかったりする等の問題があ
った。2. Description of the Related Art Conventionally, flame resistance, flexibility and dimensional stability of insulating films for motors and flexible printed circuit boards,
In the fields where anti-fusing property, chemical resistance, etc. are required, these performances are not sufficient with films of thermoplastic resins such as polyesters and polyamides for general clothing and industrial materials, and there are restrictions on the use conditions. Further, high heat resistant resins such as polyetheretherketone and polyimide have problems such as high cost and poor film formability.
【０００３】熱硬化性樹脂等の架橋型の樹脂は、一般に
安価で寸法安定性、防融性、耐薬品性もよいが、硬化さ
せると脆くなって可撓性が得られなくなる。その点、ポ
リエステル樹脂とその硬化剤からなる熱硬化性樹脂組成
物は芳香族成分と脂肪族成分を適度に含有しており、硬
化後も可撓性を有しているのでフィルム化が可能であ
る。そして、このフィルムは、寸法安定性、防融性、耐
薬品性にも優れているという架橋型樹脂の特徴も有して
いる。しかし、脂肪族成分を多く含有しているので本質
的に耐炎性が十分でなく、耐炎性の付与が必要である。Crosslinking resins such as thermosetting resins are generally inexpensive and have good dimensional stability, melting resistance and chemical resistance, but when they are cured, they become brittle and cannot provide flexibility. In that respect, a thermosetting resin composition comprising a polyester resin and a curing agent thereof appropriately contains an aromatic component and an aliphatic component, and has flexibility even after curing, so that a film can be formed. is there. Further, this film also has a characteristic of a cross-linkable resin that is excellent in dimensional stability, melting resistance and chemical resistance. However, since it contains a large amount of aliphatic components, the flame resistance is essentially insufficient, and it is necessary to impart flame resistance.
【０００４】従来、耐炎性付与には、テトラブロモビス
フェノールＡ型エポキシ樹脂をポリエステル樹脂の硬化
剤として用いる方法や、テトラブロモビスフェノールＡ
のエチレンオキサイド付加体をポリエステル樹脂に共重
合する方法等が知られている。しかし、これらの方法で
は、接炎時に有毒なハロゲン系のガスを発生するという
問題があった。Conventionally, for imparting flame resistance, a method using a tetrabromobisphenol A type epoxy resin as a curing agent for a polyester resin, or tetrabromobisphenol A has been used.
There is known a method of copolymerizing the ethylene oxide adduct of (1) with a polyester resin. However, these methods have a problem that a toxic halogen-based gas is generated at the time of flame contact.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記のよう
な欠点を解消し、安価で耐炎性、可撓性、寸法安定性、
防融性、耐薬品性にも優れ、しかも、接炎時に有毒ガス
を発生することのないポリエステル系耐炎性熱硬化フィ
ルムを提供するものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks and is inexpensive, flame resistant, flexible, dimensional stable, and
It is intended to provide a polyester flame-resistant thermosetting film which is excellent in anti-fusing property and chemical resistance and does not generate toxic gas during flame contact.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、このよう
な状況に対して、上記のごとき問題のないポリエステル
系耐炎性熱硬化フィルムについて鋭意研究を重ねた結
果、主たる末端が水酸基であるポリエステル樹脂と、二
個以上の水酸基を官能基として有する有機リン化合物と
を、水酸基と反応する硬化剤を用いて硬化させることに
より得られる三次元架橋した熱硬化フィルムが耐炎性を
有し、かつ、可撓性、寸法安定性、防融性、耐薬品性に
ついても満足し得るものであることを見いだし本発明に
到達した。Under the circumstances, the inventors of the present invention have conducted intensive studies on the above-mentioned polyester flame-resistant thermosetting film having no problem, and as a result, the main terminal is a hydroxyl group. Polyester resin and an organic phosphorus compound having two or more hydroxyl groups as functional groups, a three-dimensional crosslinked thermosetting film obtained by curing with a curing agent that reacts with hydroxyl groups has flame resistance, and The inventors have found that they are also satisfactory in flexibility, dimensional stability, anti-fusing property, and chemical resistance, and have reached the present invention.
【０００７】すなわち、本発明の要旨は次のとおりであ
る。主たる末端が水酸基であるポリエステル樹脂と、下
記一般式（１）で表される有機リン化合物および水酸基
と反応する硬化剤の三成分からなる三次元架橋したポリ
エステル系耐炎性熱硬化フィルムである。That is, the gist of the present invention is as follows. A three-dimensionally crosslinked polyester flame-resistant thermosetting film comprising a polyester resin having a hydroxyl group as a main terminal, an organic phosphorus compound represented by the following general formula (1), and a curing agent that reacts with a hydroxyl group.
【化１】（Ｒ1 、Ｒ2 はアルキル基、アリール基、アル
コキシ基、及びアリロキシ基から選ばれた同種または異
種の基であり、Ｒ1 、Ｒ2 は互いに環を形成していても
よい。また、Ｘは三価の有機基であり、Ｙは脂肪族の骨
格からなる一価以上のアルコールである。）Embedded image (R 1 and R 2 are the same or different groups selected from an alkyl group, an aryl group, an alkoxy group, and an aryloxy group, and R 1 and R 2 may form a ring with each other. Further, X is a trivalent organic group, and Y is a monovalent or higher alcohol having an aliphatic skeleton.)
【０００８】本発明において、一般式（１）で表される
有機リン化合物としては次式で示される化合物が挙げら
れる。In the present invention, examples of the organic phosphorus compound represented by the general formula (1) include compounds represented by the following formula.
【化４】 [Chemical 4]
【化５】 [Chemical 5]
【化６】 [Chemical 6]
【化７】 [Chemical 7]
【化８】 [Chemical 8]
【化９】 これらのなかでも、リン化合物の安定性、リン原子含有
率の高さ、フィルム化工程でのリン化合物の揮発、飛散
の少なさ、フィルムの可撓性への影響等を総合的に判断
すると、[Chemical 9] Among these, the stability of phosphorus compounds, high phosphorus atom content rate, volatilization of phosphorus compounds in the film forming process, small scattering, the effect on the flexibility of the film, etc.
【化４】で示されるリン化合物ジフェニル−（２，５−
ビスβヒドロキシエトキシフェニル）−ホスフィンオキ
シド、または、The phosphorus compound represented by the following formula: diphenyl- (2,5-
Bisβhydroxyethoxyphenyl) -phosphine oxide, or
【化５】で示されるリン化合物９，１０−ジヒドロ−９
−オキサ−１０−（２’，５’−ビスβヒドロキシエト
キシフェニル）−ホスファフェナントレン−１０−オキ
シドが好ましい。Phosphorus compound 9,10-dihydro-9 represented by
-Oxa-10- (2 ', 5'-bisβhydroxyethoxyphenyl) -phosphaphenanthrene-10-oxide is preferred.
【０００９】本発明において、ポリエステル樹脂の構成
成分としてはジカルボン酸成分としてテレフタル酸、イ
ソフタル酸等の芳香族ジカルボン酸を主体とし、ジオー
ル成分としてエチレングリコール、ネオペンチルグリコ
ール等の脂肪族ジオールを主体とするもの、あるいはジ
カルボン酸、ジオールおよびオキシカルボン酸を主体と
するもの、あるいはオキシカルボン酸を構成成分とする
ものがよく、オキシカルボン酸としては、例えば、酒石
酸や４−ヒドロキシ安息香酸等がある。そして、これら
にアジピン酸やアゼライン酸等の脂肪族ジカルボン酸、
トリメリット酸やピロメリット酸等の三価以上のカルボ
ン酸、トリメチロールプロパン、ペンタエリスリトール
等の三価以上のアルコール等を少量含んでいるものは溶
融流動性、架橋反応性が向上するのでより好ましい。In the present invention, as constituent components of the polyester resin, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid are mainly used as dicarboxylic acid components, and aliphatic diols such as ethylene glycol and neopentyl glycol are mainly used as diol components. Of these, or those mainly containing dicarboxylic acids, diols and oxycarboxylic acids, or those containing oxycarboxylic acids as constituent components are preferred. Examples of oxycarboxylic acids include tartaric acid and 4-hydroxybenzoic acid. And to these, aliphatic dicarboxylic acids such as adipic acid and azelaic acid,
Those containing a small amount of trivalent or more carboxylic acid such as trimellitic acid or pyromellitic acid, and trivalent or more alcohol such as trimethylolpropane and pentaerythritol are more preferable because the melt fluidity and the crosslinking reactivity are improved. .
【００１０】また、ポリエステル樹脂の平均重合度は５
〜５０ｗｔ％の範囲のものが好ましい。これより重合度
が低いものはフィルムにしたとき十分な強度が得られな
かったり、これより重合度が高いものはフィルム化が困
難になる場合がある。The average degree of polymerization of the polyester resin is 5
It is preferably in the range of ˜50 wt%. If the degree of polymerization is lower than this, sufficient strength may not be obtained when formed into a film, and if the degree of polymerization is higher than this, it may be difficult to form a film.
【００１１】本発明において、ポリエステル樹脂と有機
リン化合物とを硬化させる硬化剤としては、ウレタン系
やメラミン系の硬化剤が好ましい。例えば、ウレタン系
の硬化剤としてはε−カプロラクタムブロックドイソシ
アナート（ダイセルヒュルス社製Ａｄｄｕｋｔ Ｂ−１
５３０やＢ−１０６５）、また、メラミン系硬化剤とし
てはメチル化メラミン（三井サイアナミッド社製サイメ
ル３０３や住友化学社製スミマールＭ−１００）等があ
る。In the present invention, a urethane-based or melamine-based curing agent is preferable as the curing agent for curing the polyester resin and the organic phosphorus compound. For example, as a urethane-based curing agent, ε-caprolactam blocked isocyanate (Adduct B-1 manufactured by Daicel Huls) is used.
530 and B-1065), and as the melamine-based curing agent, there are methylated melamine (Cymel 303 manufactured by Mitsui Cyanamid Co., Ltd. and Sumimar M-100 manufactured by Sumitomo Chemical Co., Ltd.).
【００１２】本発明において、ポリエステル樹脂、有機
リン化合物、硬化剤の配合割合は、ポリエステル樹脂の
末端基、有機リン化合物の官能基、硬化剤の官能基各々
の量により異なるが、全樹脂量に対するポリエステル樹
脂の割合は１０〜９０ｗｔ％の範囲が好ましい。ポリエ
ステル樹脂の割合がこれより少ないとフィルムの可撓性
が劣ったり、ポリエステル樹脂の割合がこれより多くな
るとフィルムの耐炎性や耐熱性が低下する場合がある。In the present invention, the mixing ratio of the polyester resin, the organic phosphorus compound, and the curing agent varies depending on the amount of each of the terminal group of the polyester resin, the functional group of the organic phosphorus compound, and the functional group of the curing agent. The proportion of polyester resin is preferably in the range of 10 to 90 wt%. If the proportion of the polyester resin is less than this, the flexibility of the film may be poor, and if the proportion of the polyester resin is more than this, the flame resistance and heat resistance of the film may be deteriorated.
【００１３】次に、全樹脂量に対する有機リン化合物の
割合は５〜４０ｗｔ％の範囲が好ましい。有機リン化合
物の割合がこれより少ないとフィルムの耐炎性が劣った
り、有機リン化合物の割合がこれより多くなるとフィル
ムの耐熱性や耐薬品性が低下したりする場合がある。Next, the ratio of the organic phosphorus compound to the total amount of resin is preferably in the range of 5 to 40 wt%. If the proportion of the organic phosphorus compound is less than this, the flame resistance of the film may be poor, and if the proportion of the organic phosphorus compound is more than this, the heat resistance and chemical resistance of the film may be deteriorated.
【００１４】次に、硬化剤は、ポリエステル樹脂の末端
基と有機リン化合物の官能基の総量と硬化剤の官能基量
が１：１となるように配合すればよい。具体的には、全
樹脂量に対する硬化剤の割合は５〜５０ｗｔ％の範囲が
好ましい。硬化剤の割合がこれより少ないと耐熱性が十
分でなかったり、硬化剤の割合がこれより多くなると可
撓性が低下したりする場合がある。Next, the curing agent may be added in such a manner that the total amount of the terminal groups of the polyester resin and the functional groups of the organic phosphorus compound and the amount of the functional groups of the curing agent are 1: 1. Specifically, the ratio of the curing agent to the total amount of resin is preferably in the range of 5 to 50 wt%. If the proportion of the curing agent is less than this, the heat resistance may not be sufficient, and if the proportion of the curing agent is greater than this, the flexibility may decrease.
【００１５】本発明のフィルムは、ポリエステル樹脂と
有機リン化合物および硬化剤、その他必要に応じて三級
アミンや有機金属錯体等の硬化促進剤や添加剤等を配合
した樹脂組成物をフィルム状に成形し、これを硬化させ
ればよいのであるが、工業的に有利に得るという点から
次の方法が好ましい。The film of the present invention comprises a resin composition in which a polyester resin, an organic phosphorus compound, a curing agent, and if necessary, a curing accelerator, an additive such as a tertiary amine or an organic metal complex, an additive, and the like are formed into a film. It may be formed and cured, but the following method is preferable from the viewpoint of industrially obtaining it.
【００１６】すなわち、熱硬化性樹脂組成物を粉末状に
粉砕し、これを基材上に均一に散布した後、この基材を
熱硬化性樹脂組成物が溶融流動し、かつ実質的に硬化反
応が可能な温度以上で熱処理することにより熱硬化性樹
脂組成物を溶融させるとともに架橋させてフィルム状と
し、基材とフィルムを分離して熱硬化フィルムを得る方
法である。実際には、熱硬化性樹脂組成物の粉砕は粒径
を５０μｍ以下にするのがよく、より好ましくは３０μ
ｍ以下にするのがよい。これより大きくなるとフィルム
表面が粗くなり平滑性が損なわれる場合がある。粉砕に
は、十分に冷却固化した熱硬化性樹脂組成物をボールミ
ルで粉砕するのが均一な粉体が得られるので好ましい。That is, the thermosetting resin composition is pulverized into a powder, and the powder is evenly dispersed on the substrate. Then, the thermosetting resin composition melts and flows on the substrate and is substantially cured. This is a method in which the thermosetting resin composition is melted and crosslinked to form a film by heat treatment at a temperature at which reaction is possible or higher, and the base material and the film are separated to obtain a thermosetting film. In practice, the thermosetting resin composition is preferably pulverized to have a particle size of 50 μm or less, more preferably 30 μm.
It is better to be m or less. If it is larger than this, the film surface becomes rough and smoothness may be impaired. For pulverization, it is preferable to pulverize a thermosetting resin composition that has been sufficiently cooled and solidified with a ball mill because a uniform powder can be obtained.
【００１７】次に、熱硬化性樹脂組成物の基材上への散
布は、粉砕した熱硬化性樹脂組成物の粉体を金属または
樹脂等の基材上に均一に散布すればよいのであるが、よ
り好ましくは粉砕した熱硬化性樹脂組成物の粉体に静電
気を帯電させ、これを金属製の板上に散布し、静電気の
作用で粉体を板の表面に吸着させる方法が簡便かつ均一
に行える。しかも静電気による吸着であるので、任意の
形状のものに、任意の厚さで熱硬化性樹脂組成物の粉体
を吸着させることができ、従って任意の形状の熱硬化フ
ィルムを製造することができる。また、基材上に分散さ
せる熱硬化性樹脂組成物の量を加減することにより容易
にフィルムの厚さを制御できる。なお、金属製の板の表
面はフィルムの分離性をよくするためにフッ素系または
シリコン系の離型剤で処理しておくのが好ましい。Next, the application of the thermosetting resin composition onto the substrate may be carried out by uniformly applying the pulverized powder of the thermosetting resin composition onto the substrate such as metal or resin. However, more preferably, a method of charging static electricity to the powder of the crushed thermosetting resin composition, spraying this on a metal plate, and adsorbing the powder to the surface of the plate by the action of static electricity is simple and Can be done uniformly. Moreover, since the adsorption is performed by static electricity, the powder of the thermosetting resin composition can be adsorbed to an arbitrary shape having an arbitrary thickness, and thus a thermosetting film having an arbitrary shape can be produced. . Further, the thickness of the film can be easily controlled by adjusting the amount of the thermosetting resin composition dispersed on the substrate. The surface of the metal plate is preferably treated with a fluorine-based or silicon-based release agent in order to improve the separability of the film.
【００１８】熱処理については、恒温の炉の中で行い、
熱硬化性樹脂組成物が溶融流動し、かつ実質的に硬化反
応が可能な温度以上で行う。また、フィルムの基材から
の分離は、熱硬化したフィルムを基材から剥離すること
により簡単に分離できる。The heat treatment is carried out in a constant temperature oven,
It is carried out at a temperature at which the thermosetting resin composition melts and flows and a curing reaction can be substantially performed. Further, the film can be easily separated from the base material by peeling the thermoset film from the base material.
【００１９】[0019]
【作用】本発明は、安価で可撓性、寸法安定性、防融
性、耐薬品性等には優れているが、耐炎性が悪いという
問題のあるポリエステル系熱硬化フィルムについて、主
たる末端が水酸基であるポリエステル樹脂と二個以上の
水酸基を官能基として有する有機リン化合物とを、水酸
基と反応する硬化剤を用いて硬化させることにより、ポ
リエステル樹脂、有機リン化合物、硬化剤の三成分から
なる三次元架橋構造を作り、フィルム中にリン原子を導
入することにより耐炎性を付与したものである。この有
機リン化合物は、その骨格に脂肪族を有しているので架
橋構造中に導入されてもフィルムの可撓性を損なうこと
がなく、また、接炎時には分解して不揮発性のリン酸の
保護膜を形成し、そして、生成したリン酸の脱水作用に
より有機物の炭化を促進して炭化被膜を形成し、酸素の
供給を遮断することにより耐炎性を発現するものであ
る。The present invention is a polyester thermosetting film which is inexpensive and excellent in flexibility, dimensional stability, fusion resistance, chemical resistance, etc., but has a problem of poor flame resistance. A polyester resin, which is a hydroxyl group, and an organic phosphorus compound having two or more hydroxyl groups as functional groups, are cured by using a curing agent that reacts with the hydroxyl group, and thus consist of three components: a polyester resin, an organic phosphorus compound, and a curing agent. Flame resistance is imparted by creating a three-dimensional crosslinked structure and introducing phosphorus atoms into the film. Since this organic phosphorus compound has an aliphatic skeleton, it does not impair the flexibility of the film even if it is introduced into the crosslinked structure, and it decomposes during flame contact to form a non-volatile phosphoric acid. By forming a protective film, and promoting the carbonization of the organic substance by the dehydrating action of the generated phosphoric acid to form a carbonized film, and blocking the supply of oxygen, flame resistance is exhibited.
【００２０】[0020]
【実施例】次に実施例によって本発明を具体的に説明す
る。なお、実施例中の特性値の測定は次の通りである。 耐炎性 耐炎性は、ＵＬ−９４規格によるフィルム評価法により
判定した。 強伸度 東洋ボールドウィン社製テンシロンＵＴＭ−４−１００
型を用い、１cm×１０cmのフィルム片を１０cm／min の
速度にて引張試験を行い、フィルムが破断した点の強
度、伸度を求めた。 熱収縮率 ２００℃の熱風乾燥機中に１０分間放置した後のフィル
ムの収縮率を測定した。 可撓性 フィルムを折り曲げて破断するかどうかをみた。破断し
ないものを○、破断したものを×とした。 平滑性 フィルム表面の平滑度合を目視にて判定した。平滑なも
のを○、やや粗いものを△、粗いものを×とした。 耐アルカリ性 フィルムを８０℃の５％NaOH水溶液中に６０分間浸漬し
て、破断強度の保持率を測定した。保持率が９０％以上
のものを○、９０％以下のものを×とした。 防融性 フィルムに火の着いたタバコを５秒間接触させ穴があく
かどうかをみた。穴のあかなかったものを○、あいたも
のを×とした。EXAMPLES The present invention will be described in detail with reference to examples. In addition, the measurement of the characteristic value in an Example is as follows. Flame resistance The flame resistance was judged by the film evaluation method according to UL-94 standard. High elongation Tensilon UTM-4-100 manufactured by Toyo Baldwin
Using a mold, a 1 cm × 10 cm film piece was subjected to a tensile test at a speed of 10 cm / min to determine the strength and elongation at the point where the film was broken. Heat Shrinkage The shrinkage of the film after standing for 10 minutes in a hot air dryer at 200 ° C. was measured. The flexible film was bent to see if it broke. Those that did not break were rated as O, and those that did break were rated as X. Smoothness The smoothness of the film surface was visually evaluated. The smooth one was marked with ◯, the slightly rough one was marked with Δ, and the rough one was marked with x. The alkali resistance film was immersed in a 5% NaOH aqueous solution at 80 ° C. for 60 minutes, and the breaking strength retention rate was measured. Those with a retention rate of 90% or more were evaluated as ◯, and those with a retention rate of 90% or less were evaluated as x. Anti-Fusion Film A fired cigarette was contacted with the film for 5 seconds to see if there was a hole. Those with no holes were marked with ◯ and those with holes were marked with x.
【００２１】実施例１ ジカルボン酸成分としてテレフタル酸、ジオール成分と
してエチレングリコール３６ｍｏｌ％ネオペンチルグリ
コール６０ｍｏｌ％、三価のグリコールとしてトリメチ
ロールプロパン４ｍｏｌ％からなる平均重合度が２５、
末端水酸基価が５５０geq ／１０6gである共重合ポリエ
ステル樹脂44重量部、ε−カプロラクタムブロックドイ
ソシアナート（ダイセルヒュルス社製Ａｄｄｕｋｔ Ｂ
−１５３０）３３重量部、Example 1 An terephthalic acid as a dicarboxylic acid component, ethylene glycol 36 mol% neopentyl glycol 60 mol% as a diol component, and trimethylolpropane 4 mol% as a trivalent glycol having an average degree of polymerization of 25,
44 parts by weight of a copolyester resin having a terminal hydroxyl value of 550 geq / 10 6 g, ε-caprolactam blocked isocyanate (Adduct B manufactured by Daicel Huls)
-1530) 33 parts by weight,
【化４】で示される有機リン化合物２３重量部、硬化促
進剤（三共有機合成社製Ｓｔａｎｎ ＯＭＦ）０．２重
量部、流展剤（ＢＡＳＦ社製アクロナール４Ｆ）０．７
重量部をヘンシェルミキサー（三井三池製作所製ＦＭ１
０Ｂ型）でドライブレンドした後、コ・ニーダー（ブッ
ス社製ＰＲ−４６型）を用いて１２０℃で溶融混練し、
冷却固化後ボールミルにて粉砕し、１４５メッシュの金
網で分離して粉体を得た。この粉体を塗装用の静電塗装
機を用いて、鋼板上に膜厚が７５μｍになるように散布
した。この鋼板を１９０℃で２０分熱風乾燥機中で熱処
理した。なお、鋼板の表面はあらかじめゴミ、油脂等を
洗浄し、フッ素系離型剤（ダイキン社製ダイフリー）を
塗布した。熱処理した鋼板を空気中で室温まで冷却した
後、鋼板からフィルムをはがして熱硬化フィルムを得
た。得られたフィルムの物性を表１に示す。このフィル
ムは可撓性があり、また、リン原子を含有しているので
優れた耐炎性を有していた。23 parts by weight of the organophosphorus compound represented by the formula: 0.2 part by weight of a curing accelerator (Stan OMF manufactured by Sansha Kisei Co., Ltd.), and a leveling agent (Acronal 4F manufactured by BASF) 0.7
Henschel mixer (Mitsui Miike Seisakusho FM1
After dry blending with OB type), melt kneading at 120 ° C. using a co-kneader (PR-46 type manufactured by Buss),
After cooling and solidification, it was pulverized with a ball mill and separated with a wire mesh of 145 mesh to obtain a powder. This powder was sprayed onto a steel plate using an electrostatic coating machine for coating so that the film thickness was 75 μm. This steel sheet was heat-treated at 190 ° C. for 20 minutes in a hot air dryer. It should be noted that the surface of the steel sheet was washed with dust, oils and fats in advance, and a fluorine-based release agent (Die-free manufactured by Daikin) was applied. After cooling the heat-treated steel sheet to room temperature in air, the film was peeled from the steel sheet to obtain a thermosetting film. Table 1 shows the physical properties of the obtained film. This film was flexible and had excellent flame resistance since it contained a phosphorus atom.
【００２２】実施例２ 有機リン化合物としてExample 2 As organic phosphorus compound
【化５】で示されるものを用いた以外は実施例１と同様
にして行った。得られたフィルムの物性を表１に示す。
このフィルムも可撓性があり、また、リン原子を含有し
ているので優れた耐炎性を有していた。The same procedure as in Example 1 was carried out except that the compound represented by the formula: was used. Table 1 shows the physical properties of the obtained film.
This film was also flexible and had excellent flame resistance because it contained phosphorus atoms.
【００２３】実施例３ 実施例１で用いた共重合ポリエステル樹脂４５重量部、
メチル化メラミン（住友化学社製スミマールＭ−１０
０）３４重量部、Example 3 45 parts by weight of the copolyester resin used in Example 1,
Methylated melamine (Sumimar M-10 manufactured by Sumitomo Chemical Co., Ltd.
0) 34 parts by weight,
【化４】で示される有機リン化合物２１重量部、流展剤
（ＢＡＳＦ社製アクロナール４Ｆ）０．７重量部を用い
て実施例１と同様にして行った。得られたフィルムの物
性を表１に示す。このフィルムも実施例１と同様に、可
撓性があり、また、優れた耐炎性を有していた。The same procedure as in Example 1 was carried out using 21 parts by weight of the organic phosphorus compound represented by the formula: and 0.7 parts by weight of a leveling agent (Acronal 4F manufactured by BASF). Table 1 shows the physical properties of the obtained film. This film was also flexible as in Example 1 and had excellent flame resistance.
【００２４】比較例１ 実施例１で用いた共重合ポリエステル樹脂８７重量部、
ε−カプロラクタムブロックドイソシアナート（ダイセ
ルヒュルス社製Ａｄｄｕｋｔ Ｂ−１５３０）１３重量
部、硬化促進剤（三共有機合成社製Ｓｔａｎｎ ＯＭ
Ｆ）０．２重量部、流展剤（ＢＡＳＦ社製アクロナール
４Ｆ）０．７重量部を用いて実施例１と同様にして行っ
た。得られたフィルムの物性を表１に示す。このフィル
ムは可撓性は良いが、リン原子を含有していないので耐
炎性も悪く自己消火性の無いものとなった。Comparative Example 1 87 parts by weight of the copolyester resin used in Example 1,
13 parts by weight of ε-caprolactam blocked isocyanate (Adduct B-1530 manufactured by Daicel Huls), a curing accelerator (Stann OM manufactured by Sansha Machinery Co., Ltd.)
The same procedure as in Example 1 was carried out using 0.2 part by weight of F) and 0.7 part by weight of a leveling agent (Acronal 4F manufactured by BASF). Table 1 shows the physical properties of the obtained film. This film had good flexibility, but since it did not contain phosphorus atoms, it had poor flame resistance and had no self-extinguishing property.
【００２５】比較例２ 実施例１で用いた末端水酸基型の共重合ポリエステル樹
脂８６重量部、メチル化メラミン（住友化学社製スミマ
ールＭ−１００）１４重量部、流展剤（ＢＡＳＦ社製ア
クロナール４Ｆ）０．７重量部を用いて実施例１と同様
にしてフイルムを得た。得られたフィルムの物性を表１
に示す。このフィルムも可撓性は良いが、リン原子を含
有していないので耐炎性も悪く自己消火性の無いものと
なった。Comparative Example 2 86 parts by weight of the terminal hydroxyl group-type copolyester resin used in Example 1, 14 parts by weight of methylated melamine (Sumimar M-100 manufactured by Sumitomo Chemical Co., Ltd.), a leveling agent (Acronal 4F manufactured by BASF). ) A film was obtained in the same manner as in Example 1 except that 0.7 parts by weight was used. The physical properties of the obtained film are shown in Table 1.
Shown in. This film also has good flexibility, but since it does not contain phosphorus atoms, it has poor flame resistance and no self-extinguishing property.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明は、安価で寸法安定性、防融性、
耐アルカリ性にも優れ、しかも耐炎性、可撓性共に満足
し、接炎時に有毒ガスを発生しない熱硬化フイルムが提
供される。INDUSTRIAL APPLICABILITY The present invention is inexpensive and has dimensional stability, fusion resistance, and
Provided is a thermosetting film which is excellent in alkali resistance, has satisfactory flame resistance and flexibility, and does not generate toxic gas during flame contact.
Claims (3)
脂と、下記一般式（１）で表される有機リン化合物およ
び水酸基と反応する硬化剤の三成分からなる三次元架橋
したポリエステル系耐炎性熱硬化フィルム。 【化１】 （Ｒ1 、Ｒ2 はアルキル基、アリール基、アルコキシ
基、及びアリロキシ基から選ばれた同種または異種の基
であり、Ｒ1 、Ｒ2 は互いに環を形成していてもよい。
また、Ｘは三価の有機基であり、Ｙは脂肪族の骨格から
なる一価以上のアルコールである。）1. A three-dimensionally crosslinked polyester flame-resistant thermosetting resin comprising a polyester resin having a hydroxyl group as a main terminal, an organic phosphorus compound represented by the following general formula (1) and a curing agent that reacts with a hydroxyl group. the film. [Chemical 1] (R 1 and R 2 are the same or different groups selected from an alkyl group, an aryl group, an alkoxy group, and an allyloxy group, and R 1 and R 2 may form a ring with each other.
Further, X is a trivalent organic group, and Y is a monovalent or more alcohol having an aliphatic skeleton. )
下記構造式（２）で表される化合物である請求項１記載
のポリエステル系耐炎性熱硬化フィルム。 【化２】 2. The polyester flame-resistant thermosetting film according to claim 1, wherein the organic phosphorus compound represented by the general formula (1) is a compound represented by the following structural formula (2). [Chemical 2]
あり、一般式（１）で表される有機リン化合物が下記構
造式（３）で表される化合物である請求項１記載のポリ
エステル系耐炎性熱硬化フィルム。 【化３】 3. The polyester-based flame resistance according to claim 1, wherein the main terminal of the polyester resin is a hydroxyl group, and the organophosphorus compound represented by the general formula (1) is a compound represented by the following structural formula (3). Thermoset film. [Chemical 3]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34548792A JPH06166764A (en) | 1992-12-01 | 1992-12-01 | Flame-resistant thermoset polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34548792A JPH06166764A (en) | 1992-12-01 | 1992-12-01 | Flame-resistant thermoset polyester film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06166764A true JPH06166764A (en) | 1994-06-14 |
Family
ID=18376919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34548792A Pending JPH06166764A (en) | 1992-12-01 | 1992-12-01 | Flame-resistant thermoset polyester film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06166764A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004061008A1 (en) * | 2002-12-27 | 2004-07-22 | Polyplastics Co., Ltd. | Flame-retardant resin composition |
| EP2186816A1 (en) * | 2008-11-14 | 2010-05-19 | Chang Chun Plastics Co., Ltd. | Phosphorus compound and method for preparing the same |
-
1992
- 1992-12-01 JP JP34548792A patent/JPH06166764A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004061008A1 (en) * | 2002-12-27 | 2004-07-22 | Polyplastics Co., Ltd. | Flame-retardant resin composition |
| JPWO2004061008A1 (en) * | 2002-12-27 | 2006-05-11 | ポリプラスチックス株式会社 | Flame retardant resin composition |
| CN1324089C (en) * | 2002-12-27 | 2007-07-04 | 宝理塑料株式会社 | Flame-retardant resin composition |
| US7411013B2 (en) | 2002-12-27 | 2008-08-12 | Polyplastics Co., Ltd. | Flame-retardant resin composition |
| JP4673626B2 (en) * | 2002-12-27 | 2011-04-20 | ポリプラスチックス株式会社 | Flame retardant resin composition |
| EP2186816A1 (en) * | 2008-11-14 | 2010-05-19 | Chang Chun Plastics Co., Ltd. | Phosphorus compound and method for preparing the same |
| JP2010116398A (en) * | 2008-11-14 | 2010-05-27 | Chang Chun Plastics Co Ltd | Phosphorus-containing compound and method for producing the same |
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