JPH0680765A - Flame-resistant thermosetting epoxy resin film - Google Patents
Flame-resistant thermosetting epoxy resin filmInfo
- Publication number
- JPH0680765A JPH0680765A JP25901392A JP25901392A JPH0680765A JP H0680765 A JPH0680765 A JP H0680765A JP 25901392 A JP25901392 A JP 25901392A JP 25901392 A JP25901392 A JP 25901392A JP H0680765 A JPH0680765 A JP H0680765A
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- JP
- Japan
- Prior art keywords
- film
- flame
- thermosetting resin
- chemical
- epoxy 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.)
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Links
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
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エポキシ系熱硬化
性樹脂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 an epoxy thermosetting resin film which is excellent in flame resistance, flexibility, dimensional stability, fusion resistance 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 field where anti-fusing property and chemical resistance are required, these performances are not sufficient with films of thermoplastic resins such as polyester and polyamide 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】エポキシ系樹脂等の熱硬化性樹脂は、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。従来、エ
ポキシ系樹脂に可撓性を付与するには、脂肪族モノマー
やポリグリコール等をエポキシ系樹脂に添加し、架橋構
造中に導入する方法が知られている。しかし、これらの
物質を架橋構造中に導入すると耐炎性が悪くなるので、
耐炎性の付与が必要である。Thermosetting resins such as epoxy resins are generally inexpensive and have good dimensional stability, melting resistance and chemical resistance, but when they are cured, they become brittle and cannot obtain flexibility. Conventionally, to impart flexibility to an epoxy resin, a method is known in which an aliphatic monomer, polyglycol, or the like is added to the epoxy resin and introduced into a crosslinked structure. However, when these substances are introduced into the crosslinked structure, the flame resistance is deteriorated,
It is necessary to impart flame resistance.
【０００４】従来、エポキシ系樹脂の耐炎性付与には、
テトラブロモビスフェノールＡ型エポキシ樹脂を通常の
エポキシ系樹脂に添加する方法や、テトラブロモ無水フ
タル酸を硬化剤として用い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ガス
を発生するという問題があった。Conventionally, for imparting flame resistance to epoxy resins,
A method of adding tetrabromobisphenol A type epoxy resin to an ordinary epoxy resin, a method of using tetrabromophthalic anhydride as a curing agent, and the like are known. However, these methods have a problem that a toxic halogen 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エポキシ系耐炎性熱硬化性樹脂フ
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 an epoxy-based flame-resistant thermosetting resin film which is excellent in anti-fusing property and chemical resistance, and does not generate toxic gas at the time of 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エポキシ系耐
炎性熱硬化性樹脂フィルムについて鋭意研究を重ねた結
果、エポキシ系樹脂を、リン原子を含有する脂肪族また
は脂肪族と芳香族を骨格に有する二価以上のカルボン酸
またはその酸無水物を硬化剤として用いて硬化させるこ
とにより得られる熱硬化性樹脂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。Means for Solving the Problems Under these circumstances, the present inventors have made earnest studies on an epoxy-based flame-resistant thermosetting resin film having no problem as described above, and as a result, , A thermosetting resin film obtained by curing using a divalent or higher carboxylic acid having a phosphorus atom-containing aliphatic or aliphatic and aromatic skeleton or an acid anhydride thereof as a curing agent has flame resistance. The present invention has been completed by discovering that it has satisfactory flexibility, dimensional stability, anti-fusing property, and chemical resistance.
【０００７】すなわち、本発明の要旨は次のとおりであ
る。エポキシ系樹脂を、下記一般式（１）で表される有
機リン化合物を硬化剤として硬化させることにより得ら
れるエポキシ系耐炎性熱硬化性樹脂フィルムである。That is, the gist of the present invention is as follows. It is an epoxy flame-resistant thermosetting resin film obtained by curing an epoxy resin with an organic phosphorus compound represented by the following general formula (1) as a curing agent.
【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は脂肪族または脂肪族と芳香族とから成る
骨格を有する二価以上のカルボン酸またはその酸無水物
である。）(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 divalent or higher carboxylic acid having an skeleton composed of aliphatic or aliphatic and aromatic, or an acid anhydride thereof.)
【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】 [Chemical 9]
【化１０】 [Chemical 10]
【化１１】 [Chemical 11]
【化１２】 [Chemical 12]
【化１３】 [Chemical 13]
【化１４】 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、化４で示されるリン化合物ジフェニルホスフィ
ンオキシドのイタコン酸付加体（以下ＰＰＡ−ＩＡと略
す）、または、化７で示されるリン化合物９，１０−ジ
ヒドロキシ−９−オキサ−１０−ホスファフェナントレ
ン−１０−オキシドのイタコン酸付加体（以下ＨＣＡ−
ＩＡと略す）が好ましい。[Chemical 14] 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. The itaconic acid adduct of the phosphorus compound diphenylphosphine oxide represented by Chemical formula 4 (hereinafter abbreviated as PPA-IA) or the phosphorus compound 9,10-dihydroxy-9-oxa-10-phosphaphenanthrene-10 represented by Chemical formula 7 -Itaconic acid adduct of oxide (hereinafter referred to as HCA-
(Abbreviated as IA) is preferable.
【０００９】本発明において、エポキシ系樹脂と有機リ
ン化合物の配合割合は、エポキシ系樹脂のエポキシ当
量、有機リン化合物の末端カルボキシル基の数により異
なるが、エポキシ系樹脂：有機リン化合物＝９：１〜
４：６（重量比）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や可撓性が得
られなくなる。また、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悪くなる。In the present invention, the mixing ratio of the epoxy resin and the organic phosphorus compound varies depending on the epoxy equivalent of the epoxy resin and the number of terminal carboxyl groups of the organic phosphorus compound, but the epoxy resin: organic phosphorus compound = 9: 1. ~
The range of 4: 6 (weight ratio) is preferable. If the proportion of the organic phosphorus compound is less than this range, the flame resistance and flexibility of the film cannot be obtained. On the other hand, if the proportion of the organic phosphorus compound is higher than this, the heat resistance and chemical resistance of the film deteriorate.
【００１０】本発明において、エポキシ系樹脂として
は、ビスフェノールＡのグリシジルエーテル型エポキシ
樹脂、クレゾールノボラック型エポキシ樹脂、トリグリ
シジルイソシアヌレート等があるが、フィルム化した場
合の耐熱性、耐薬品性の良さを考慮するとクレゾールノ
ボラック型エポキシ樹脂が好ましい。In the present invention, as the epoxy resin, there are glycidyl ether type epoxy resin of bisphenol A, cresol novolac type epoxy resin, triglycidyl isocyanurate, and the like, which have good heat resistance and chemical resistance when formed into a film. Considering the above, a cresol novolac type epoxy resin is preferable.
【００１１】本発明のフィルムは、エポキシ系樹脂と有
機リン化合物の硬化剤、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 containing a curing agent for an epoxy resin and an organic phosphorus compound, and if necessary, a curing accelerator such as a tertiary amine or an organometallic complex and an additive. It may be molded into a resin and cured, but the following method is preferable from the viewpoint of industrially obtaining it.
【００１２】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性樹脂フィルムを
得る方法である。That is, the thermosetting resin composition is pulverized into a powder, and the powder is evenly dispersed on a substrate. Then, the thermosetting resin composition melts and flows on the substrate and is substantially cured. In this method, 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 substrate and the film are separated to obtain a thermosetting resin film.
【００１３】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３０
μｍ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。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。In practice, the thermosetting resin composition should be ground to a particle size of 50 μm or less, more preferably 30
It is preferable that the thickness is μm or less. If it is larger than this, the film surface becomes rough and smoothness is 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.
【００１４】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性
樹脂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 it is adsorbed by static electricity, it is possible to adsorb the thermosetting resin composition powder with an arbitrary thickness to an arbitrary shape, and therefore to produce a thermosetting resin film of an arbitrary shape. You can 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.
【００１５】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はがすことに
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.
【００１６】[0016]
【作用】本発明は、安価で寸法安定性、防融性、耐薬品
性等には優れているが、耐炎性が悪く、可撓性に乏しい
という問題のある熱硬化性樹脂組成物を硬化させて得ら
れるフィルムについて、エポキシ系樹脂を、リン原子を
含有する脂肪族または脂肪族と芳香族を骨格に有する二
価以上のカルボン酸またはその酸無水物を硬化剤として
用いて硬化させることによりフィルムに耐炎性と可撓性
を持たせ、実用に供し得る熱硬化性樹脂フィルムとした
ものである。この有機リン化合物の硬化剤は、熱硬化性
樹脂の架橋構造中に脂肪族鎖を導入して可撓性を発現さ
せると共に、接炎時に分解して不揮発性のリン酸の保護
膜を形成し、また、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 cures a thermosetting resin composition which is inexpensive and has excellent dimensional stability, anti-fusing property, chemical resistance, etc., but has poor flame resistance and poor flexibility. The film obtained by curing the epoxy resin by using an aliphatic resin containing a phosphorus atom or a divalent or higher carboxylic acid having an aliphatic and aromatic skeleton or an acid anhydride thereof as a curing agent. The film has flame resistance and flexibility, and is a thermosetting resin film that can be put to practical use. This organic phosphorus compound curing agent introduces an aliphatic chain into the crosslinked structure of the thermosetting resin to exhibit flexibility, and decomposes during flame contact to form a nonvolatile phosphoric acid protective film. In addition, by promoting the carbonization of an organic substance by the dehydrating action of the generated phosphoric acid to form a carbonized film and cutting off the supply of oxygen, flame resistance is exhibited.
【００１７】[0017]
【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法は次の通りであ
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 measuring method 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 rated as ◯, and those with a retention rate of 90% or less 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.
【００１８】実施例１ クレゾールノボラック型エポキシ樹脂（チバカイギー社
製アラルダイトＥＣＮ−１２９９）５７重量部、化４で
示される硬化剤（ＰＰＡ−ＩＡ）４１重量部、硬化促進
剤（四国化成工業社製キュアゾールＣ11Ｚ）０．２重量
部、流展剤（ＢＡＳＦ社製アクロナル４Ｆ）１重量部を
ヘンシェルミキサー（三井三池製作所製ＦＭ１０Ｂ型）
でドライブレンドした後、コ・ニーダー（ブッス社製Ｐ
Ｒ−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性樹脂フィルムを得
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、優れた耐炎性を有していた。Example 1 57 parts by weight of a cresol novolak type epoxy resin (Araldite ECN-1299 manufactured by Ciba Kaiggy), 41 parts by weight of a curing agent (PPA-IA) represented by Chemical formula 4, a curing accelerator (Curesol manufactured by Shikoku Chemicals Co., Ltd.) C 11 Z) 0.2 parts by weight and a leveling agent (Acronal 4F made by BASF) 1 part by weight Henschel mixer (Mitsui Miike Seisakusho FM10B type)
After dry blending with a co kneader (Bus Co. P
R-46 type) was melt-kneaded at 120 ° C., cooled and solidified, 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.
In addition, the surface of the steel plate should be washed with dust, oil, etc.
A fluorine-based release agent (Die-free manufactured by Daikin) was applied. After the heat-treated steel sheet was cooled in air to room temperature, the film was peeled off from the steel sheet to obtain a thermosetting resin film. Table 1 shows the physical properties of the obtained film. This film was flexible and had excellent flame resistance.
【００１９】実施例２ クレゾールノボラック型エポキシ樹脂（チバカイギー社
製アラルダイトＥＣＮ−１２９９）５７重量部、化７で
示される硬化剤（ＨＣＡ−ＩＡ）４３重量部、硬化促進
剤（四国化成工業社製キュアゾールＣ11Ｚ）０．２重量
部、流展剤（ＢＡＳＦ社製アクロナル４Ｆ）１重量部を
用いて実施例１と同様に行った。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。Example 2 57 parts by weight of a cresol novolac type epoxy resin (Araldite ECN-1299 manufactured by Ciba Kaiggy), 43 parts by weight of a curing agent (HCA-IA) represented by Chemical formula 7, a curing accelerator (Curesol manufactured by Shikoku Chemicals Co., Ltd.) The same procedure as in Example 1 was carried out using 0.2 part by weight of C 11 Z) and 1 part 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.
【００２０】実施例３ トリグリシジルイソシアヌレート（チバガイギー社製ア
ラルダイトＰＴ−８１０）５０重量部、化４で示される
硬化剤（ＰＰＡ−ＩＡ）４９重量部、硬化促進剤（四国
化成工業社製キュアゾールＣ11Ｚ）０．２重量部、流展
剤（ＢＡＳＦ社製アクロナル４Ｆ）１重量部を用いて実
施例１と同様に行った。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。Example 3 50 parts by weight of triglycidyl isocyanurate (Araldite PT-810 manufactured by Ciba-Geigy), 49 parts by weight of a curing agent (PPA-IA) represented by Chemical formula 4, a curing accelerator (Curezol C manufactured by Shikoku Chemicals Co., Ltd.) The same procedure as in Example 1 was performed using 0.2 parts by weight of 11 Z) and 1 part by weight of a leveling agent (Acronal 4F manufactured by BASF). The physical properties of the obtained film are shown in Table 1.
Shown in. This film was also flexible as in Example 1 and had excellent flame resistance.
【００２１】実施例４ トリグリシジルイソシアヌレート（チバガイギー社製ア
ラルダイトＰＴ−８１０）５０重量部、化７で示される
硬化剤（ＨＣＡ−ＩＡ）５０重量部、硬化促進剤（四国
化成工業社製キュアゾールＣ11Ｚ）０．２重量部、流展
剤（ＢＡＳＦ社製アクロナル４Ｆ）１重量部を用いて実
施例１と同様に行った。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。Example 4 50 parts by weight of triglycidyl isocyanurate (Araldite PT-810 manufactured by Ciba Geigy), 50 parts by weight of a curing agent (HCA-IA) represented by Chemical formula 7, a curing accelerator (Curezol C manufactured by Shikoku Chemicals Co., Ltd.) The same procedure as in Example 1 was performed using 0.2 parts by weight of 11 Z) and 1 part by weight of a leveling agent (Acronal 4F manufactured by BASF). The physical properties of the obtained film are shown in Table 1.
Shown in. This film was also flexible as in Example 1 and had excellent flame resistance.
【００２２】比較例１ クレゾールノボラック型エポキシ樹脂（チバカイギー社
製アラルダイトＥＣＮ−１２９９）７６重量部、硬化剤
（無水フタル酸）２４重量部、流展剤（ＢＡＳＦ社製ア
クロナル４Ｆ）１重量部を用いて実施例１と同様にして
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、硬化剤として芳香族を骨格に有す
る無水フタル酸を用いているので可撓性に乏しく脆いも
のであり、また、耐炎性も悪く自己消火性の無いものと
なった。Comparative Example 1 Using 76 parts by weight of a cresol novolac type epoxy resin (Araldite ECN-1299 manufactured by Ciba Kaiggy), 24 parts by weight of a curing agent (phthalic anhydride) and 1 part by weight of a leveling agent (Acronal 4F manufactured by BASF). A film was obtained in the same manner as in Example 1. Table 1 shows the physical properties of the obtained film. Since this film uses phthalic anhydride having an aromatic skeleton as a curing agent, it has poor flexibility and brittleness, and also has poor flame resistance and no self-extinguishing property.
【００２３】比較例２ クレゾールノボラック型エポキシ樹脂（チバカイギー社
製アラルダイトＥＣＮ−１２９９）８０重量部、硬化剤
（コハク酸）２０重量部、硬化促進剤（四国化成工業社
製キュアゾールＣ11Ｚ）０．２重量部、流展剤（ＢＡＳ
Ｆ社製アクロナル４Ｆ）１重量部を用い実施例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、硬化剤として脂肪族を骨格に有するコ
ハク酸を用いているので可撓性は良いが、耐炎性に乏し
く自己消火性の無いものとなった。Comparative Example 2 80 parts by weight of a cresol novolac type epoxy resin (Araldite ECN-1299 manufactured by Ciba Kaiggy), 20 parts by weight of a curing agent (succinic acid), a curing accelerator (Curezol C 11 Z manufactured by Shikoku Chemicals Co., Ltd.). 2 parts by weight, extender (BAS
The same procedure as in Example 1 was carried out using 1 part by weight of Acronal 4F manufactured by Company F). Table 1 shows the physical properties of the obtained film.
Since this film uses succinic acid having an aliphatic skeleton as a curing agent, it has good flexibility, but has poor flame resistance and no self-extinguishing property.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【発明の効果】本発明は、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性樹脂フィルムが安
価に得られる。INDUSTRIAL APPLICABILITY According to the present invention, a thermosetting resin film which is excellent in dimensional stability, anti-fusing property, alkali resistance, satisfactory in flame resistance and flexibility, and which does not generate toxic gas during flame contact is inexpensive. can get.
Claims (3)
される有機リン化合物を硬化剤として硬化させることに
より得られるエポキシ系耐炎性熱硬化性樹脂フィルム。 【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は脂肪族または脂肪族と芳香族とから成る骨格を
有する二価以上のカルボン酸またはその酸無水物であ
る。）1. An epoxy flame-resistant thermosetting resin film obtained by curing an epoxy resin with an organic phosphorus compound represented by the following general formula (1) as a curing agent. [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. X is X. A divalent or higher carboxylic acid having an skeleton composed of an aliphatic or an aliphatic and an aromatic, or an acid anhydride thereof.)
下記構造式（２）で表される化合物である請求項１記載
のエポキシ系耐炎性熱硬化性樹脂フィルム。 【化２】 2. The epoxy flame-resistant thermosetting resin 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]
下記構造式（３）で表される化合物である請求項１記載
のエポキシ系耐炎性熱硬化性樹脂フィルム。 【化３】 3. The epoxy flame-resistant thermosetting resin 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 (3). [Chemical 3]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25901392A JP3244539B2 (en) | 1992-09-02 | 1992-09-02 | Epoxy flame-resistant thermosetting resin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25901392A JP3244539B2 (en) | 1992-09-02 | 1992-09-02 | Epoxy flame-resistant thermosetting resin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0680765A true JPH0680765A (en) | 1994-03-22 |
| JP3244539B2 JP3244539B2 (en) | 2002-01-07 |
Family
ID=17328141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25901392A Expired - Fee Related JP3244539B2 (en) | 1992-09-02 | 1992-09-02 | Epoxy flame-resistant thermosetting resin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3244539B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0665237A1 (en) * | 1994-01-29 | 1995-08-02 | Hoechst Aktiengesellschaft | Process for the preparation of phosphorus containing dicarboxylic acid esters and dicarboxylic acids |
| EP0799850A1 (en) * | 1996-04-01 | 1997-10-08 | Hoechst Aktiengesellschaft | Phosphorus modified epoxy resins and a method for their preparation |
| EP0799847A1 (en) * | 1996-04-01 | 1997-10-08 | Hoechst Aktiengesellschaft | Phosphorus modified epoxy resin compositions based on epoxy resins, phosphor containing compounds and a curing agent |
| US5773533A (en) * | 1996-04-01 | 1998-06-30 | Hoechst Aktiengesellschaft | Epoxy resin reacted with carboxy-functional phosphinic or phosphonic acid and hardener |
| US5854361A (en) * | 1996-04-01 | 1998-12-29 | Hoechst Aktiengesellschaft | Process for preparing phosphorus-modified epoxy resins |
| JP2006124477A (en) * | 2004-10-27 | 2006-05-18 | Nof Corp | Flame-retarded polyester film |
| EP2123712A1 (en) | 2008-05-19 | 2009-11-25 | Evonik Degussa GmbH | Epoxy resin composition and electronic part |
| CN105623192A (en) * | 2015-12-28 | 2016-06-01 | 上海华谊树脂有限公司 | Preparing method for modified flame-retardant TGMDA (tetra-glycidyl diaminodiphenyl methane) composition |
-
1992
- 1992-09-02 JP JP25901392A patent/JP3244539B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0665237A1 (en) * | 1994-01-29 | 1995-08-02 | Hoechst Aktiengesellschaft | Process for the preparation of phosphorus containing dicarboxylic acid esters and dicarboxylic acids |
| EP0799850A1 (en) * | 1996-04-01 | 1997-10-08 | Hoechst Aktiengesellschaft | Phosphorus modified epoxy resins and a method for their preparation |
| EP0799847A1 (en) * | 1996-04-01 | 1997-10-08 | Hoechst Aktiengesellschaft | Phosphorus modified epoxy resin compositions based on epoxy resins, phosphor containing compounds and a curing agent |
| US5773533A (en) * | 1996-04-01 | 1998-06-30 | Hoechst Aktiengesellschaft | Epoxy resin reacted with carboxy-functional phosphinic or phosphonic acid and hardener |
| US5854361A (en) * | 1996-04-01 | 1998-12-29 | Hoechst Aktiengesellschaft | Process for preparing phosphorus-modified epoxy resins |
| US5880247A (en) * | 1996-04-01 | 1999-03-09 | Hoechst Aktiengesellschaft | Phosphorus-containing dicarboxylic acid (anhydride)-modified epoxy resin |
| EP0799845A3 (en) * | 1996-04-01 | 1999-03-31 | Clariant GmbH | Phosphorus-modified epoxy resin compositions |
| US5959043A (en) * | 1996-04-01 | 1999-09-28 | Clariant Gmbh | Phosphorus-containing dicarboxylic reaction product of epoxy resins and phosphorus acid (anhydride) with hardener |
| EP0799849B1 (en) * | 1996-04-01 | 2003-08-20 | Clariant GmbH | Process for the preparation of phosphorus modified epoxy resins |
| JP2006124477A (en) * | 2004-10-27 | 2006-05-18 | Nof Corp | Flame-retarded polyester film |
| EP2123712A1 (en) | 2008-05-19 | 2009-11-25 | Evonik Degussa GmbH | Epoxy resin composition and electronic part |
| CN105623192A (en) * | 2015-12-28 | 2016-06-01 | 上海华谊树脂有限公司 | Preparing method for modified flame-retardant TGMDA (tetra-glycidyl diaminodiphenyl methane) composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3244539B2 (en) | 2002-01-07 |
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