JPS6172023A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:A thermosetting resin composition that contains, as essential components, an adduct from bismaleimide and an aminobenzoic acid with heat and polyether imide, which are represented by specific formulas, respectively, thus showing high heat resistance, good processability and mechanical properties. CONSTITUTION:The objective composition is obtained by adding, as essential components, (A) an addition product, which is prepared by reaction between a bismaleimide such as 4, 4'-methylenebis (N-phenylmaleimide) and an aminobenzoic acid at 100 deg.C-150 deg.C, then cooling the reaction product and is represented by formula I (R<1> is H, alkyl; R<2> is -O-, -CH2-, -SO2-, -S-S-; R<3> is H, alkyl, C1), and (B) a polyether imide of formula II (n is positive integer).

Description

【発明の詳細な説明】 ［・発明の技術分野］ 本発明は、耐熱性、加工性、機械的特性の優れた熱硬化
性樹脂組成物に関する。Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a thermosetting resin composition having excellent heat resistance, processability, and mechanical properties.

〔発明の技術的背景とその問題点］ ポリイミド系樹脂は、耐熱性、耐薬品性等に優れている
ので、従来から高温で使用するフィルム、電線被覆、積
層品、塗料、接着剤、成形品等の種々の用途に使われて
いる。[Technical background of the invention and its problems] Polyimide resins have excellent heat resistance and chemical resistance, so they have traditionally been used in films, wire coatings, laminates, paints, adhesives, and molded products that are used at high temperatures. It is used for various purposes such as.

その中！ビスマレイミドとアミノ安息香酸との１合物や
ビスマレイミド単独重合物又はビスマレイミドとモノマ
レイミドとの共重合物は、熱的性質においては非常に優
れているが、その分子構造から明らかなように機械的強
度が十分でない。In it! Monomers of bismaleimide and aminobenzoic acid, homopolymers of bismaleimide, and copolymers of bismaleimide and monomaleimide have excellent thermal properties, but as is clear from their molecular structures. Mechanical strength is not sufficient.

そのため、他の材料と共重合させることによりその熱的
性質をある程度犠牲にし、機械的強度を改良し使用して
いる。　また、ビスマレイミドは、融点が１５０℃以上
のものが多く成形材料の加熱混線など加工するのに困難
であり、しかもその融点以上でのラジカル連鎖重合は速
度が非常に速いため成形の許容範囲が狭く、更に急速な
硬化による発熱のために硬化した成形品に歪を生じ易く
、ビスマレイミド単独やモノマレイミドとの共重合樹脂
は、実用化に難しい問題がある。　一方、ウルテム（Ｇ
Ｅ社製商品名）に代表されるポリエーテルイミドは、機
械的特性、熱的特性に優れているが熱可塑性のため、１
６０℃以上の高温では寸法変化、熱変形が大きいという
欠点があった。Therefore, it is used by copolymerizing it with other materials, sacrificing some of its thermal properties and improving its mechanical strength. In addition, many bismaleimides have melting points of 150°C or higher, making it difficult to process them by heating and cross-linking the molding materials.Furthermore, the rate of radical chain polymerization above the melting point is extremely fast, so the tolerance range for molding is limited. Due to narrow and rapid heat generation during curing, the cured molded product tends to be distorted, and bismaleimide alone or copolymer resins with monomaleimide have problems in practical application. On the other hand, Ultem (G
Polyetherimide (trade name manufactured by Company E) has excellent mechanical and thermal properties, but because it is thermoplastic,
At high temperatures of 60° C. or higher, dimensional changes and thermal deformation are large.

［発明の目的］ 本発明の目的は、前記の欠点を解消するためになされた
もので、耐熱性、機械的特性が良好で、かつ加工性に優
れた、積層用または成形材として広く用いることができ
る熱硬化性樹脂組成物を提供しようとするものである。[Object of the Invention] The object of the present invention was to solve the above-mentioned drawbacks, and to provide a material having good heat resistance, mechanical properties, and excellent workability, and widely used as a laminating or molding material. The purpose is to provide a thermosetting resin composition that can

［発明の概要１ 本発明は、上記目的を達成すべく鋭意研究を重ねた結果
、ビスマレイミドと７ミノ安息香酸との付加反応物にポ
リエーテルイミドを加えて使用することにより、前記目
的を達成できることを見いだしたものである。[Summary of the Invention 1] As a result of extensive research to achieve the above object, the present invention achieves the above object by adding polyetherimide to an addition reaction product of bismaleimide and 7-minobenzoic acid. I found out what I can do.

即ら本発明は、（Ａ）一般式（’Ｉ）で示される（ａ）
ビスマレイミドと（ｂ）アミノ安息香酸とを加熱反応せ
しめてなる付加反応物と、・・・（Ｉ＞ （式中Ｒ１は水素原子又はアルキル基を、Ｒ２は−０−
１ＣＨ２−１−８０２−又は−５−Ｓ−を、Ｒ３は水素
原子、アルキル基又は塩素原子を表す） （Ｂ）一般式（ＩＩ）で示されるポリエーテルイミド ・・・　（ＩＩ） （式中、ｎは正の整数を表す） とを必須成分とすることを特徴とする熱硬化性樹脂組成
物である。That is, the present invention provides (A) (a) represented by the general formula ('I)
An addition reaction product obtained by heat-reacting bismaleimide and (b) aminobenzoic acid, ... (I> (wherein R1 is a hydrogen atom or an alkyl group, R2 is -0-
1CH2-1-802- or -5-S-, R3 represents a hydrogen atom, an alkyl group or a chlorine atom) (B) Polyetherimide represented by the general formula (II)... (II) (In the formula , n represents a positive integer) as essential components.

本発明に用いる（ａ）ビスマレイミドは、マレイン酸お
よびその誘導体とジアミノとの縮合反応物で具体的には
、４．４′−メチレンビス（Ｎ−）工二ルマレイミド）
、４，４′　−オキシビス（Ｎ−フェニレンマレイミド
）　　４．４’　−スルホンビス（Ｎ−フェニルマレイ
ミド）、４．４′　−ジチオビス（Ｎ−フェニルマレイ
ミド）等が挙げられこれらは単独又は２種以上混合して
用いる。(a) Bismaleimide used in the present invention is a condensation reaction product of maleic acid and its derivatives with diamino, specifically, 4,4'-methylenebis(N-)enylmaleimide)
, 4,4'-oxybis(N-phenylenemaleimide), 4,4'-sulfonebis(N-phenylmaleimide), 4,4'-dithiobis(N-phenylmaleimide), etc. These may be used alone or in combination of two or more. and use it.

本発明に用いる（ｂ）アミノ安息香酸としては、たとえ
ば、ｐ−アミノ安息香酸、ドアミノ安息香酸、Ｏ−７ミ
ノ安息香酸等が挙げられ、これらは単独又は２種以上の
組合せとして用いる。　アミノ安息酸はいかなる量でも
ヒスマレイミドに付加重合させることができるが、硬化
時間や成形加工性を適当にするためにはビスマレイミド
１モルに対してアミノ安息香酸０．２〜１．０モル、特
に０．４〜０．８モル使用することが好ましい。　ビス
マレイミドとアミノ安息香酸との付加重合は、溶融下で
加熱反応させることによって行うがジオキサン、Ｎ。Examples of the aminobenzoic acid (b) used in the present invention include p-aminobenzoic acid, doaminobenzoic acid, O-7 minobenzoic acid, and the like, and these are used alone or in combination of two or more. Aminobenzoic acid can be addition-polymerized to hismaleimide in any amount, but in order to make the curing time and moldability appropriate, aminobenzoic acid should be added in an amount of 0.2 to 1.0 mol per mol of bismaleimide. It is particularly preferable to use 0.4 to 0.8 mol. Addition polymerization of bismaleimide and aminobenzoic acid is carried out by a heating reaction in the melt using dioxane and N.

Ｎ′−ジメチルアセトアミド、ジメチルホルムアミド、
Ｎ−メチル−２−ピロリドン等の溶媒中で加熱反応させ
ることもできる。　溶媒下の加熱反応ではビスマレイミ
ドとアミノ安息香酸とを攪拌しつつ温度上昇させると１
００℃前後で溶融し、１００〜１５０℃の温度に保持す
れば付加重合反応を起こし、常温に冷却して固体又は粘
稠な付加反応物を（Ｊることができる。N'-dimethylacetamide, dimethylformamide,
The reaction can also be carried out by heating in a solvent such as N-methyl-2-pyrrolidone. In a heating reaction in a solvent, when bismaleimide and aminobenzoic acid are stirred and the temperature is raised, 1
If it is melted at around 00°C and maintained at a temperature of 100 to 150°C, an addition polymerization reaction will occur, and a solid or viscous addition reaction product can be produced by cooling to room temperature.

（Ａ）の付加反応物の配合割合は、樹脂組成物に対して
１５〜８５重帝％含有することが望ましい。The blending ratio of the addition reaction product (A) is preferably 15 to 85% by weight based on the resin composition.

１５重量％未満では所望の加工性が得られず、また８５
重母％を超えると作業性が向上するものの機械的強度が
低下し好ましくない。If it is less than 15% by weight, the desired processability cannot be obtained;
If it exceeds the weight percentage, the workability will improve, but the mechanical strength will decrease, which is not preferable.

本発明の熱硬化性樹脂組成物の１成分である（Ｂ）ポリ
エーテルイミドとしては、例えばウルテム（ＧＥ社製商
品名）が挙げられる。　本発明の樹脂組成物は通常、例
えばＮ−メチル−２−ピロリドン、ジメチルアセトアミ
ド、ジメチルホルムアミド、ジオキサン、メチルセロソ
ルブ、エチルセロソルブ等の単独又は混合溶媒に溶解し
、これにガラス布等の積層品用基材に含浸塗布して樹脂
溶液を被着させる。　次いで溶媒を揮散除去して得たプ
リプレグを重ね合わせ、加熱、加圧成形して、優れた耐
熱性、電気特性および機械的特性−を備えた積層品を得
ることができる。　また成形材料に応用する場合、樹脂
溶液を大過剰の水中に注ぎ樹脂分のみ分離乾燥して、１
８０〜２００℃で成形可能な粉末材料を得ることができ
る。　　（Ａ）の粉末と（Ｂ）の粉末とをトライブレン
ドすることによっても同様に１８０〜２５０℃で成形可
能な粉末成形材料が得られる。　これらの成形材料は機
械的特性および熱的に優れた成形品を得ることができる
。Examples of the polyetherimide (B) which is one component of the thermosetting resin composition of the present invention include Ultem (trade name, manufactured by GE). The resin composition of the present invention is usually dissolved in a single or mixed solvent such as N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dioxane, methyl cellosolve, ethyl cellosolve, etc., and is used for laminated products such as glass cloth. The resin solution is applied to the base material by impregnation coating. Next, the prepregs obtained by volatilizing the solvent are superimposed, heated, and pressure-molded to obtain a laminate having excellent heat resistance, electrical properties, and mechanical properties. When applied to molding materials, the resin solution is poured into a large excess of water and only the resin is separated and dried.
A moldable powder material can be obtained at 80-200°C. A powder molding material that can be molded at 180 to 250°C can also be obtained by triblending the powders of (A) and (B). These molding materials make it possible to obtain molded articles with excellent mechanical properties and thermal properties.

［発明の実施例〕 以下本発明を実施例によって具体的に説明するが、本発
明はこれらに限定されるものではない。[Examples of the Invention] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

実施例　１ ４．４′　−メチレンビス（Ｎ−７エニルマレイミド）
（分子ｆｆｉ　３５８）　　１モルにｐ−アミノ安息香
酸（分子ｆｉ　１３７）　　０．６モルを混合し、攪拌
しながら１００℃に昇温し、一様に溶解した液体とした
。Example 1 4.4'-methylenebis(N-7enylmaleimide)
(Molecular ffi 358) 1 mole was mixed with 0.6 mole of p-aminobenzoic acid (molecule fi 137), and the mixture was heated to 100° C. with stirring to form a uniformly dissolved liquid.

この液体を１３０℃に昇温し３０分間保持し、常温に冷
却して固形の付加反応物を得た。　粉砕した付加反応物
２００ｇにＮ−メチル−２−ピロリドン２００１；ｌを
加え、次いでウルテム（ＧＥ社製ポリエーテルイミド商
品名）６０ｇをジメチルホルムアミド３００ｇとＮ−メ
チル−２−ピロリドン３００９との混合溶媒に溶解した
溶液を添加して、９０℃で１時間加熱攪拌して均一な樹
脂組成物を得た。　なお樹脂組成物の熱分解曲線を第１
図に示した。This liquid was heated to 130°C, held for 30 minutes, and cooled to room temperature to obtain a solid addition reaction product. 2001; 1 of N-methyl-2-pyrrolidone was added to 200 g of the pulverized addition reaction product, and then 60 g of Ultem (trade name of polyetherimide manufactured by GE) was added to a mixed solvent of 300 g of dimethylformamide and N-methyl-2-pyrrolidone 3009. A uniform resin composition was obtained by adding a solution dissolved in the mixture and heating and stirring at 90° C. for 1 hour. Note that the thermal decomposition curve of the resin composition is
Shown in the figure.

この溶液をγ−アミノプロピルトリエトキシシラン処理
したサテン型ガラスクロスに塗布し、１１０℃で５分間
、１５０℃で１０分間、１７０℃で５分間乾燥してプリ
プレグを得た。　次いでこのプリプレグを複数枚重ね合
わせ、２００℃に加熱したプレスで、２回ガス扱きを行
いながら予備成形してから６０　ｋａｆ／ａ１の圧力で
６０分間保持した後、圧力を除去して積層板を得た。　
得られた積層板を２３０℃で１５時間保ち後硬化させて
、曲げ強さを測定したところ、室温で５７　ｋｇｆ／１
ｍ’　、また２００℃で５０　ｋｏｆ／ｍｎ＋２の強度
を保持し、さらに２３０℃で２０日間劣化後でも５２　
ｋｇｆ／ａｍ２の値を示した。This solution was applied to a satin-type glass cloth treated with γ-aminopropyltriethoxysilane and dried at 110°C for 5 minutes, 150°C for 10 minutes, and 170°C for 5 minutes to obtain a prepreg. Next, a plurality of sheets of this prepreg were stacked, preformed in a press heated to 200°C while being treated with gas twice, and held at a pressure of 60 kaf/a1 for 60 minutes, then the pressure was removed and the laminate was formed. Obtained.
The resulting laminate was kept at 230°C for 15 hours and then cured, and its bending strength was measured; it was 57 kgf/1 at room temperature.
m', also maintains a strength of 50 kof/mn+2 at 200°C, and further maintains a strength of 52 kof/mn+2 even after deterioration for 20 days at 230°C.
The value of kgf/am2 is shown.

実施例　２ ４．４′　−オキシビス（Ｎ−フェニルマレイミド）（
分子ｆｆｉ　３６０）　　１モルとｐ−アミノ安息香酸
（分子ｆｆｉ　１３７）　　０．４モルとを混合し、攪
拌しながら１１０℃にし一様に溶解して液状とする。　
この液体を１４０℃で昇温して３０分間保持しその後常
温まで冷却して付加反応物を得た。　粉砕した付加反応
物４０１　ｆｆ１％、ウルテム（ＧＥ社製ポリエーテル
イミド商品名）１０ｍｆｆｉ％、シリカ粉末２５重量％
、アミノシラン処理したガラスチョップ２５重量％とを
よく混合し、１４０℃で１０分間混練して冷加した後、
粉砕して成形材料を得た。　この成形材料を２４０℃に
加熱した金型内におき３００ｋｇ　ｒ／　ｃｍ２の圧力
で５分間加圧成形したところ外観の良い成形品を得るこ
とができた。　成形品を２５０°Ｃで５時間保ら１！！
硬化した模、引張り強さＬＪ　Ｉｓ−に６９１１による
）の試験を行ったところ、室温で１１．７　ｋす【／ｌ
ｌｌｌｌ１２．２５０℃でも１０．２　ｋ＋Ｊｆ／ｍｍ
２の強度をもち、２５０℃で２０日間加熱劣化後でも８
．６　ｋｏｆ／＋＋＋ｍ２（室温測定）の強度を保持し
ていた。　なお、充填剤混線前の熱分解曲線を第１図に
示した。Example 2 4.4'-oxybis(N-phenylmaleimide) (
1 mole of molecule ffi 360) and 0.4 mole of p-aminobenzoic acid (molecule ffi 137) are mixed and heated to 110° C. with stirring to uniformly dissolve and form a liquid.
This liquid was heated to 140°C, held for 30 minutes, and then cooled to room temperature to obtain an addition reaction product. Pulverized addition reaction product 401 ff1%, Ultem (GE's polyetherimide brand name) 10mffi%, silica powder 25% by weight
, and 25% by weight of aminosilane-treated glass chops, kneaded at 140°C for 10 minutes, and cooled.
It was crushed to obtain a molding material. When this molding material was placed in a mold heated to 240° C. and pressure molded for 5 minutes at a pressure of 300 kg r/cm 2 , a molded product with a good appearance could be obtained. The molded product can be kept at 250°C for 5 hours! !
When the cured specimen was tested for tensile strength LJ Is-6911), it had a tensile strength of 11.7 k/l at room temperature.
lllll12.10.2 k+Jf/mm even at 250℃
It has a strength of 2, and even after heat aging at 250℃ for 20 days, it has a strength of 8.
．． The strength was maintained at 6 kof/+++m2 (measured at room temperature). Incidentally, the thermal decomposition curve before filler crosstalk is shown in FIG.

実施例　３ ４．４′　−メチレンビス（Ｎ−フェニルマレイミド）
　（分子口３５８）　１７９ｇと、０−アミノ安息香酸
２５９とをジメチルアセトアミド９０ｇに溶解し、１１
０℃で１４時間反応させ６０℃に冷却後、ウルテム（Ｇ
Ｅ社製ポリエーテルイミド商品名）９０９を３００ｇの
Ｎ−メチル−２＝ピロリドンに溶解した溶液に加えて、
６０℃で３０分間攪拌して均一な樹脂組成物溶液とした
。　得られた溶液を１．５ｘ　２５ｘ　１００ｍｍの軟
鋼板の端的１Ｏｎ＋ｍ幅に厚さ３０μｍになるように塗
布して、１１０℃で５分間、１５０℃で１０分間、　　
１８０’Ｃで５分間熱風乾燥処理した。　その後２枚の
軟鋼板を幅約１０ｍｍオーバーラツプしてセットし、２
００℃、１０ｋＭｃｍ２．３０分間熱板プレスで加熱加
圧した後、２５０℃で５時間保ち侵硬化を行って曲げ強
度を測定した。　室温で２４　ｋｇｆ／ｃｍ２．２００
°ｃｒ２２ｋｇ「／Ｃｌｌ１２の強度を持ら、２５０℃
で２００時間加熱侵でも２１　ｋｇｆ／ｃｍ２（ｉ７温
測定）の強度を保持していた。Example 3 4.4'-methylenebis(N-phenylmaleimide)
(Molecular mouth 358) 179 g and 0-aminobenzoic acid 259 were dissolved in 90 g of dimethylacetamide, and 11
After reacting at 0°C for 14 hours and cooling to 60°C, Ultem (G
Add to a solution of polyetherimide (trade name) 909 manufactured by Company E dissolved in 300 g of N-methyl-2=pyrrolidone,
The mixture was stirred at 60° C. for 30 minutes to obtain a uniform resin composition solution. The obtained solution was applied to a 1On+m width of a mild steel plate measuring 1.5 x 25 x 100 mm to a thickness of 30 μm, and heated at 110°C for 5 minutes and at 150°C for 10 minutes.
Hot air drying treatment was performed at 180'C for 5 minutes. After that, set two mild steel plates with an overlap of about 10 mm in width, and
After heating and pressing with a hot plate press for 2.30 minutes at 00° C. and 10 kmcm, the specimens were kept at 250° C. for 5 hours to undergo erosion hardening, and the bending strength was measured. 24 kgf/cm2.200 at room temperature
°cr22kg/Cll12 strength, 250℃
It maintained a strength of 21 kgf/cm2 (I7 temperature measurement) even after heating for 200 hours.

［発明の効果］ 以上の説明および図面から明らかなように、本発明の樹
脂組成物はビスマレイミドとアミノ安息香酸との付加反
応物にポリエーテルイミドを配合することによって、従
来の欠点をカバーした、耐熱性、加工性、礪械的特性の
優れた樹脂組成物として得られたものであり、８１Ｍ用
、成形材料用として好適なものである。[Effects of the Invention] As is clear from the above description and drawings, the resin composition of the present invention overcomes the conventional drawbacks by blending polyetherimide into the addition reaction product of bismaleimide and aminobenzoic acid. The resin composition was obtained as a resin composition with excellent heat resistance, processability, and mechanical properties, and is suitable for use in 81M and as a molding material.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は本発明に係る熱硬化性樹脂組成物の熱分解温度
を示す曲線図である。FIG. 1 is a curve diagram showing the thermal decomposition temperature of the thermosetting resin composition according to the present invention.

Claims (1)

【特許請求の範囲】 １　（Ａ）一般式（ I ）で示される（ａ）ビスマレイ
ミドと（ｂ）アミノ安息香酸とを加熱反応せしめてなる
付加反応物と、 ▲数式、化学式、表等があります▼…（ I ） （式中、Ｒ＾１は水素原子又はアルキル基を、Ｒ＾２は
−Ｏ−、−ＣＨ＿２−、−ＳＯ＿２−又は−Ｓ−Ｓ−を
、 Ｒ＾３は水素原子、アルキル基又は塩素原子を表す） （Ｂ）一般式（II）で示されるポリエーテルイミド ▲数式、化学式、表等があります▼…（II） （式中、ｎは正の整数を表す） とを必須成分とすることを特徴とする熱硬化性樹脂組成
物。 ２　（Ａ）の付加反応物を１５〜８５重量％、（Ｂ）の
ポリエーテルイミドを８５〜１５重量％含有することを
特徴とする特許請求の範囲第１項記載の熱硬化性樹脂組
成物。 ３　（Ａ）の付加反応物は、（ａ）のビスマレイミド１
モルに対し（ｂ）のアミノ安息香酸０．２〜１モルを反
応せしめることを特徴とする特許請求の範囲第１項又は
第２項記載の熱硬化性樹脂組成物。[Scope of Claims] 1 (A) An addition reaction product obtained by heating and reacting (a) bismaleimide and (b) aminobenzoic acid represented by general formula (I); Yes▼...(I) (In the formula, R^1 is a hydrogen atom or an alkyl group, R^2 is -O-, -CH_2-, -SO_2- or -S-S-, and R^3 is a hydrogen atom , represents an alkyl group or a chlorine atom) (B) Polyetherimide represented by the general formula (II)▲There are numerical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, n represents a positive integer) and A thermosetting resin composition comprising as an essential component. 2. The thermosetting resin composition according to claim 1, which contains 15 to 85% by weight of the addition reaction product (A) and 85 to 15% by weight of the polyetherimide (B). . 3 The addition reaction product of (A) is the bismaleimide 1 of (a)
3. The thermosetting resin composition according to claim 1 or 2, wherein 0.2 to 1 mol of the aminobenzoic acid (b) is reacted per mol.