JPS62127316A - Thermosetting resin composition - Google Patents
Thermosetting resin compositionInfo
- Publication number
- JPS62127316A JPS62127316A JP26561385A JP26561385A JPS62127316A JP S62127316 A JPS62127316 A JP S62127316A JP 26561385 A JP26561385 A JP 26561385A JP 26561385 A JP26561385 A JP 26561385A JP S62127316 A JPS62127316 A JP S62127316A
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- Japan
- Prior art keywords
- parts
- aryl
- resin
- component
- epoxidized
- 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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- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は熱硬化性樹脂組成物に関し、更に詳しくは、加
工性、耐熱性、接着性に優れた熱硬化性樹脂組成物に関
する〇
熱硬化性樹脂は、注型、含浸、積層、成形用材料として
、各種電気絶縁材料、構造材料などに使用されている0
近年これらの各用途において材料の使用条件は厳しくな
る傾向にあり、特に材料の耐熱性は重要な特性になって
いる〇又、積層板等においては、耐熱性と同時に基材と
の接着性も重要な特性となってきている〇従来、このよ
うな目的には熱硬化性のポリイミド樹脂が使用されてい
るが、硬化に至る着でに高温で長時間の加熱を必要とし
、更に基材との接着性が不充分であった。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition, and more particularly to a thermosetting resin composition having excellent processability, heat resistance, and adhesive properties. 0 is used in various electrical insulation materials, structural materials, etc. as impregnation, lamination, and molding materials.
In recent years, the conditions for using materials in each of these applications have tended to become stricter, and the heat resistance of materials has become an especially important property.In addition, in laminates, etc., it is important to have not only heat resistance but also adhesion to the base material. Traditionally, thermosetting polyimide resins have been used for this purpose, but they require heating at high temperatures and for long periods of time to harden, and they also have problems with the base material. Adhesion was insufficient.
また、1#熱性に改良を加えたエポキシ樹脂は加工性、
接着性に侵れているものの、高温時の機械特性、電気特
性および艮期の耐熱劣(?、性など高度の附勢性能は不
充分であった。In addition, 1# epoxy resin with improved thermal properties has excellent processability.
Although the adhesion was impaired, the mechanical properties at high temperatures, electrical properties, and high-level energization performance such as poor heat resistance during the mounting stage were insufficient.
これらに代る材料の一つとして、例えばポリイミド、特
定の構造を有するアリル基含南エポキシ化合物および五
史化剤からなる熱硬化性混合物(特開昭52−1548
97)が提案されているが、ここで使用されているアリ
ρ基含有エポキシ化合物は、アリルエーテル化合物のク
ライゼン転移動をエポキシ化せしめたものであり、核置
換アリル基とエポキシ基が向−芳香環のオルソ位に位置
しているためか、均一なε史化物を得ることがむつかし
く、特にノボラックタイプの場合、いずれかの基が未反
喧0廿壕残存しやすいためか、硬化物性、面1熱特性′
9に問題があった。As an alternative material to these materials, for example, a thermosetting mixture consisting of polyimide, an allyl group-containing epoxy compound having a specific structure, and a five-year-old agent (Japanese Unexamined Patent Publication No. 52-1548
97) has been proposed, but the allyl ρ group-containing epoxy compound used here is an epoxidized Claisen rearrangement of an allyl ether compound, in which the nuclear substituted allyl group and the epoxy group are anti-aromatic. Perhaps because it is located at the ortho position of the ring, it is difficult to obtain a uniform ε-formed compound, and especially in the case of novolak type, one of the groups tends to remain unresolved. 1 Thermal characteristics'
There was a problem with 9.
このよう々背景から、本発明者らは耐熱特性に優れた樹
脂岨成物について峰琶倹771.た結果、特定の樹脂、
マレイミド系化合物および必要に応じ硬化司を含む1旬
1]i組成物が前記目的に適うことを見出し本発明を完
成するに至った。Against this background, the present inventors have developed a resin composite material with excellent heat resistance properties. As a result, certain resins,
The present inventors have discovered that a composition containing a maleimide compound and, if necessary, a curing agent is suitable for the above-mentioned purpose and has completed the present invention.
即ち、本発明は、(5)フェノール性水酸基がエポキシ
化およびアリルエーテル化されたフェノール類ノ承フッ
ク樹8)1、(B)分子中に2個以上のマレイミド基を
有するポリマレイミド化合物、および必要に応じ(C1
硬化剤を含有してなる熱硬化性樹!嘴組成物を提供する
。That is, the present invention provides (5) a hook tree of phenols having epoxidized and allyl etherified phenolic hydroxyl groups, (B) a polymaleimide compound having two or more maleimide groups in the molecule, and As necessary (C1
A thermosetting tree containing a hardening agent! A beak composition is provided.
本発明で使用される(3)成分は、ア/L’″fル基、
アリー/V基、アフルキル基、ア〃ケ二ル基或いはハロ
ゲン1卓子で′fft換された、或いは無置換のフェノ
ール類、具体的にはフェノール、クレゾール、エチルフ
ェノール、イソプロピルフェノール、ブチルフェノール
、オクチルフェノール、ノニルフェノール、ビニルフェ
ノール、インプロペニルフェノール、フェニルフェノー
ル、ベンジルフェノール、クロルフェノール、ブロムフ
ェノール、キシレノール、メチルブチルフェノール、メ
トキシフェノール、エトキシフェノール、α−メチルベ
ンジルフェノール、β−フェニルエチルフェノール、ジ
ヒドロキシベンゼン(夫々異性体を含む)、ビスフェノ
−/vA等のフェノール類の一種又は二種以上とホルム
アルデヒド、フルフラール、アクロレイン、グリオキザ
ール等のアルデヒド類を公知の方法で縮合反応させて得
られる通常2〜15の平均核停数を有するノボフック樹
脂と塩化アリ〜、臭化アリル、ヨウ化アリル等のハロゲ
ン化アリ〜とをアルカリの存在下反応させて得られるア
リルエーテル化フェノール類ノボフック樹脂を部分的に
エポキシ化することによシ得られる0部分的にエポキシ
化する方法としては、フェノール類ノボヲック樹脂を所
望のアリルエーテル化ぷと々るよう、部分的にアリルエ
ーテル化させた後、残余の水酸基をエピクロルヒドリン
、エビブロモヒドリン、メチルエピクロルヒドリン券の
エビハロヒドリンとアルカリの存在下反応させる方法、
或いは、はぼ完全にアリルエーテル化させた後、過酸化
水素、過酸等の過酸化物により所望のエポキシ化率とな
るように部分的にエポキシ化する方法がある。Component (3) used in the present invention is an a/L'″f group,
ary/V group, afurkyl group, akenyl group, or unsubstituted or unsubstituted phenols, specifically phenol, cresol, ethylphenol, isopropylphenol, butylphenol, octylphenol, Nonylphenol, vinylphenol, impropenylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, xylenol, methylbutylphenol, methoxyphenol, ethoxyphenol, α-methylbenzylphenol, β-phenylethylphenol, dihydroxybenzene (isomers of each ), bispheno-/vA, etc., and an aldehyde such as formaldehyde, furfural, acrolein, glyoxal, etc. by a known method. By partially epoxidizing the allyl etherified phenol Novohook resin obtained by reacting the Novohook resin having the following with an allyl halide such as allyl chloride, allyl bromide, allyl iodide, etc. in the presence of an alkali. The method for partially epoxidizing the phenolic Novowoc resin is to partially epoxidize the phenolic Novowoc resin to the desired allyl etherification compound, and then convert the remaining hydroxyl groups to epichlorohydrin, shrimp bromohydrin, etc. A method of reacting methylepichlorohydrin with shrimp halohydrin in the presence of an alkali,
Alternatively, after almost completely allyl etherification, there is a method of partially epoxidizing with a peroxide such as hydrogen peroxide or peracid to achieve a desired epoxidation rate.
ここで、エポキシ化された水酸基に対するアリルエーテ
ル化された水酸基の比は好ましくは0.5〜90より好
ましくは07〜4.0とすべきである。Here, the ratio of allyl etherified hydroxyl groups to epoxidized hydroxyl groups should preferably be between 0.5 and 90, more preferably between 07 and 4.0.
アリルエーテル基の比が大きいと、接着性が低下し、一
方その比が小さいとIIthIP性が低下する0
本発明で使用されるfB)成分は一般式[I)で表わさ
れるマレイミド基を分子中に2個以上含有する化合物で
ある。If the ratio of allyl ether groups is large, the adhesion properties will be reduced, while if the ratio is small, the IIthIP properties will be reduced. It is a compound containing two or more.
(式中、Rは水素原子または低級アルキルハを表わす。(In the formula, R represents a hydrogen atom or a lower alkyl group.
)
その具体例としては、N、N−ビスマレイミド化合物と
しては、N 、 N’−ジフェニルメタンビスマレイミ
ド、N、N’−フェニレンビスマレイミF、N、N’−
ジフェニルエーテルビスマレイミト、N、N′−)フェ
ニルスルホニイミド、N,N’−ジシクロヘキシルメタ
ンビスマレイミF、N,N−キシレンビスマレイミド、
N,N’−トリレンビスマレイミド、N,N−キンリレ
ンビスマレイミド、 N 、 N’−ノフェニμスマレ
イミド、N 、 N’−ジフェニルメタンビスメチルマ
レイミド、N,N’−ジフェニルエーテルビスメチルマ
レイミド、N 、 N’−ジフェニルヌルホンビスメチ
ルマレイミド(大々異性体を含b>、N.*−エチレン
ビスマレイミド、N。) Specific examples of the N,N-bismaleimide compounds include N,N'-diphenylmethane bismaleimide, N,N'-phenylenebismaleimide F, N,N'-
diphenyl ether bismaleimide, N,N'-)phenylsulfoniimide, N,N'-dicyclohexylmethane bismaleimide F, N,N-xylene bismaleimide,
N,N'-tolylene bismaleimide, N,N-quinrylene bismaleimide, N,N'-nophenyμsmaleimide, N,N'-diphenylmethane bismethylmaleimide, N,N'-diphenyl ether bismethylmaleimide, N, N'-Diphenylnurphonebismethylmaleimide (including major isomers), N. *-Ethylene bismaleimide, N.
N゛−へキサメチレンビスマレ4ミ)−1N、N’−ヘ
キサメチレンビスメチルマレイミド、及びこれうN、N
’−ビスマレイミド化合物とジアミン類を灼加させて得
られる末端がN 、 N’−ビスマレイミド骨核を有す
るプレポリマー、およびアニリン・ホルマリン@縮合物
のマレイミド化物またはメチルマレイミド化物等が例示
できる。N'-hexamethylene bismethylmaleimide, N'-hexamethylene bismethylmaleimide, and N, N
Examples include a prepolymer having an N, N'-bismaleimide core at the end obtained by cauterizing a '-bismaleimide compound and a diamine, and a maleimide or methylmaleimide of an aniline/formalin@condensate.
特(てN 、 N’−ジフェニルメタンビスマレイミド
、N、N−ジフェニルエーテルビスマレイミドが好“ま
しい。Particularly preferred are N,N'-diphenylmethane bismaleimide and N,N-diphenyl ether bismaleimide.
本発明で・必要に応じて使用される(C)成分としては
例えばビスフェノールA、テトラブロモビスフェノール
A。ビスフェノ−A/P、ビヌフェノーlvS、ビス(
4−ヒドロキシフェニル)シクロヘキサン、ビス(4−
ヒドロキシフェニルエタン、1,3.3−)リメチ〜−
1−m−ヒドロキシフェニルインダン−5−または7−
オール、1.8.8−)リメf IV −1−p−ヒド
ロキンフェニルインダン−6−オール、レゾルシン、ハ
イドロキノン、カテコーA/、n記した回収分の原料と
なるフェノール類ノボヲック等のポリフェノール化合物
、マレイン酸、フタ/l/9、ナジク酸、メチルーテト
フヒドロフタ/L’^y1メチルナジク酸等のポリカル
ホン酸およびその虱水物、ジアミノジフェニルメタン、
ジアミノジフェニルスルホン、ソアミノジフェニルエー
テル、フェニレンジアミン、ジアミノシンクロヘキシル
メタン、ギシリレンジアミン、トルエンジアミン、キシ
レンジアミン、ジアミノジフエシ
ニルジクロヘキサン、ジクロロ−ジアミノジフェニルメ
タン(夫々異性体ヲ含ム)、エチレンジアミン、ヘキサ
メチレンジアミン等のポリアミン化合物、三弗化ホウ素
工’/−/L/アミン錯体、三弗化ホウ素ピペリジン錯
体などの三弗化7トウ素アミン錯体、イミダゾール誘導
体、第三級アミン、第4級アンモニウム塩、さらにはジ
シアンジアミド、テトラメチルグアニジン等、エポキシ
基と反応可能な活性水素含有化合物が例示できる0
本発明になるall脂組成物において、各成分の量的割
合は、用途、所望の耐熱性などに応じて適宜選択できる
が、一般的には回収分の二重結合に対するFB)成分の
二重結合の比が0.5〜3、(C)の成分を用いる場合
は回収分のエポキシ基に対する(C)成分の活性水素の
比が8以下となるように選ぶことが好ましい。Examples of component (C) used in the present invention as needed include bisphenol A and tetrabromobisphenol A. Bispheno-A/P, BinuphenolvS, Bis(
4-hydroxyphenyl)cyclohexane, bis(4-
Hydroxyphenylethane, 1,3.3-)rimethyl-
1-m-hydroxyphenylindan-5- or 7-
All, 1.8.8-) Limef IV -1-p-Hydroquine phenyl indan-6-ol, resorcinol, hydroquinone, catechol A/, polyphenol compounds such as phenols Novowoc, which are raw materials for the recovered portions listed in n. , maleic acid, lid/l/9, nadic acid, methyl-tetophhydrophtha/L'^y1 polycarphonic acids such as methylnadic acid and their hydrates, diaminodiphenylmethane,
Diaminodiphenylsulfone, soaminodiphenyl ether, phenylenediamine, diaminocyclohexylmethane, gysylylenediamine, toluenediamine, xylenediamine, diaminodiphecinyl diclohexane, dichloro-diaminodiphenylmethane (each containing isomers), ethylenediamine, hexamethylene Polyamine compounds such as diamines, boron trifluoride complexes, heptamine trifluoride amine complexes such as boron trifluoride piperidine complexes, imidazole derivatives, tertiary amines, quaternary ammonium salts In addition, active hydrogen-containing compounds that can react with epoxy groups such as dicyandiamide and tetramethylguanidine can be exemplified. This can be selected as appropriate depending on the situation, but in general, the ratio of the double bonds in the FB component to the double bonds in the recovered component is 0.5 to 3, and when using the component (C), the ratio of ( It is preferable to select component C) so that the active hydrogen ratio is 8 or less.
本発明において各成分はゲル化が起こらない程度に予め
反応させておくことができるが、8ミ分を用いる場合は
、先ず回収分とFC)成分を反応させた後、FB)成分
を反応させるのが硬化物性上好ましい。In the present invention, each component can be reacted in advance to the extent that gelation does not occur, but when using 8 min, the recovered component is first reacted with the FC) component, and then the FB) component is reacted. is preferable in terms of cured physical properties.
本発明になる樹脂組成物は熱により容易に硬化せしめる
ことができる。この場合、アゾ化合物、有機過酸化物等
のラジカル重合開始剤、三級アミン類、四級アンモニウ
ム塩類、イミダゾール類、三フフ化ホウ素・アミン塩等
のイオン触媒を添加することにより硬化を促進すること
もできる。The resin composition of the present invention can be easily cured by heat. In this case, curing is accelerated by adding radical polymerization initiators such as azo compounds and organic peroxides, ionic catalysts such as tertiary amines, quaternary ammonium salts, imidazoles, and boron trifluoride/amine salts. You can also do that.
本発明の樹脂組成物は比較的低温でミキサー、ニーダ−
、ロール等を用いて各種の充填剤、強化材を配合し、注
型又は成形材料を調製することが可能であり、更に、溶
4jに溶解させガラス繊維、炭素vR雉等各種強化繊維
に塗布して情し材料にも使用することができる。また、
目的に応じて、他の公知の熱硬化性樹脂、例えば他のア
リル系樹脂、エポキシ鞠脂、不飽和ポリエステ/L’樹
脂、フェノ−A/樹月旨、シリコーン情閂旨、トリアジ
ン樹脂等を添加してもよい。The resin composition of the present invention can be processed in a mixer or kneader at a relatively low temperature.
It is possible to prepare a casting or molding material by blending various fillers and reinforcing materials using a roll, etc. Furthermore, it can be dissolved in molten 4J and applied to various reinforcing fibers such as glass fibers and carbon VR pheasants. It can also be used as a complimentary material. Also,
Depending on the purpose, other known thermosetting resins such as other allyl resins, epoxy resin, unsaturated polyester/L' resin, pheno-A/jugetsuji, silicone jyojinji, triazine resin, etc. may be used. May be added.
かくして本発明の1N指組成物は、加工性、j町j熱性
、接着性に擾れた熱硬化性樹脂組5+y、物として、注
型、含浸、積り、成形用材料に有用であるO
次に本発明の詳細な説明するためにに素側及び実施例を
示すが本発明はこれらに限定されるものではない0例中
、部とあるのは重i?F、単位を示す。Thus, the 1N finger composition of the present invention has excellent processability, thermal properties, and adhesive properties, and is useful as a material for casting, impregnation, lamination, and molding. In order to explain the present invention in detail, elements and examples are shown, but the present invention is not limited thereto. F indicates units.
e考例1
(部分アリルエーテル化)
温度計、攪拌器、滴下p斗および連流冷却器を付けた反
応器に軟化点90℃の0−タレゾールツボフック樹脂2
36部(2当f、)及びy応溶謀トしてジメチルホルム
アミド840部を仕込与、樹脂を完全に溶解きせてから
9796荀性ソ一ダ62部(1,5当が)を加え、よく
攪拌する。反応糸の温度を40℃に保ちながら塩化アリ
ル120部(1,58当針)を1時間で滴下し死後50
℃壕で昇温し、同温度で6時間保持する。次いでジメチ
ルホルムアミドを留去後トルエン300部を仕込み樹脂
を溶解させた後、水洗及び濾過により無機塩を除去し、
p液を濃縮することによシ、核置換アリ、/L/基を有
さないアリルエーテル化率75g6、OH当量5921
/・qの赤橙色粘稠液状樹脂282部を得た0(エポキ
シ化)
温度針、攪拌器、部下p斗およびグ応水回収i1+If
fをつけた反応器に、上記部分アリルエーテル化率28
6.8部(0,4当景)とエピクロルヒドリン870部
(4,0当景)を仕込み、反応系の圧力を150■HP
とし、糸を徐々に加熱して沸とうさせなから48優苛性
ソ一ダ水溶液85部(0,42当光)を反応温度62℃
に保持しながら2時…1にわたって徐々に加える。反応
中ば水ヲエピクロルヒドリンとの共沸混合物の形で反応
系から除去し、エピクロルヒドリンヲimさせる0苛性
ソ一ダ滴下終了後、更に30分間同じ条件を保持する。eExample 1 (Partial allyl etherification) O-Taresol pot hook resin 2 with a softening point of 90°C was placed in a reactor equipped with a thermometer, a stirrer, a dropping port and a continuous flow condenser.
Add 36 parts (2 parts) and 840 parts of dimethylformamide, and after completely dissolving the resin, add 62 parts (1.5 parts) of 9796 soda. Stir well. While maintaining the temperature of the reaction thread at 40°C, 120 parts of allyl chloride (1,58 parts per needle) was added dropwise over 1 hour.
Raise the temperature in a ℃ oven and hold at the same temperature for 6 hours. Next, after distilling off dimethylformamide, 300 parts of toluene was added to dissolve the resin, and the inorganic salts were removed by washing with water and filtration.
By concentrating the p solution, allyl etherification rate 75 g6, OH equivalent 5921
0 (Epoxidation) Obtained 282 parts of red-orange viscous liquid resin of /・q Temperature needle, stirrer, lower pot and water recovery i1+If
The above partial allyl etherification rate 28 was added to the reactor marked with f.
Charge 6.8 parts (0.4 parts) and 870 parts (4.0 parts) of epichlorohydrin, and increase the pressure of the reaction system to 150 HP.
Then, gradually heat the thread and bring it to a boil, then add 85 parts of 48 eucaustic soda aqueous solution (0.42% light) to a reaction temperature of 62°C.
Gradually add over 2 hours to 1 hour while holding at a temperature of 2 hours. During the reaction, water is removed from the reaction system in the form of an azeotrope with epichlorohydrin, and after the completion of dropping caustic soda to imitate epichlorohydrin, the same conditions are maintained for an additional 30 minutes.
次いで、反応混合物から食塩を戸別し、母液を濃縮する
ことにより、エポキシ当量658P/eqの黄橙色粘稠
液体240部を得た。(AEN−1とする))
参考例2
(部分アリルエーテル化)
参考例1においてジメチルホルムアミドに代えてジメチ
ルスルホキシド600部97%苛性ソーダ41部(1,
0当黄)、塩化アリ/L/82部(1,08当A1゜)
を用いた以外は同様にして核置換アリ〃基を有さないア
リルエーテル化率50優、OR当量276 F/・qの
赤褐色半固型樹脂262部を得た。Next, the salt was separated from the reaction mixture and the mother liquor was concentrated to obtain 240 parts of a yellow-orange viscous liquid with an epoxy equivalent of 658 P/eq. (referred to as AEN-1)) Reference Example 2 (Partial allyl etherification) In Reference Example 1, 600 parts of dimethyl sulfoxide and 41 parts of 97% caustic soda (1,
0 equivalent yellow), ant chloride/L/82 parts (1,08 equivalent A1°)
262 parts of a reddish-brown semi-solid resin having an allyl etherification rate of 50 or more and an OR equivalent of 276 F/·q, which does not have a nuclear substituted aryl group, was obtained in the same manner except that .
(エポキシ化)
参考例1において、上記部分アリルエーテル化物220
.8部(0,8当量)、エピクロルヒドリン444部(
4,8当量)、48g6苛性ソ一ダ水溶M70部(0,
84当量)を用いた以外は同様にしてエポキシ当m 8
48 P/eq O黄橙色半iH型樹脂248部を得
たo (AEN−2とする。)実施例1
β素側−1で得られるAEN−1,200部トN、N’
−!/フェニルメタンビスマレイミド269ffit7
00部のN、N−ジメチルホルムアミド(DMF’ )
に溶解し、この溶液をガフヌクロス(鑓紡P11KS−
1600,A−1100) K含浸する。(Epoxidation) In Reference Example 1, the above partially allyl etherified product 220
.. 8 parts (0.8 equivalents), 444 parts of epichlorohydrin (
4,8 equivalents), 48g6 Caustic soda aqueous solution M70 parts (0,
84 equivalents) was used in the same manner, except that 84 equivalents of epoxy were used.
48 P/eq O 248 parts of yellow-orange semi-iH type resin were obtained (referred to as AEN-2) Example 1 1,200 parts of AEN-obtained in β element side-1 N, N'
-! /phenylmethane bismaleimide 269ffit7
00 parts of N,N-dimethylformamide (DMF')
Dissolve this solution in Gafnu Cloth (Yaribo P11KS-
1600, A-1100) Impregnated with K.
次いで180℃オーブン中で10分間処増し、プリプレ
グをイnた。このプリプレグを6枚重ね180℃プレス
で50νHの圧力下60分成型シフ、次いで180℃オ
ーブン中で2日後硬化させ積層板を得九〇同様にして、
プリプレグ6枚物性を表−1に示す。Next, the prepreg was heated in an oven at 180° C. for 10 minutes, and the prepreg was injected. Six sheets of this prepreg were stacked and molded at 180°C under a pressure of 50 νH for 60 minutes, and then cured in a 180°C oven for 2 days to obtain a laminate in the same manner as in 90.
Table 1 shows the physical properties of the six prepregs.
実施例−2
参考例−2で得られるA EN−2,386部とN、N
’−ジフェニμメタンビビスレイミド269部を900
部のDMFに溶解し実施例−1と同様にして積層板及び
銅張り積層板を得た・物性を表−1に示す。Example-2 386 parts of A EN-2 obtained in Reference Example-2 and N, N
'-269 parts of dipheniμ methane bisleimide 900 parts
A laminate and a copper-clad laminate were obtained in the same manner as in Example 1.The physical properties are shown in Table 1.
実施例−8
参考例−2で得られるAEN−2,886部とビスフェ
ノ−A/A55部及び2,4.6−)リス(ジメチルア
ミノメチ/L/)フェノ−/I10.2部を180℃で
80分反応させ、次いでN、N’−ジフェニルメタンビ
スマレイミド269部を加え990部のDMFK溶解さ
せる。この溶液を用いて実施例−1と同様にして積層板
及び銅張シ積層板を得た@物性を表−1に示す。Example-8 2,886 parts of AEN-2 obtained in Reference Example-2, 55 parts of bispheno-A/A, and 10.2 parts of 2,4.6-)lis(dimethylaminomethy/L/)pheno-/I were combined at 180 parts. The mixture was reacted for 80 minutes at °C, and then 269 parts of N,N'-diphenylmethane bismaleimide was added to dissolve 990 parts of DMFK. Using this solution, a laminate and a copper-clad laminate were obtained in the same manner as in Example 1. The physical properties are shown in Table 1.
比較例
N、N−ジフェニルメタンビスマレイミド179部に4
.4’−ジフェニyメタン37部を加え180℃で5分
攪拌する。次いでDMFJ20部を加え均一に溶解させ
る◇この溶液を用いて実施例−1と同様にして積層板及
び銅張シ積層板を得た。Comparative Example N, 4 to 179 parts of N-diphenylmethane bismaleimide
.. Add 37 parts of 4'-diphenymethane and stir at 180°C for 5 minutes. Next, 20 parts of DMFJ was added and dissolved uniformly. Using this solution, a laminate and a copper-clad laminate were obtained in the same manner as in Example-1.
物性を表−1に示す。The physical properties are shown in Table-1.
表−1より明らかな様に、本発明による組成物で得られ
る硬化物は優れた附熱性、耐水性、電気絶縁性及び接着
性を有していることがわかる。さらに1本発明による組
成物は溶剤に対する溶解性に優れ、かつ180℃稈度の
温度で硬化する等の優れた加工性を有していることがわ
かる。As is clear from Table 1, the cured product obtained from the composition of the present invention has excellent heat resistance, water resistance, electrical insulation and adhesive properties. Furthermore, it can be seen that the composition according to the present invention has excellent solubility in solvents and excellent processability such as curing at a temperature of 180°C.
Claims (2)
リルエーテル化されたフェノール類ノボラック樹脂 (B)分子中に2個以上のマレイミド基を有するポリマ
レイミド化合物、および必要に応じ (C)硬化剤を含有してなる熱硬化性樹脂組成物。(1) (A) A phenolic novolak resin in which the phenolic hydroxyl group is epoxidized and allyl etherified (B) A polymaleimide compound having two or more maleimide groups in the molecule, and (C) a curing agent if necessary. A thermosetting resin composition comprising:
ル化された水酸基の比が0.5〜9.0であるところの
特許請求の範囲第一項記載の熱硬化性樹脂組成物。(2) The thermosetting resin composition according to claim 1, wherein the ratio of allyl etherified hydroxyl groups to epoxidized hydroxyl groups is from 0.5 to 9.0.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26561385A JPH0653786B2 (en) | 1985-11-26 | 1985-11-26 | Thermosetting resin composition |
EP19910203025 EP0487164A3 (en) | 1985-11-26 | 1986-11-26 | Thermosetting resin composition and a composite material comprising the cured product of the resin composition as its matrix |
EP86309243A EP0225174A3 (en) | 1985-11-26 | 1986-11-26 | Thermosetting resin composition and a composite material comprising the cured product of the resin composition as its matrix |
US07/360,589 US5041507A (en) | 1985-11-26 | 1989-06-02 | Thermosetting resin composition composed of a polymaleimide compound, a phenolic novolac resin and an epoxy resin |
US07/971,263 US5300592A (en) | 1985-11-26 | 1992-11-04 | Thermosetting resin composition and a composite material comprising cured product and said resin composition and its matrix |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26561385A JPH0653786B2 (en) | 1985-11-26 | 1985-11-26 | Thermosetting resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62127316A true JPS62127316A (en) | 1987-06-09 |
JPH0653786B2 JPH0653786B2 (en) | 1994-07-20 |
Family
ID=17419562
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP26561385A Expired - Lifetime JPH0653786B2 (en) | 1985-11-26 | 1985-11-26 | Thermosetting resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0653786B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6470513A (en) * | 1987-08-07 | 1989-03-16 | Ciba Geigy Ag | Thermosettable composition containing unsaturated imide and benzaldehyde derivative |
US5272377A (en) * | 1990-10-31 | 1993-12-21 | Kabushiki Kaisha Toshiba | Maleimide resin composition and resin encapsulated semiconductor device manufactured using the composition |
-
1985
- 1985-11-26 JP JP26561385A patent/JPH0653786B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6470513A (en) * | 1987-08-07 | 1989-03-16 | Ciba Geigy Ag | Thermosettable composition containing unsaturated imide and benzaldehyde derivative |
US5272377A (en) * | 1990-10-31 | 1993-12-21 | Kabushiki Kaisha Toshiba | Maleimide resin composition and resin encapsulated semiconductor device manufactured using the composition |
Also Published As
Publication number | Publication date |
---|---|
JPH0653786B2 (en) | 1994-07-20 |
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