JPH0460139B2 - - Google Patents
Info
- Publication number
- JPH0460139B2 JPH0460139B2 JP58170240A JP17024083A JPH0460139B2 JP H0460139 B2 JPH0460139 B2 JP H0460139B2 JP 58170240 A JP58170240 A JP 58170240A JP 17024083 A JP17024083 A JP 17024083A JP H0460139 B2 JPH0460139 B2 JP H0460139B2
- Authority
- JP
- Japan
- Prior art keywords
- polyaminobisimide
- prepolymer
- ether
- solvent
- producing
- 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.)
- Expired - Lifetime
Links
- 239000002904 solvent Substances 0.000 claims description 23
- 150000001451 organic peroxides Chemical class 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- -1 alkylene glycol alkyl ether Chemical class 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 claims 1
- 230000000694 effects Effects 0.000 description 5
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 3
- 238000007348 radical reaction Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、ポリアミノビスイミド樹脂の製造方
法に関し、その目的とするところは、溶剤の乾燥
除去時には熱的に安定で三次元硬化が起こらず、
しかも硬化性に優れ、硬化後優れた耐熱性を有す
るポリアミノビスイミド樹脂の製造方法を提供す
ることにある。
従来、高度な耐熱性、寸法安定性、電気特性等
を要求される耐熱性接着剤、耐熱性積層板等の分
野には、ポリアミノビスマレイミド樹脂が使用さ
れてきた。しかし、このポリアミドビスマレイミ
ドプレポリマーは、高温で長時間の硬化を要する
（例えば200℃、48時間あるいは250℃、24時間位
の後硬化が必要）、あるいはＮ−メチル−２−ピ
ロリドン等の高沸点の特殊溶剤にしか溶解しな
い、あるいは使用できる溶剤が作業環境上好まし
くない等の欠点を有していた。
又、硬化性を向上させるため、有機過酸化物を
用いても、使用できる溶剤が高沸点のため、溶剤
を乾燥除去する際に、有機過酸化物が分解してし
まうという欠点を有していた。
本発明者らはこの様な点を鑑み、有機過酸化物
の種類と溶剤の種類を種々検討した結果、本発明
に至つた。
本発明は、有機過去酸化物を含有するポリアミ
ノビスイミドプレポリマー溶液から溶剤を乾燥除
去し、その後、加熱硬化させてポリアミノビスイ
ミド樹脂を製造する方法において、有機過酸化物
が２，５−ジメチル−２，５−ジ（ｔ−ブチルパ
ーオキシ）ヘキシン−３で、溶剤がアルキレング
リコールアルキルエーテルであり、しかも、その
沸点（760mmHg）が２，５−ジメチル−２，５−
ジ（ｔ−ブチルパーオキシ）ヘキシン−３の半減
期が１分になる分解温度（以下Td（1/2）と略す）
193℃より低く、ポリアミノビスイミドプレポリ
マーが不飽和ビスイミドとジアミンとを前記アル
キレングリコールアルキルエーテル中にて加熱反
応させて得られたポリアミノビスイミドプレポリ
マーであることを特徴とするものである。この様
な方法で製造された有機過酸化物を含有するポリ
アミノビスイミドプレポリマーのアルキレングリ
コールアルキルエーテル溶液から溶剤を乾燥除去
するに際し、有機過酸化物のTd（1/2）が溶剤の
沸点より高いので、ポリアミノビスイミドプレポ
リマーは熱的に安定で、この乾燥除去工程では三
次元硬化は起こらない。しかも、次にこのポリア
ミノビスイミドプレポリマーを加熱三次元硬化す
るに際し、有機過酸化物のラジカル反応開始剤と
して作用によりも、有機過酸化物が添加されてい
ない系より、硬化温度を低くすることが可能とな
り、あるいは硬化時間を短くすることができる。
更に、三次元硬化されたポリアミノビスイミド樹
脂は優れた耐熱性を有している。
尚、特公昭44−20625公報に、ポリアミノビス
イミドプレポリマー溶液に有機過酸化物を用いる
ことが記載されているが、溶剤の沸点が高いた
め、溶剤を乾燥除去する際に、有機過酸化物が分
解してしまう。又、特公昭50−25956公報にもポ
リアミノビスイミドプレポリマーと溶剤と有機過
酸化物の使用が記載されているが、溶剤はアルキ
レングリコールアルキルエーテルではなく、特殊
溶剤なので、作業環境上の問題、あるいは溶剤の
乾燥除去時に、有機過酸化物の分解が生じる可能
性が高い。
次に本発明について、更に具体的に説明する。
本発明に用いる有機過酸化物は、２，５−ジメ
チル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキ
シン−３（Td（1/2）；193℃）である。Td（1/2）
が比較的高い有機過酸化物としては、上記以外に
も、ｔ−ブチルパーオキシベンゾエート（Td（1/
２）；170℃）、ｔ−ブチルパーオキシイソプロピル
カーボネート（Td（1/2）；158℃）等があるが、
これらのエステル基を有している有機過酸化物を
本発明に用いても、全く効果が現れなかつた。効
果が現れなかつた理由は今のところ不明である
が、微量な水分により、エステル基が加水分解し
たのではないかと思われる。
本発明に用いる有機過酸化物の配合量はポリア
ミノビスイミドプレポリマーの重量に対し、0.1
〜５重量％の範囲である。0.1重量部より少ない
と硬化性向上の効果があまり見られなく、５重量
％より多いと効果が速くなり過ぎてしまい、成形
時の流動性のコントロールができなくなつてしま
う。これらの有機過酸化物は単独、あるいは２種
以上併用して用いられ、又、ラジカル反応促進
剤、あるいはラジカル反応禁止剤と併用して硬化
性をコントロールすることも可能である。
本発明に用いられる溶剤は、その沸点（760mm
Hg）b.p.が前記、有機過酸化物のTd（1/2）193℃
よりも低いアルキレングリコールモノアルキルエ
ーテルあるいはアルキレングリコールジアルキル
エーテルであり、例えばエチレングリコールモノ
メチルエーテル（b.p.125℃）、エチレングリコー
ルジメチルエーテル（b.p.93℃）、エチレングリ
コールモノ−エチルエーテル（b.p.136℃）、プロ
ピレングリコールモノメチルエーテル（b.p.121
℃）、プロピレングリコールモノ−ｎ−プロピル
エーテル（b.p.150℃）、エチレングリコールモノ
−ｎ−プロピルエーテル（b.p.151℃）、エチレン
グリコール−モノｉ−プロピルエーテル（b.
p.139℃）等である。これらの溶剤は単独、ある
いは２種以上の混合溶剤として用いられる。
本発明に用いるポリアミノビスイミドプレポリ
マーは不飽和ビスイミドとジアミンとを前述のア
ルキレングリコールアルキルエーテル溶液中にて
加熱反応させて得られる。
不飽和ビスイミドは一般式
（式中、R3は炭素−炭素二重結合を有する２価
の有機基を表わし、例えば−CH＝CH−、
The present invention relates to a method for producing a polyaminobisimide resin, and its purpose is to be thermally stable and free from three-dimensional curing when the solvent is removed by drying.
Moreover, it is an object of the present invention to provide a method for producing a polyaminobisimide resin which has excellent curability and excellent heat resistance after curing. Conventionally, polyamino bismaleimide resins have been used in fields such as heat-resistant adhesives and heat-resistant laminates that require high heat resistance, dimensional stability, electrical properties, and the like. However, this polyamide bismaleimide prepolymer requires curing at high temperatures for a long time (for example, post-curing at 200°C for 48 hours or 250°C for about 24 hours), or requires high-temperature curing such as N-methyl-2-pyrrolidone. They have drawbacks such as being soluble only in special solvents with a boiling point, or the solvents that can be used being unfavorable in terms of the working environment. Furthermore, even if an organic peroxide is used to improve curability, the solvent that can be used has a high boiling point, so the organic peroxide decomposes when the solvent is dried and removed. Ta. In view of these points, the present inventors conducted various studies on the types of organic peroxides and the types of solvents, and as a result, they arrived at the present invention. The present invention provides a method for producing a polyaminobisimide resin by drying and removing a solvent from a polyaminobisimide prepolymer solution containing an organic past oxide, and then heating and curing the solution, in which the organic peroxide is 2,5-dimethyl -2,5-di(t-butylperoxy)hexyne-3, the solvent is alkylene glycol alkyl ether, and its boiling point (760 mmHg) is 2,5-dimethyl-2,5-
Decomposition temperature at which the half-life of di(t-butylperoxy)hexine-3 is 1 minute (hereinafter abbreviated as Td (1/2))
The temperature is lower than 193°C, and the polyaminobisimide prepolymer is a polyaminobisimide prepolymer obtained by subjecting an unsaturated bisimide and a diamine to a heating reaction in the alkylene glycol alkyl ether. When drying and removing the solvent from an alkylene glycol alkyl ether solution of a polyaminobisimide prepolymer containing an organic peroxide produced by such a method, the Td (1/2) of the organic peroxide is lower than the boiling point of the solvent. Because of its high temperature, the polyaminobisimide prepolymer is thermally stable and no three-dimensional curing occurs during this dry stripping step. Moreover, when this polyaminobisimide prepolymer is then heated and three-dimensionally cured, the curing temperature can be lowered than in a system to which no organic peroxide is added, due to the action of the organic peroxide as a radical reaction initiator. or the curing time can be shortened.
Furthermore, the three-dimensionally cured polyaminobisimide resin has excellent heat resistance. Note that Japanese Patent Publication No. 44-20625 describes the use of an organic peroxide in the polyaminobisimide prepolymer solution, but since the boiling point of the solvent is high, when the solvent is dried and removed, the organic peroxide is will decompose. In addition, Japanese Patent Publication No. 50-25956 also describes the use of polyaminobisimide prepolymer, a solvent, and an organic peroxide, but since the solvent is not an alkylene glycol alkyl ether but a special solvent, there are problems in the working environment. Alternatively, there is a high possibility that decomposition of the organic peroxide will occur during dry removal of the solvent. Next, the present invention will be explained in more detail. The organic peroxide used in the present invention is 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 (Td(1/2); 193°C). Td(1/2)
In addition to the above, t-butyl peroxybenzoate (Td(1/
2); 170℃), t-butylperoxyisopropyl carbonate (Td(1/2); 158℃), etc.
Even when organic peroxides having these ester groups were used in the present invention, no effect was obtained at all. The reason why no effect was observed is currently unknown, but it is thought that the ester group was hydrolyzed by a small amount of water. The amount of organic peroxide used in the present invention is 0.1% based on the weight of the polyaminobisimide prepolymer.
-5% by weight. If it is less than 0.1 part by weight, the effect of improving curability will not be seen much, and if it is more than 5% by weight, the effect will be too rapid, making it impossible to control fluidity during molding. These organic peroxides can be used alone or in combination of two or more, and can also be used in combination with radical reaction promoters or radical reaction inhibitors to control curability. The solvent used in the present invention has a boiling point (760 mm
Hg) bp is above, Td of organic peroxide (1/2) 193℃
alkylene glycol monoalkyl ether or alkylene glycol dialkyl ether, such as ethylene glycol monomethyl ether (bp 125℃), ethylene glycol dimethyl ether (bp 93℃), ethylene glycol mono-ethyl ether (bp 136℃), propylene glycol monomethyl ether ( bp121
°C), propylene glycol mono-n-propyl ether (bp 150 °C), ethylene glycol mono-n-propyl ether (bp 151 °C), ethylene glycol mono-i-propyl ether (b.
p.139℃) etc. These solvents may be used alone or as a mixed solvent of two or more. The polyamino bisimide prepolymer used in the present invention is obtained by subjecting unsaturated bisimide and diamine to a heating reaction in the above-mentioned alkylene glycol alkyl ether solution. Unsaturated bisimide has the general formula (In the formula, R3 represents a divalent organic group having a carbon-carbon double bond, such as -CH=CH-,
以下、本発明について実施例をもつて詳細に説
明する。但し、本発明は以下の実施例に限定され
るものではない。
実施例 １
冷却管、撹拌械、温度計を具備した４つ口フラ
スコを用いて以下の合成を行つた。
Ｎ，N′−４，4′−ジフエニルメタンビスマレイ
ミド
100重量部と、４，4′−ジアミノジフエニルメタ
ン16.5重量部（ビスイミドとジアミンのモル比は
１：0.30）とを117.6重量部のエチレングリコー
ルモノメチルエーテル中にて、オイルバス温度
130℃で30分間撹拌し、加熱反応させてポリアミ
ノビスイミドプレポリマーを合成した。その後室
温まで冷却し、この溶液は２，５−ジメチル−
２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−
３を1.16添加し、よく撹拌して均一な溶液を得
た。（この時の溶液の濃度は50重量％である。）
この溶液を日東紡績製ガラスクロスＧ−9020−
BY52（0.2mm厚）に含浸させた後、160℃の温度で
３分間乾燥し、樹脂分45重量％のプリプレグを得
た。このプリプレグの揮発分（160℃、15分加熱
処理前後の重量差より算出）は0.72重量％であ
り、溶剤はほとんど残存していなかつた。
このプリプレグからポリアミノビスイミドプレ
ポリマーの粉をもみほぐし、パーキンエルマー社
製の示差走査熱量計DSC−11を用いて発熱反応
ピーク温度を調べたところ、197℃であつた。
（昇温速度は10℃／min）
上記プリプレグを８枚重ね、その上下に古河サ
ーキツトフオイル社製の35μｍ銅箔FC−TAI−35
を重ね、これらを２枚の鏡板で挟んで、加熱加圧
硬化させ、板厚が1.6mmの銅張積層板を得た。こ
の時の硬化条件は、温度200℃、時間２時間、圧
力40Kgｆ／cm2であつた。
この銅張積層板の特性を表１に示すが、後硬化
しなくても耐熱性が非常に優れたものであつた。
比較例 １〜４
実施例１における２，５−ジメチル−２，５−
ジ（ｔ−ブチルパーオキシ）ヘキシン−３の代わ
りに、表１に揚げる有機過酸化物を用いる以外は
実施例１と同様にしてポリアミノビスイミドプレ
ポリマーを得た。実施例１のポリアミノビスイミ
ドプレポリマーのDSCによる発熱反応ピーク温
度は、比較例１〜３のポリアミノビスイミドの
DSCによる発熱反応ピーク温度よりも20〜40℃
以上低かつた。
Hereinafter, the present invention will be explained in detail using examples. However, the present invention is not limited to the following examples. Example 1 The following synthesis was carried out using a four-necked flask equipped with a condenser, a stirring machine, and a thermometer. N,N'-4,4'-diphenylmethane bismaleimide 100 parts by weight and 16.5 parts by weight of 4,4'-diaminodiphenylmethane (mole ratio of bisimide and diamine is 1:0.30) in 117.6 parts by weight of ethylene glycol monomethyl ether at oil bath temperature.
The mixture was stirred at 130°C for 30 minutes and reacted by heating to synthesize a polyaminobisimide prepolymer. Thereafter, the solution was cooled to room temperature, and the solution was dissolved in 2,5-dimethyl-
2,5-di(t-butylperoxy)hexyne-
1.16 of 3 was added and stirred well to obtain a homogeneous solution. (The concentration of the solution at this time is 50% by weight.) This solution was mixed with Nittobo's glass cloth G-902-
After impregnating it with BY52 (0.2 mm thick), it was dried at a temperature of 160° C. for 3 minutes to obtain a prepreg with a resin content of 45% by weight. The volatile content of this prepreg (calculated from the weight difference before and after heat treatment at 160° C. for 15 minutes) was 0.72% by weight, and almost no solvent remained. A powder of polyaminobisimide prepolymer was loosened from this prepreg, and the exothermic reaction peak temperature was examined using a differential scanning calorimeter DSC-11 manufactured by PerkinElmer, and it was found to be 197°C. (Temperature increase rate is 10℃/min) 8 sheets of the above prepreg are stacked, and 35 μm copper foil FC-TAI-35 manufactured by Furukawa Circuit Oil Co., Ltd. is placed on top and bottom of the prepreg.
These were stacked on top of each other, sandwiched between two mirror plates, and cured under heat and pressure to obtain a copper-clad laminate with a thickness of 1.6 mm. The curing conditions at this time were a temperature of 200° C., a time of 2 hours, and a pressure of 40 Kgf/cm 2 . The properties of this copper-clad laminate are shown in Table 1, and it was found that it had excellent heat resistance even without post-curing. Comparative Examples 1 to 4 2,5-dimethyl-2,5- in Example 1
A polyaminobisimide prepolymer was obtained in the same manner as in Example 1, except that the organic peroxides shown in Table 1 were used instead of di(t-butylperoxy)hexyne-3. The exothermic reaction peak temperature measured by DSC of the polyaminobisimide prepolymer of Example 1 is the same as that of the polyaminobisimide of Comparative Examples 1 to 3.
20~40℃ higher than the exothermic reaction peak temperature by DSC
It was lower than that.
【表】
｜ ｜ ｜ ｜
CH３ CH３ CH３ CH３
[Table] ｜ ｜ ｜ ｜
CH 3 CH 3 CH 3 CH 3
【表】【table】
【表】【table】
以上、説明してきたように、本発明による２，
５−ジメチル−２，５−ジ（ｔ−ブチルパーオキ
シ）ヘキシン−３を含有するポリアミノビスイミ
ドプレポリマーは、溶剤の乾燥除去時に、熱的に
安定で、しかも有機過酸化物の作用により、比較
的硬化温度が低く、硬化時間を短くすることが可
能で、三次元硬化後は、優れた耐熱性を有するポ
リアミノビスイミド樹脂が得られ、この工業的価
値は大である。
As explained above, 2,
The polyaminobisimide prepolymer containing 5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 is thermally stable when the solvent is removed by drying, and due to the action of organic peroxide, The curing temperature is relatively low, the curing time can be shortened, and after three-dimensional curing, a polyaminobisimide resin having excellent heat resistance can be obtained, and this has great industrial value.
Claims (1)
ドプレポリマー溶液から、溶剤を乾燥除去し、そ
の後、加熱硬化させてポリアミノビスイミド樹脂
を製造する方法において、(1)有機過酸化物とし
て、２，５−ジメチル−２，５−ジ（ｔ−ブチル
パーオキシ）ヘキシン−３、(2)溶剤としてアルキ
レングリコールアルキルエーテルで、しかも、そ
の沸点（760mmHg）が前記過酸化物の半減期が１
分になる温度より低く、(3)ポリアミノビスイミド
プレポリマーが不飽和ビスイミドとジアミンとを
前記溶剤中にて加熱反応させて得たプレポリマー
であることを特徴とするポリアミノビスイミド樹
脂の製造方法。 ２ アルキレングリコールアルキルエーテルが、
エチレングリコールモノメチルエーテル、エチレ
ングリコールジメチルエーテル、エチレングリコ
ールモノエチルエーテル、プロピレングリコール
モノメチルエーテル、プロピレングリコールモノ
−ｎ−プロピルエーテル、エチレングリコールモ
ノ−ｉ−プロピルエーテル、またはこれらの混合
物である特許請求の範囲第１項記載のポリアミノ
ビスイミド樹脂の製造方法。 ３ 有機過酸化物の配合量がポリアミノビスイミ
ドプレポリマーの重量に対し、0.1〜５重量％の
範囲である特許請求の範囲第１項記載のポリアミ
ノビスイミド樹脂の製造方法。 ４ 不飽和ビスイミドとジアミンのモル比が１：
0.8の範囲である特許請求の範囲第１項記載のポ
リアミノビスイミド樹脂の製造方法。[Scope of Claims] 1. A method for producing a polyaminobisimide resin by drying and removing a solvent from a polyaminobisimide prepolymer solution containing an organic peroxide, and then heating and curing the solution, comprising: (1) organic peroxide-containing polyaminobisimide prepolymer solution; 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, (2) alkylene glycol alkyl ether as a solvent, and its boiling point (760 mmHg) is half that of the peroxide. period is 1
(3) a method for producing a polyaminobisimide resin, characterized in that the polyaminobisimide prepolymer is a prepolymer obtained by subjecting an unsaturated bisimide and a diamine to a heat reaction in the above-mentioned solvent; . 2 alkylene glycol alkyl ether is
Claim 1 which is ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, or a mixture thereof. A method for producing a polyaminobisimide resin as described in Section 1. 3. The method for producing a polyaminobisimide resin according to claim 1, wherein the amount of the organic peroxide is in the range of 0.1 to 5% by weight based on the weight of the polyaminobisimide prepolymer. 4 The molar ratio of unsaturated bisimide and diamine is 1:
A method for producing a polyaminobisimide resin according to claim 1, wherein the polyamino bisimide resin has a polyimide content of 0.8.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17024083A JPS6060132A (en) | 1983-09-14 | 1983-09-14 | Production of polyaminobisimide resin |
| EP84306272A EP0137750B1 (en) | 1983-09-14 | 1984-09-13 | Polyamino-bis-maleimide prepolymer, its manufacture, its use in manufacturing laminates |
| US06/650,905 US4598115A (en) | 1983-09-14 | 1984-09-13 | Polyamino-bis-maleimide prepolymer, method for manufacture thereof, and method for manufacture of laminate using said prepolymer |
| DE8484306272T DE3483901D1 (en) | 1983-09-14 | 1984-09-13 | POLYAMINO-BIS-MALEIMID PREPOLYMER, THE PRODUCTION AND USE THEREOF IN THE PRODUCTION OF LAMINATES. |
| US06/850,122 US4707316A (en) | 1983-09-14 | 1986-04-10 | Polyamino-bis-maleimide prepolymer, method for manufacture thereof, and method for manufacture of laminate using said prepolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17024083A JPS6060132A (en) | 1983-09-14 | 1983-09-14 | Production of polyaminobisimide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6060132A JPS6060132A (en) | 1985-04-06 |
| JPH0460139B2 true JPH0460139B2 (en) | 1992-09-25 |
Family
ID=15901263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17024083A Granted JPS6060132A (en) | 1983-09-14 | 1983-09-14 | Production of polyaminobisimide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6060132A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63130637A (en) * | 1986-11-21 | 1988-06-02 | Shin Kobe Electric Mach Co Ltd | Production of polyimide molding material |
| JPS63207852A (en) * | 1987-02-25 | 1988-08-29 | Shin Kobe Electric Mach Co Ltd | Production of molding material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5137680A (en) * | 1974-09-27 | 1976-03-30 | Tokyo Shibaura Electric Co | SHINCHIREE SHONKA MERA |
| JPS52134694A (en) * | 1976-05-04 | 1977-11-11 | Sumitomo Bakelite Co Ltd | Preparation of molding thermosetting resins |
| JPS5733288A (en) * | 1980-08-01 | 1982-02-23 | Hitachi Ltd | Pipe table for branching |
| JPS5749621A (en) * | 1980-09-09 | 1982-03-23 | Hitachi Ltd | Preparation of heat-resistant resin |
-
1983
- 1983-09-14 JP JP17024083A patent/JPS6060132A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5137680A (en) * | 1974-09-27 | 1976-03-30 | Tokyo Shibaura Electric Co | SHINCHIREE SHONKA MERA |
| JPS52134694A (en) * | 1976-05-04 | 1977-11-11 | Sumitomo Bakelite Co Ltd | Preparation of molding thermosetting resins |
| JPS5733288A (en) * | 1980-08-01 | 1982-02-23 | Hitachi Ltd | Pipe table for branching |
| JPS5749621A (en) * | 1980-09-09 | 1982-03-23 | Hitachi Ltd | Preparation of heat-resistant resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6060132A (en) | 1985-04-06 |
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