JPS6322814A - Production of thermosetting heat-resistant resin composition - Google Patents
Production of thermosetting heat-resistant resin compositionInfo
- Publication number
- JPS6322814A JPS6322814A JP16633486A JP16633486A JPS6322814A JP S6322814 A JPS6322814 A JP S6322814A JP 16633486 A JP16633486 A JP 16633486A JP 16633486 A JP16633486 A JP 16633486A JP S6322814 A JPS6322814 A JP S6322814A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- polybutadiene
- polymaleimide
- solvent
- resistant 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
- 239000011342 resin composition Substances 0.000 title claims description 27
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 14
- 229920006015 heat resistant resin Polymers 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 20
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 20
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 125000000962 organic group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000007731 hot pressing Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
- 238000000465 moulding Methods 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920003192 poly(bis maleimide) Polymers 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PUKLCKVOVCZYKF-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C=CC1=O PUKLCKVOVCZYKF-UHFFFAOYSA-N 0.000 description 1
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 description 1
- RJRJRBZNTQITSM-UHFFFAOYSA-N 1-[4-[2-[4-[2-[4-(2,5-dioxopyrrol-1-yl)phenyl]propan-2-yl]phenyl]propan-2-yl]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(C(C)(C)C=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1N1C(=O)C=CC1=O RJRJRBZNTQITSM-UHFFFAOYSA-N 0.000 description 1
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- FOVKMHAHFBKDSW-UHFFFAOYSA-N C1(C=CC(N1)=O)=O.C1(C=CC(N1)=O)=O.C1(=CC(=CC=C1)C)C Chemical compound C1(C=CC(N1)=O)=O.C1(C=CC(N1)=O)=O.C1(=CC(=CC=C1)C)C FOVKMHAHFBKDSW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は誘電率が低く、耐熱性の高い無溶剤型の熱硬化
性耐熱樹脂組成物の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a solvent-free thermosetting heat-resistant resin composition having a low dielectric constant and high heat resistance.
従来、誘電率が低く、しかも耐熱性の高い有機高分子材
料として、ポリテトラフルオロエチレン、あるいは特公
昭５９−５２０７号公報、特公昭６０−１１６３４号公
報に示されている１、 ２−ポリブタジエンとマレイ
ミド化合物との混合物が使用されている。Conventionally, as an organic polymer material with a low dielectric constant and high heat resistance, polytetrafluoroethylene or 1,2-polybutadiene, which is disclosed in Japanese Patent Publication No. 59-5207 and Japanese Patent Publication No. 60-11634, has been used. Mixtures with maleimide compounds have been used.
しかしながら、ポリテトラフルオロエチレンは、その融
点が３２７℃であり、成形温度を融点以上にする必要が
あり、成形加工が難しいという問題点があった。However, polytetrafluoroethylene has a melting point of 327° C., which requires the molding temperature to be higher than the melting point, making it difficult to mold.
また、１．２−ポリブタジエンとマレイミド化合物の混
合物は、成形時に樹脂の流動性の調節ができないという
欠点を有していた。すなわち、エポキシ樹脂やポリアミ
ノビスマレイミド樹脂等の熱硬化性樹脂においては、成
形時の樹脂の流動性を調節する方法として、これらの樹
脂の分子量を加熱条件により変化させる方法（いわゆる
Ｂステージ状態を逐次付加反応を利用して変化させる方
法）がとられているのに対し、１．２−ポリブタジエン
とマレイミド化合物の混合物はラジカル連鎖反応だけで
高分子化が進むため、Ｂ−ステージ状態がなく、加熱す
るとＣステージ（三次元硬化状Ｂ）まで進んでしまうと
いう問題があった。Furthermore, the mixture of 1,2-polybutadiene and maleimide compound has the disadvantage that the fluidity of the resin cannot be controlled during molding. In other words, for thermosetting resins such as epoxy resins and polyamino bismaleimide resins, a method of adjusting the fluidity of the resin during molding is to change the molecular weight of these resins depending on heating conditions (sequentially changing the so-called B stage state). In contrast, a mixture of 1,2-polybutadiene and a maleimide compound undergoes polymerization only by a radical chain reaction, so there is no B-stage state and it is difficult to heat the mixture. Then, there was a problem in that it progressed to the C stage (three-dimensionally cured state B).
また、製造方式として樹脂組成物を溶剤にとかして使用
する溶液方式も考えられるが、省エネルギー（溶剤の乾
燥除去のため多大のエネルギーを必要とする）、環境汚
染の防止の点から、無溶剤型の樹脂組成物による製造方
式が要望されていた。In addition, a solution method in which the resin composition is dissolved in a solvent is also considered as a manufacturing method, but from the viewpoint of energy saving (a large amount of energy is required to dry and remove the solvent) and prevention of environmental pollution, a solvent-free method is considered. There has been a demand for a manufacturing method using a resin composition.
本発明は、かかる状況に鑑みなされたものであって、無
溶剤で、Ｂステージ状態の調節が可能で、比較的低温成
形が可能で、三次元硬化した硬化物の誘電率が低く、耐
熱性が高い熱硬化性耐熱樹脂組成物の製造方法を提供せ
んとするものである。The present invention was developed in view of the above circumstances, and is solvent-free, B-stage state controllable, relatively low-temperature molding possible, three-dimensionally cured material with low dielectric constant, and heat resistant. It is an object of the present invention to provide a method for producing a thermosetting heat-resistant resin composition with high heat resistance.
かかる目的は本発明によれば、特定のポリブタジェンと
特定のポリマレイミドとを無溶剤で予備反応せしめて製
造した熱硬化性耐熱樹脂組成物によって達成することが
できる。According to the present invention, this object can be achieved by a thermosetting heat-resistant resin composition produced by preliminarily reacting a specific polybutadiene and a specific polymaleimide without a solvent.
すなわち本発明は数平均分子量がｔｏ、０００以下であ
るカルボキシル基末端１．４−ポリブタジエンと、
一般式
（ここでＲ１は少なくとも２個の炭素原子を有するａ価
の有機基を表し、ａは２以上１０以下の数を表す。）
で表されるポリマレイミドとを無溶剤で予備反応せしめ
ることにより熱硬化性耐熱樹脂組成物を製造する方法を
提供するものである。That is, the present invention provides a carboxyl group-terminated 1,4-polybutadiene having a number average molecular weight of 0,000 or less, and a carboxyl group-terminated 1,4-polybutadiene having a general formula (where R1 represents an a-valent organic group having at least 2 carbon atoms, and a is 2 The present invention provides a method for producing a thermosetting heat-resistant resin composition by preliminarily reacting a polymaleimide represented by the formula (10 or less) in the absence of a solvent.
本発明において使用するポリブタジェンはシスおよびト
ランスの１，４構造を主体とし、残りの構造として１．
２構造を含んでいてもよく、各分子の両末端にカルボキ
シル基を含有しているポリブタジェンである。The polybutadiene used in the present invention mainly has cis and trans 1,4 structures, with the remaining structure being 1.
It is a polybutadiene which may contain two structures and contains carboxyl groups at both ends of each molecule.
また、本発明において使用するカルボキシル基末端１．
４−ポリブタジエンの数平均分子量は、１０．０００以
下であり、１０．０００より大きいとポリマレイミドと
予備反応せしめた熱硬化性樹脂組成物の流動性が非常に
低下してしまう。In addition, the carboxyl group terminal used in the present invention 1.
The number average molecular weight of 4-polybutadiene is 10.000 or less, and if it is larger than 10.000, the fluidity of the thermosetting resin composition pre-reacted with the polymaleimide will be extremely reduced.
また、本発明において使用するポリマレイミド（１）と
しては、Ｎ、Ｎ’−エチレンビスマレイミＪ’、ｐＪ、
Ｎ’−ｍ−フェニレンビスマレイミド、Ｎ、Ｎ’−ｐ−
フェニレンビスマレイミド、Ｎ。In addition, the polymaleimide (1) used in the present invention includes N,N'-ethylene bismaleimide J', pJ,
N'-m-phenylene bismaleimide, N, N'-p-
Phenylene bismaleimide, N.
Ｎ′−ヘキサメチレンビスマレイミド、Ｎ、Ｎ’−ｐ、
ｐ’−ジフェニルジメチルシリルビスマレイミド、Ｎ、
Ｎ’−ｐ、ｐ’−ジフェニルメタンビスマレイミド、Ｎ
、Ｎ’−ｐ、ｐ’−ジフェニルエーテルビスマレイミド
、Ｎ、 Ｎ ’ ｐ、 ｐ ’−ジフェニルスル
ホンビスマレイミド、Ｎ、Ｎ’−ジシクロヘキシルメタ
ンビスマレイミド、Ｎ。N'-hexamethylene bismaleimide, N, N'-p,
p'-diphenyldimethylsilyl bismaleimide, N,
N'-p, p'-diphenylmethane bismaleimide, N
, N'-p, p'-diphenyl ether bismaleimide, N, N' p, p'-diphenyl sulfone bismaleimide, N, N'-dicyclohexylmethane bismaleimide, N.
Ｎ７ ｍ−キシレンビスマレイミド、Ｎ、Ｎ’−（３
，３’−ジクロロ−ｐ、ｐ’−ビスフェニレン）ビスマ
レイミド、Ｎ、Ｎ’−（３，３’−ジフェニルオキシ）
ビスマレイミド、２．２−ビス（４−（４−マレイミド
フェノキシ）フェニル〕プロパン、１．４−ビス（ｐ−
マレイミドクミル）ベンゼン、３．３’、４．４’−ジ
フェニルメタンテトラマレイミドおよび一般式
（この式でＲ２は１から８の炭素原子を有する有機基を
表し、ｂは平均値が０．１から８．０までの範囲の数を
表す、）
で表されるポリマレイミド等であり、好ましくはＮ、Ｎ
’−ｐ、Ｉ）’−ジフェニルメタンビスマレイミドと式
ＩＩ （Ｒ１はＣｔ＋Ｚ基）のポリマレイミドである。N7 m-xylene bismaleimide, N, N'-(3
,3'-dichloro-p,p'-bisphenylene)bismaleimide, N,N'-(3,3'-diphenyloxy)
Bismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 1,4-bis(p-
maleimidocumyl)benzene, 3.3',4.4'-diphenylmethanetetramaleimide and the general formula (in which R2 represents an organic group having from 1 to 8 carbon atoms, and b has an average value of from 0.1 to ) representing a number in the range up to 8.0, preferably N, N
'-p,I)'-diphenylmethane bismaleimide and a polymaleimide of formula II (R1 is a Ct+Z group).
本発明者らは、カルボキシル基末端１．４−ポリブタジ
エンと前記マレイミドとを無溶剤で加熱により予備反応
させると、均一な樹脂組成物が得られ、この樹脂組成物
はＢステージ状態の調節が可能であることを見出した。The present inventors have found that by pre-reacting carboxyl group-terminated 1,4-polybutadiene and the maleimide by heating in the absence of a solvent, a uniform resin composition can be obtained, and the B-stage state of this resin composition can be adjusted. I found that.
予備反応温度は１００℃から２００℃の範囲で、好まし
くは１５０℃から１７０℃の範囲である。The pre-reaction temperature ranges from 100°C to 200°C, preferably from 150°C to 170°C.
予備反応温度が１００°Ｃより低いと反応に時間がかか
りすぎ、２００℃より高いとポリマレイミド同志の反応
が起こり、ゲル化してしまう。If the pre-reaction temperature is lower than 100°C, the reaction will take too long, and if it is higher than 200°C, reactions between the polymaleimides will occur, resulting in gelation.
予備反応に要する時間は用いる１、４−ポリブタジエン
、ポリマレイミド等に応じて変化するが、樹脂組成物が
Ｂステージ状態あるいはＣステージ状態で均一な状態を
保っているようになるまで続けられる。予備反応時間が
短いと樹脂組成物は二層分離を起こしてしまい、また予
備反応時間が長すぎるとゲル化が起きてしまう。The time required for the preliminary reaction varies depending on the 1,4-polybutadiene, polymaleimide, etc. used, but it is continued until the resin composition remains uniform in the B-stage or C-stage state. If the pre-reaction time is too short, the resin composition will separate into two layers, and if the pre-reaction time is too long, gelation will occur.
さらに、樹脂組成物が均一となる適当な予備反応時間の
範囲内で、予備反応時間が短ければ、Ｂステージ状態が
進まず（高分子化せず）、成形時における樹脂の溶融粘
度を低くすることができ、また、予備反応時間が長けれ
ば、Ｂステージ状態が進み（高分子化が進み）、成形時
における樹脂の溶融粘度を高くすることができ、Ｂステ
ージ状態の調節が可能である。Furthermore, if the pre-reaction time is short within an appropriate pre-reaction time range that makes the resin composition uniform, the B-stage state will not progress (polymerization will not occur) and the melt viscosity of the resin during molding will be lowered. Moreover, if the pre-reaction time is long, the B-stage state progresses (polymerization progresses), the melt viscosity of the resin during molding can be increased, and the B-stage state can be adjusted.
カルボキシル基末端１．４−ポリブタジエンおよびポリ
マレイミドの総量に対するカルボキシル基末端１．４−
ポリブタジエンの割合は２０ｗｔ％から８０ｗｔ％の割
合が好ましく、２Ｑｗｔ％より少ないと誘電率が高くな
ってしまい、また８Ｑｗｔ％より多いと耐熱性が低くな
ってしまう。Carboxyl-terminated 1,4-carboxyl-terminated 1,4- with respect to the total amount of polybutadiene and polymaleimide
The proportion of polybutadiene is preferably from 20 wt% to 80 wt%; if it is less than 2 Qwt%, the dielectric constant will be high, and if it is more than 8 Qwt%, the heat resistance will be low.
本発明において、ポリブタジェンとポリマレイミドを均
一に混合する装置としては、攪拌機を具備したフラスコ
、ニーダ、コニーダ、ロール等が使用できる。In the present invention, as an apparatus for uniformly mixing polybutadiene and polymaleimide, a flask equipped with a stirrer, a kneader, a co-kneader, a roll, etc. can be used.
このようにして予備反応せしめた熱硬化性耐熱樹脂組成
物は、加熱加圧成形することにより三次元硬化する。加
熱温度は１５０℃から３００℃の範囲であり、好まじ（
は１８０℃から２５０℃の間である。圧力は組成物をあ
る程度流動させるため、５ｋｇｆ／−以上必要である。The thermosetting heat-resistant resin composition pre-reacted in this way is three-dimensionally cured by heating and pressure molding. The heating temperature is in the range of 150°C to 300°C, preferably (
is between 180°C and 250°C. A pressure of 5 kgf/- or more is required to cause the composition to flow to some extent.
本発明の熱硬化性樹脂組成物にラジカル反応開始剤とし
て適当な有機過酸化物を添加すると、硬化時間を短縮す
ることができる。When an appropriate organic peroxide is added as a radical reaction initiator to the thermosetting resin composition of the present invention, the curing time can be shortened.
また、本発明の熱硬化性樹脂組成物にはシリカ、ガラス
パウダー、水酸化アルミニウム等の充填剤および難燃剤
等を併用することも可能である。Further, fillers such as silica, glass powder, aluminum hydroxide, flame retardants, etc. can also be used in combination with the thermosetting resin composition of the present invention.
さらに、本発明の熱硬化性樹脂組成物を、ガラスクロス
、ガラスペーパー、紙、カーボンファイバークロス、芳
香族ポリアミドクロス、石英繊維クロス等の基材に含浸
させて用いることも可能である。Furthermore, it is also possible to use the thermosetting resin composition of the present invention by impregnating it into a base material such as glass cloth, glass paper, paper, carbon fiber cloth, aromatic polyamide cloth, or quartz fiber cloth.
本発明により、カルボキシル基末端１．４−ポリブタジ
エン−ポリマレイミドの均一樹脂組成物が得られ、Ｂス
テージ状態の調節が可能となる理由は、カルボキシル基
末端１．４−ポリブタジエンとポリマレイミドが付加反
応するためと考えられる。この反応の詳細については定
かではないが、ポリマレイミドの炭素−炭素二重結合に
カルボキシル基末端１，４−ポリブタジエンの活性水素
が付加反応すると考えられる。According to the present invention, a homogeneous resin composition of carboxyl group-terminated 1,4-polybutadiene-polymaleimide can be obtained, and the reason why the B-stage state can be adjusted is that the carboxyl group-terminated 1,4-polybutadiene and the polymaleimide undergo an addition reaction. This is thought to be for the purpose of Although the details of this reaction are not certain, it is thought that the active hydrogen of the carboxyl group-terminated 1,4-polybutadiene undergoes an addition reaction to the carbon-carbon double bond of the polymaleimide.
また、カルボキシル基末端１．４−ポリブタジエン成分
が誘電率の低下に作用し、ポリマレイミドが耐熱性の向
上に作用するものと考えられる。It is also believed that the carboxyl group-terminated 1,4-polybutadiene component acts to lower the dielectric constant, and the polymaleimide acts to improve heat resistance.
以下、本発明の実施例につき説明する。ただし、本発明
は以下の実施例に限定されるものではない。Examples of the present invention will be described below. However, the present invention is not limited to the following examples.
実施例１〜３、比較例１〜３
攪拌装置と冷却管と温度計を具備した三つロフラスコに
カルボキシル基末端１．４−ポリブタジエン、ＨＹＣＡ
ＲＣＴＢ （１，４構造が８８ｗｔ％で、数平均分子量
が４．８００．１モル当たりの末端カルボキシル基数が
２．０であるがルボキシル基末端１．４−ポリブタジエ
ン、室温で液状、米国ＢＦ Ｇｏｏｄｒｉｃｈ社製商
品名）５０重量部とＮ、Ｎ’−ｐ、ｐ’−ジフェニルメ
タンビスマレイミド（融点１５５℃）５０重量部とを入
れ、オイルバスを用いて１７０℃に加温し、フラスコ内
の温度が１００℃に達した時点を０分とし、３０分置き
にサンプリングし、１５０分間撹拌を続けた。各サンプ
リング時点での樹脂組成物の性状と、各々の樹脂組成物
を２２０℃、２時間加熱硬化させたときの硬化物の状態
を表１に示す。Examples 1 to 3, Comparative Examples 1 to 3 Carboxyl group-terminated 1,4-polybutadiene, HYCA was placed in a three-bottle flask equipped with a stirrer, a cooling tube, and a thermometer.
RCTB (1,4-polybutadiene with a 1,4 structure of 88 wt% and a number average molecular weight of 4.800. The number of terminal carboxyl groups per mole is 2.0 and a carboxyl group terminal, liquid at room temperature, manufactured by BF Goodrich, USA) (trade name) and 50 parts by weight of N,N'-p,p'-diphenylmethane bismaleimide (melting point 155°C) were added and heated to 170°C using an oil bath until the temperature inside the flask reached The time when the temperature reached 100°C was defined as 0 minutes, sampling was carried out every 30 minutes, and stirring was continued for 150 minutes. Table 1 shows the properties of the resin composition at each sampling time and the state of the cured product when each resin composition was heated and cured at 220° C. for 2 hours.
以下余白
反応時間が０分、３０分の比較例１．２の樹脂組成物は
、フラスコ内では均一状態となっていたが、加熱硬化時
には２層に分離してしまった。The resin composition of Comparative Example 1.2, which had a margin reaction time of 0 minutes and 30 minutes, was in a uniform state in the flask, but separated into two layers upon heating and curing.
反応時間が６０分、９０分、１２０分の実施例１．２．
３の樹脂組成物は、フラスコ内、硬化物の状態いずれも
均一状態で、しかも成形時の樹脂溶融粘度の目安となる
１４０℃での溶融粘度を、反応時間を変えることにより
、幅広く調節可能であることがわかった。Examples 1.2. with reaction times of 60 minutes, 90 minutes, and 120 minutes.
The resin composition No. 3 is uniform both in the flask and in the cured product, and the melt viscosity at 140°C, which is a guideline for the resin melt viscosity during molding, can be adjusted over a wide range by changing the reaction time. I found out something.
反応時間が１５０分の比較例３ではフラスコ内の予備反
応中にゲル化してしまった。In Comparative Example 3 where the reaction time was 150 minutes, gelation occurred during the preliminary reaction in the flask.
実施例４
実施例１と同様にしてＨＹＣＡＲＣＴＢ ５０重量部
とＮ、Ｎ’−ｐ、ｐ’−ジフェニルメタンビスマレイミ
ド５０重量部とを、１７０℃で６０分間加熱溶融し、そ
の後温度を１３０℃まで下げてからラジカル反応開始剤
としてジクミルパーオキサイドを１．０重量部添加し、
５分間攪拌後、室温まで冷却した。Example 4 In the same manner as in Example 1, 50 parts by weight of HYCARCTB and 50 parts by weight of N,N'-p,p'-diphenylmethane bismaleimide were melted by heating at 170°C for 60 minutes, and then the temperature was lowered to 130°C. Then, 1.0 parts by weight of dicumyl peroxide was added as a radical reaction initiator,
After stirring for 5 minutes, the mixture was cooled to room temperature.
この樹脂組成物を！１００關、横１００ ｘ＊、高さ】
、６龍の金型に充填し、プレス成形機を使用して、圧力
４０ ｋ＋ｒｆ／ｃｊ、温度２２０℃、時間１２０分の
条件で加熱加圧し、硬化樹脂板を作製した。This resin composition! 100cm, width 100x*, height]
, 6 dragon molds, and heated and pressed using a press molding machine at a pressure of 40 k+rf/cj, a temperature of 220° C., and a time of 120 minutes to produce a cured resin plate.
この硬化樹脂板の耐熱性（ガラス転移温度、５％加熱減
量温度）および誘電率を測定した。結果を表２に示すが
、耐熱性に優れており、誘電率が低いことがわかった。The heat resistance (glass transition temperature, 5% heating loss temperature) and dielectric constant of this cured resin plate were measured. The results are shown in Table 2, and it was found that the heat resistance was excellent and the dielectric constant was low.
比較例４
ポリアミノビスマレイミド樹脂、ケルイミド６０１（フ
ランス、ローヌブーラン社製 商品名）を、実施例４と
同じ金型を用いて、同じ条件でプレス成形し、硬化樹脂
板を作製した。Comparative Example 4 A polyamino bismaleimide resin, Kerimide 601 (trade name, manufactured by Rhone-Bourand, France) was press-molded using the same mold as in Example 4 under the same conditions to produce a cured resin plate.
この硬化樹脂板の耐熱性、誘電率を測定した。The heat resistance and dielectric constant of this cured resin plate were measured.
結果を表２に示す。The results are shown in Table 2.
表２ 硬化樹脂板の特性
ｌ）真空理工調熱機械試験機ＴＭＡ−１５００を使用し
、昇温速度５℃／ｌｌｌ１ｎ、５ｇｒ荷重の条件で測定
した。Table 2 Characteristics of cured resin plate 1) Measured using a Vacuum Riko thermomechanical testing machine TMA-1500 under conditions of a temperature increase rate of 5° C./ll1n and a load of 5 gr.
２）真空理工製示唆熱天秤ＤＴＧ−３０００ＲＨを使用
し、昇温速度１０℃／ａｋｉｎの条件で測定した。2) Measurement was performed using a suggested thermobalance DTG-3000RH manufactured by Shinku Riko under conditions of a temperature increase rate of 10° C./akin.
３）ＪＩＳ−Ｃ−６４８１に準拠し、ＩＭＨｚの周波数
で測定した。3) Measured at a frequency of IMHz in accordance with JIS-C-6481.
以上詳細に説明した如く、本発明によれば、カルボキシ
ル基末端１．４−ポリブタジエンとポリマレイミドとの
無溶剤均一樹脂組成物が得られ、Ｂステージ状態の調節
が可能で、比較的低温成形が可能で、三次元硬化した硬
化物の誘電率が低く、耐熱性が高い熱硬化性耐熱樹脂組
成物が得られ、その工業的価値は大である。As explained in detail above, according to the present invention, a solvent-free homogeneous resin composition of carboxyl group-terminated 1,4-polybutadiene and polymaleimide can be obtained, the B-stage state can be adjusted, and relatively low temperature molding is possible. It is possible to obtain a thermosetting heat-resistant resin composition which is three-dimensionally cured and has a low dielectric constant and high heat resistance, and has great industrial value.
Claims (1)
ル基末端１，４−ポリブタジエンと、一般式 ▲数式、化学式、表等があります▼ （ここでＲ＿１は少なくとも２個の炭素原子を有するａ
価の有機基を表し、ａは２以上１０以下の数を表す。） で表されるポリマレイミドとを無溶剤で予備反応せしめ
ることを特徴とする熱硬化性耐熱樹脂組成物の製造方法
。 ２、ポリマレイミドがＮ，Ｎ′−ｐ，ｐ′−ジフェニル
メタンビスマレイミドである特許請求の範囲第１項記載
の熱硬化性耐熱樹脂組成物の製造方法。[Claims] 1. A carboxyl-terminated 1,4-polybutadiene with a number average molecular weight of 10,000 or less, and a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R_1 is at least two carbon atoms a with atoms
represents a valent organic group, and a represents a number of 2 or more and 10 or less. ) A method for producing a thermosetting heat-resistant resin composition, which comprises preliminarily reacting a polymaleimide represented by the following formula in the absence of a solvent. 2. The method for producing a thermosetting heat-resistant resin composition according to claim 1, wherein the polymaleimide is N,N'-p,p'-diphenylmethane bismaleimide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16633486A JPS6322814A (en) | 1986-07-15 | 1986-07-15 | Production of thermosetting heat-resistant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16633486A JPS6322814A (en) | 1986-07-15 | 1986-07-15 | Production of thermosetting heat-resistant resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6322814A true JPS6322814A (en) | 1988-01-30 |
Family
ID=15829437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16633486A Pending JPS6322814A (en) | 1986-07-15 | 1986-07-15 | Production of thermosetting heat-resistant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6322814A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02251844A (en) * | 1989-03-24 | 1990-10-09 | Konica Corp | Image forming method of silver halide photographic sensitive material |
| US5429864A (en) * | 1993-10-06 | 1995-07-04 | E. I. Du Pont De Nemours And Company | High efficiency filter fabric for hot gas filtration |
-
1986
- 1986-07-15 JP JP16633486A patent/JPS6322814A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02251844A (en) * | 1989-03-24 | 1990-10-09 | Konica Corp | Image forming method of silver halide photographic sensitive material |
| JP2704287B2 (en) * | 1989-03-24 | 1998-01-26 | コニカ株式会社 | Image forming method for silver halide photographic material |
| US5429864A (en) * | 1993-10-06 | 1995-07-04 | E. I. Du Pont De Nemours And Company | High efficiency filter fabric for hot gas filtration |
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