JPH0224305A - Thermosetting resin composition - Google Patents
Thermosetting resin compositionInfo
- Publication number
- JPH0224305A JPH0224305A JP17266788A JP17266788A JPH0224305A JP H0224305 A JPH0224305 A JP H0224305A JP 17266788 A JP17266788 A JP 17266788A JP 17266788 A JP17266788 A JP 17266788A JP H0224305 A JPH0224305 A JP H0224305A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- molecular weight
- phenol
- organic
- maleimide
- 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 description 6
- 229920001187 thermosetting polymer Polymers 0.000 title description 6
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000005011 phenolic resin Substances 0.000 abstract description 19
- 150000001451 organic peroxides Chemical class 0.000 abstract description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 14
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012778 molding material Substances 0.000 abstract description 6
- 230000009477 glass transition Effects 0.000 abstract description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 abstract description 4
- 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 abstract description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 abstract description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 abstract description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 229930003836 cresol Natural products 0.000 abstract description 2
- 229920000768 polyamine Polymers 0.000 abstract description 2
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 abstract description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 13
- 229920001568 phenolic resin Polymers 0.000 description 13
- 150000003003 phosphines Chemical class 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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
- 230000007774 longterm Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 description 3
- 239000011134 resol-type phenolic resin Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- -1 t-butylperoxy-33 Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は耐熱性で、しかも硬化性、靭性に優れた成形材
料用熱硬化性樹脂組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermosetting resin composition for molding materials that is heat resistant and has excellent curability and toughness.
近年、軽量化、製造工程の合理化、コストダウン等のた
め金属のプラスチック材料への代替が活発に進められて
いる。In recent years, metals have been actively replaced by plastic materials in order to reduce weight, rationalize manufacturing processes, and reduce costs.
従来、一般に７ボランク型フエノール樹脂が多く用いら
れているが、成形品を高温で長時間処理すると、強度、
寸法変化などが大巾に悪化し、信頼性に欠けている。Conventionally, 7-borane phenolic resins have been commonly used, but when molded products are treated at high temperatures for long periods of time, their strength and
Dimensional changes, etc. have significantly worsened, and reliability is lacking.
一方、耐熱性の良好なポリアミノビスマレイミド樹脂を
含む マレイミド樹脂は、一般に硬化物が硬すぎて靭性
に乏しい。On the other hand, maleimide resins including polyamino bismaleimide resins having good heat resistance generally produce cured products that are too hard and have poor toughness.
本発明者らは、マレイミド樹脂、融点が５０℃以上１２
０℃以下のレゾール型フェノール樹脂とホスフィン類、
有機過酸化物およびアルカリ土類金属酸化物又は水酸化
物から成る熱硬化性樹脂組成物について検討を進めて来
ている。The present inventors have developed a maleimide resin with a melting point of 50°C or higher and 12°C.
resol type phenolic resin and phosphines below 0℃,
Studies have been underway on thermosetting resin compositions comprising organic peroxides and alkaline earth metal oxides or hydroxides.
しかしながら、これらの系においては耐熱性、硬化性お
よび靭性に優れておるが、最近では、これらの特性に加
えて、更に−そうの長期にわたる耐熱性と、より高度の
靭性をもつものが要求されて来ている。However, these systems have excellent heat resistance, hardenability, and toughness, but recently, in addition to these properties, materials with even longer heat resistance and higher toughness are required. It's coming.
〔発明が解決しようとする課題］
本発明は、成形品の高温における長時間処理による強度
、寸法変化の大巾な低下を克服せんとして研究した結果
、ガラス転移温度が高く、低熱膨張のマレイミド樹脂を
用いることにより、成形品の耐熱劣化性が改善されると
の知見を得、更にこの知見を基に種々研究を進めて、本
発明を完成するに至ったものである。その目的とすると
ころは、長時間の耐熱性が良好で、しかも、硬化性、靭
性に優れた成形材料用熱硬化性樹脂組成物を提供するに
ある。[Problems to be Solved by the Invention] The present invention was developed as a result of research aimed at overcoming the drastic decline in strength and dimensional changes caused by long-term processing at high temperatures of molded products. The inventors have found that the heat deterioration resistance of molded products can be improved by using this method, and based on this knowledge, they have carried out various studies and have completed the present invention. The objective is to provide a thermosetting resin composition for molding materials that has good long-term heat resistance and excellent curability and toughness.
本発明は、マレイミド樹脂、融点が１２０℃以上２５０
℃以下であり、かつ数平均分子量が１，５００以上１０
．０００以下の高分子量のフェノール樹脂および硬化用
触媒から成ることを特徴とする熱硬化性樹脂組成物であ
る。The present invention uses a maleimide resin having a melting point of 120°C or higher and 250°C or higher.
℃ or less, and the number average molecular weight is 1,500 or more 10
．． The present invention is a thermosetting resin composition characterized by comprising a phenolic resin having a high molecular weight of 000 or less and a curing catalyst.
本発明において用いられるマレイミド樹脂は一般式（＋
）
（ただし０２０ｍ１（ｉは０〜ｎの整数）、ｍＲ＊１、
ｍ７．２、ｆｆ１ｌ、 ｆｆｉ、、、、ｌ□２は１ま
たは２
Ｘは−ＣＩｌ□−
−ＳＯ□
一
５−Ｓ−
またはベンゼン核どうしが直接結合していることを示す
。The maleimide resin used in the present invention has the general formula (+
) (However, 020m1 (i is an integer from 0 to n), mR*1,
m7.2, ff1l, ffi, ..., l□2 is 1 or 2.
Ｙは−ＣＩ＋□＝
〇−
−ＳＯ□−
Ｓ
Ｓ−Ｓ
またはベンゼン核どうしが直接結合していることを示す
ものであり、Ｙは上記各結合基の１種又はそれ以上の結
合基の混合でベンゼン核どうしが結合していることを示
す。Y indicates -CI+□= 〇- -SO□- S S-S or benzene nuclei are directly bonded to each other, and Y indicates a mixture of one or more of the above bonding groups. shows that the benzene nuclei are bonded to each other.
Ｒは１１、Ｃ１ｈ、またはＣ山を示す、）で示される化
合物で、例えば４．４”−ジアミノジフェニルメタン、
４．４’−Ｉアミノジフェニルエーテル、３，３゛−ジ
アミノジフェニルスルホン、２．２−シ（ρ−アミノフ
ェニル）プロパン、３，４，３”、４゜−テトラアミノ
−ジフェニルメタンとか、アニリンとホルムアルデヒド
から得られるアニリン樹脂などの芳香族ポリアミンをマ
レイミド化したものをあげることもできる。R is 11, C1h, or C mountain), for example, 4.4''-diaminodiphenylmethane,
4.4'-I aminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 2,2-(ρ-aminophenyl)propane, 3,4,3'',4'-tetraamino-diphenylmethane, aniline and formaldehyde Maleimidated aromatic polyamines such as aniline resins obtained from
高分子量フェノール樹脂は、フェノール、クレゾール、
キシレノールなどのフェノール類とホルムアルデヒドか
ら得られる融点が１２０℃以上、２５０℃以下、好まし
くは１５０℃以上、２２０℃以下でかつ数平均分子量が
１，５００以上１０，０００以下で好ましくは２．００
０以上、９，０００以下のものでフリーフェノールはな
るべく少ないものが良い。融点が１２０℃以下で、かつ
数平均分子量が１．５０００以下では、より高度な靭性
は得られず、融点が２５０’Ｃ以上で、かつ数平均分子
量が１０，０００以上ではゲル化物が含まれ、マレイミ
ド樹脂との相溶性が悪く、溶融粘度が高くて作業性が悪
く、好ましくない。High molecular weight phenolic resins include phenol, cresol,
The melting point obtained from phenols such as xylenol and formaldehyde is 120°C or more and 250°C or less, preferably 150°C or more and 220°C or less, and the number average molecular weight is 1,500 or more and 10,000 or less, preferably 2.00.
It is preferable that the free phenol content is 0 or more and 9,000 or less and has as little free phenol as possible. If the melting point is 120°C or lower and the number average molecular weight is 1.5000 or less, a higher degree of toughness cannot be obtained, and if the melting point is 250'C or higher and the number average molecular weight is 10,000 or higher, gelled products will be contained. It is not preferred because it has poor compatibility with maleimide resins, has a high melt viscosity, and has poor workability.
高分子量フェノール樹脂はマレイミド樹脂１００重量部
に対し５〜２００重量部が好ましい。少な過ぎると靭性
に乏しく脆い。多過ぎると硬化性と耐熱性が低下する。The amount of the high molecular weight phenol resin is preferably 5 to 200 parts by weight per 100 parts by weight of the maleimide resin. If it is too small, it will lack toughness and become brittle. If the amount is too large, curability and heat resistance will decrease.
硬化用触媒としては、有機ホスフィン類、有機過酸化物
または両者の併用が好ましく、特に有機ホスフィン類と
有機過酸化物の併用は有効である。The curing catalyst is preferably an organic phosphine, an organic peroxide, or a combination of both, and a combination of an organic phosphine and an organic peroxide is particularly effective.
有機ホスフィン類としては、例えばトリフェニルホスフ
ィン、トリー４−メチルフェニルホスフィン、トリー４
−メトキシフェニルホスフィン、トリブチルホスフィン
、トリオクチルホスフィン、トリー２−シアノエチルホ
スフィンなどをあげることができる。Examples of organic phosphines include triphenylphosphine, tri-4-methylphenylphosphine, tri-4
-methoxyphenylphosphine, tributylphosphine, trioctylphosphine, tri-2-cyanoethylphosphine, and the like.
ホスフィン類の使用量はマレイミド樹脂と高分子量フェ
ノール樹脂の総量１００重量部に対し、０．１〜１０重
景部重量ましい、少な過ぎると靭性に乏しく機械強度が
低下する。多過ぎるとロール混練時反応が進み過ぎてゲ
ル化したり、保存性が悪化する。The amount of phosphines to be used is preferably 0.1 to 10 parts by weight per 100 parts by weight of the total amount of maleimide resin and high molecular weight phenol resin; if it is too small, the toughness will be poor and the mechanical strength will be reduced. If the amount is too high, the reaction during roll kneading will proceed too much, resulting in gelation or poor storage stability.
有機過酸化物としては、ジーｔ−ブチルパーオキサイド
、Ｌ−１′チルクミルパーオキサイド、ジクミルパーオ
キサイド、１．３−ビス−（ｔ−ブチルパーオキシ−イ
ソプロビル）ベンゼン、１．１ジーｔ−ブチルパーオキ
シ−３３，５−）リメチルシクロヘキサン、１，１−ジ
ーＬ−フ゛チルパーオキシシクロヘキサンなどのジアル
キルパーオキサイド、Ｌ−フ゛チルパーベンゾエートな
どのアルキルパーエステルをあげることができる。有機
過酸化物の添加量は、マレイミド樹脂１００重量部に対
し、０．０５〜５重量部が好ましい。Examples of organic peroxides include di-t-butyl peroxide, L-1'-ticumyl peroxide, dicumyl peroxide, 1.3-bis-(t-butylperoxy-isopropyl)benzene, and 1.1-di-t-butyl peroxide. Examples include dialkyl peroxides such as t-butylperoxy-33,5-)limethylcyclohexane and 1,1-di-L-butylperoxycyclohexane, and alkyl peresters such as L-butylperbenzoate. The amount of organic peroxide added is preferably 0.05 to 5 parts by weight per 100 parts by weight of the maleimide resin.
有機過酸化物が少な過ぎると、ガラス転移温度の向上が
十分でなく、多過ぎると、脆くなり、機械強度が低下す
る。If the amount of organic peroxide is too small, the glass transition temperature will not be improved sufficiently, and if it is too large, the material will become brittle and the mechanical strength will decrease.
有機ホスフィン類と有機過酸化物を併用した時の配合比
率は、有機ホスフィン類１に対し有機過酸化物０．２〜
５．Ｏが好ましい、有機ホスフィン類に対する有機過酸
化物の配合比率は少な過ぎるとガラス転移温度や機械強
度が多少低下する傾向がみられる。When organic phosphines and organic peroxides are used together, the blending ratio is 1 part organic phosphine to 0.2 to 0.2 organic peroxides.
5. If the blending ratio of the organic peroxide to the organic phosphine, preferably O, is too small, the glass transition temperature and mechanical strength tend to decrease to some extent.
有機ホスフィン類と有機過酸化物を併用した時の使用量
は、マレイミド樹脂と高分子量フェノール樹脂の総量１
００重景重量対し、０．０５〜１０重量部が好ましい、
少な過ぎると硬化性が十分でなく、成形時間に長時間を
要する。多過ぎると、ロール混練時反応が進み過ぎてゲ
ル化したり、保存性が悪化する。When using organic phosphines and organic peroxides together, the amount used is the total amount of maleimide resin and high molecular weight phenolic resin 1
Preferably 0.05 to 10 parts by weight based on 0.00 weight.
If the amount is too small, the curing properties will be insufficient and the molding time will take a long time. If the amount is too high, the reaction during roll kneading will proceed too much, resulting in gelation or poor storage stability.
本発明の組成物は必要に応じて、充填剤、表面処理剤、
離型剤、着色剤などを配合し、混合または混練して成形
材料にすることが出来る。The composition of the present invention may contain fillers, surface treatment agents,
A molding material can be obtained by adding a mold release agent, a coloring agent, etc., and mixing or kneading it.
本発明に従うと、硬化性が良好で、ガラス転移温度が高
く、長期にわたる耐熱性と、高度な靭性に優れた硬化樹
脂が得られるので、成形材料用熱硬化性樹脂組成物とし
て好適である。According to the present invention, a cured resin with good curability, a high glass transition temperature, long-term heat resistance, and high toughness can be obtained, so it is suitable as a thermosetting resin composition for molding materials.
〈高分子量フェノール樹脂の合成例〉
合成例１
２２のセパラブルフラスコに水２５０ｇと３５重量％の
塩酸４５０ｇと３７重量％のホルマリン８００ｇの混合
水溶液を入れ、さらにフェノール５０ｇと３７重量％ホ
ルマリン１５ｇの混合水溶液を添加した。添加後３０分
間撹拌し、９０分間静置した０次いで時々攪拌しなから
９０”Ｃまで昇温し、１５分間保持して高分子量フェノ
ール樹脂（ＰＰ−Ａ）を得た。<Synthesis example of high molecular weight phenolic resin> Synthesis example 1 A mixed aqueous solution of 250 g of water, 450 g of 35 wt% hydrochloric acid, and 800 g of 37 wt% formalin was placed in a 22 separable flask, and then 50 g of phenol and 15 g of 37 wt% formalin were added. A mixed aqueous solution was added. After the addition, the mixture was stirred for 30 minutes and allowed to stand for 90 minutes.Then, while stirring occasionally, the temperature was raised to 90''C and held for 15 minutes to obtain a high molecular weight phenol resin (PP-A).
かくして得た高分子量フェノール樹脂（ＰＰ−Ａ）を４
０″〜５０℃の温水で３回洗浄後、３０℃で１時間乾燥
した。The thus obtained high molecular weight phenolic resin (PP-A) was
After washing three times with warm water of 0'' to 50°C, it was dried at 30°C for 1 hour.
この高分子量フェノール樹脂（ＰＰ−Ａ）の融点は、１
７３“Ｃで数平均分子量は３．５００であった。The melting point of this high molecular weight phenolic resin (PP-A) is 1
73"C and the number average molecular weight was 3.500.
合成例２
水７００ｇにホルムアルデヒ）２８０ｇ、塩酸３５ｇを
溶かし、これにメタクレゾール５３０ ｇ。Synthesis Example 2 280 g of formaldehyde and 35 g of hydrochloric acid were dissolved in 700 g of water, and 530 g of metacresol was dissolved therein.
ノニルフェノール２００ｇの混合液を加えて静置したま
ま、２０℃で５時間反応させた。A mixed solution of 200 g of nonylphenol was added, and the mixture was left standing to react at 20° C. for 5 hours.
沈澱した樹脂を攪拌下に十分水洗いした後冷却し、高分
子量フェノール樹脂（ＰＰ−８）を得た。高分子量フェ
ノール樹脂（ＰＰ−８）の融点は２０５℃１数平均分子
量は５，２００であった。The precipitated resin was thoroughly washed with water while stirring and then cooled to obtain a high molecular weight phenol resin (PP-8). The melting point of the high molecular weight phenolic resin (PP-8) was 205°C and the number average molecular weight was 5,200.
実施例１〜４
第１表に示す配合でマレイミド樹脂に合成例１２で得ら
れた高分子量フェノール樹脂、ホスフィン類、有機過酸
化物、ガラス繊維、アミノシラン及び離型剤を配合し、
ロール混練して成形材料を得た。これをトランスファー
成形により１８０℃３分で成形した。成形品は２００℃
４時間ポストキュアーした。その特性は第１表に示す。Examples 1 to 4 The high molecular weight phenolic resin obtained in Synthesis Example 12, phosphines, organic peroxide, glass fiber, aminosilane and mold release agent were blended with maleimide resin in the formulation shown in Table 1,
A molding material was obtained by roll kneading. This was molded by transfer molding at 180°C for 3 minutes. Molded products at 200℃
Post cured for 4 hours. Its properties are shown in Table 1.
比較例１
実施例１のホスフィン類と有機過酸化物を２メチルイミ
ダゾール（以下、２ＭＺという）に替えておこなった。Comparative Example 1 Comparative Example 1 was conducted by replacing the phosphines and organic peroxide in Example 1 with 2-methylimidazole (hereinafter referred to as 2MZ).
ただし成形時間は１０分であった。However, the molding time was 10 minutes.
比較例２
実施例１の高分子量フェノール樹脂を４，４゛−ジアミ
ノジフェニルメタン（以下、ＤＤＭという）に、ホスフ
ィン類と有機過酸化物を２ＭＺに替えておこなった。成
形時間は１０分であった。Comparative Example 2 A test was carried out by replacing the high molecular weight phenolic resin of Example 1 with 4,4'-diaminodiphenylmethane (hereinafter referred to as DDM), and replacing the phosphines and organic peroxide with 2MZ. The molding time was 10 minutes.
比較例３
実施例１の高分子量フェノール樹脂を融点９５℃２数平
均分子１７５０のレゾール型フェノール樹脂に替え、さ
らに硬化用触媒として酸化マグ不シウムを加えておこな
った。硬化性はマレイミド樹脂、高分子量フェノール樹
脂および硬化用触媒からなる配合物の熱板（１７０℃）
ゲルタイムで示した。Comparative Example 3 The high molecular weight phenolic resin of Example 1 was replaced with a resol type phenolic resin having a melting point of 95° C. and a 2-number average molecular weight of 1750, and magnonium oxide was added as a curing catalyst. Curing properties were determined using a hot plate (170°C) of a compound consisting of maleimide resin, high molecular weight phenolic resin, and curing catalyst.
Shown as gel time.
ホスフィン類および有機過酸化物の硬化用触媒が入った
実施例１〜４は硬化性に優れている。Examples 1 to 4 containing curing catalysts of phosphines and organic peroxides have excellent curability.
これらは、ガラス転移温度が高く、耐熱劣化性に優れ、
破壊エネルギーも大巾に向上している。These have a high glass transition temperature and excellent heat deterioration resistance.
Destructive energy has also been greatly improved.
（注）※ＩＢＭＩ ：三井東圧化学株式会社製ビス
マレイミド。(Note) *IBM: Bismaleimide manufactured by Mitsui Toatsu Chemical Co., Ltd.
※２ＢＭＩ−Ｍ：三井東圧化学株式会社製ポリマレイミ
ド。*2 BMI-M: Polymaleimide manufactured by Mitsui Toatsu Chemical Co., Ltd.
※３ ＢＭＩ−ＤＡ：三井東圧化学株式会社製ビスマレ
イミド。*3 BMI-DA: Bismaleimide manufactured by Mitsui Toatsu Chemical Co., Ltd.
※４ ＤＤＭ ：４．４’−ジアミノジフェニルメ
タン。*4 DDM: 4.4'-diaminodiphenylmethane.
※５ＰＲ：融点９５℃１数平均分子 量７５０の固形レゾール 型フェノール樹脂。*5PR: Melting point 95℃ 1 number average molecule 750 solid resol Type phenolic resin.
※６ＴＰＰ ：）リフェニルホスフィン。*6TPP:) Riphenylphosphine.
※７２ＭＺ ：２−メチルイミダゾール。*72MZ: 2-methylimidazole.
※８ＤＣニジクミルパーオキサイド。*8DC rainbow cum mill peroxide.
※９ＢＢ ：Ｌ−ブチルパーベンゾエート。*9BB: L-butyl perbenzoate.
※ｌＯマレイミド樹脂、高分子量フェノール樹脂および
硬化用触媒からなる配
合物のＶ′、！反ゲルタイム。* V′ of a formulation consisting of lO maleimide resin, high molecular weight phenolic resin, and curing catalyst,! Anti-gel time.
なお、ＢＭＩとＤＤＭから常法によ ※１１ ※１２ り得られるポリアミノビスマレイミ ド（２Ｍ２１％添加）のゲルタイム は２’４２’であった。In addition, from BMI and DDM using the usual method. *11 *12 polyamino bismaleium obtained by Gel time of de (2M21% addition) was 2'42'.
２５０℃で１ケ月熱処理し室温で測定。Heat treated at 250℃ for 1 month and measured at room temperature.
曲げ試験での、応カー歪み曲線から 破壊に要するエネルギーを算出。From the stress strain curve in the bending test Calculate the energy required for destruction.
Claims (1)
以下であり、かつ数平均分子量が１，５００以上、１０
，０００以下の高分子量フェノール樹脂および硬化用触
媒から成ることを特徴とする熱硬化性樹脂組成物。(1) Maleimide resin, melting point of 120℃ or higher, 250℃
or less, and the number average molecular weight is 1,500 or more, 10
,000 or less and a curing catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17266788A JPH0224305A (en) | 1988-07-13 | 1988-07-13 | Thermosetting resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17266788A JPH0224305A (en) | 1988-07-13 | 1988-07-13 | Thermosetting resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0224305A true JPH0224305A (en) | 1990-01-26 |
Family
ID=15946139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17266788A Pending JPH0224305A (en) | 1988-07-13 | 1988-07-13 | Thermosetting resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0224305A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2664605A1 (en) * | 1990-07-16 | 1992-01-17 | Rhone Poulenc Chimie | IMIDA GROUPED POLYMERS AND PROCESS FOR PREPARATION. |
| JP2005314656A (en) * | 2004-03-08 | 2005-11-10 | Dainippon Ink & Chem Inc | Thermosetting composition and cured product thereof |
| JP2011056496A (en) * | 2009-08-11 | 2011-03-24 | Kurita Water Ind Ltd | Water treatment method and water treatment flocculant |
| JP2013255923A (en) * | 2009-08-11 | 2013-12-26 | Kurita Water Ind Ltd | Water treatment method and water treatment flocculant |
-
1988
- 1988-07-13 JP JP17266788A patent/JPH0224305A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2664605A1 (en) * | 1990-07-16 | 1992-01-17 | Rhone Poulenc Chimie | IMIDA GROUPED POLYMERS AND PROCESS FOR PREPARATION. |
| JP2005314656A (en) * | 2004-03-08 | 2005-11-10 | Dainippon Ink & Chem Inc | Thermosetting composition and cured product thereof |
| JP4534802B2 (en) * | 2004-03-08 | 2010-09-01 | Ｄｉｃ株式会社 | Thermosetting composition and cured product thereof |
| JP2011056496A (en) * | 2009-08-11 | 2011-03-24 | Kurita Water Ind Ltd | Water treatment method and water treatment flocculant |
| JP2013255923A (en) * | 2009-08-11 | 2013-12-26 | Kurita Water Ind Ltd | Water treatment method and water treatment flocculant |
| US9403704B2 (en) | 2009-08-11 | 2016-08-02 | Kurita Water Industries, Ltd. | Water treatment method and water treatment flocculant |
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