JPH0335018A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH0335018A JPH0335018A JP16889289A JP16889289A JPH0335018A JP H0335018 A JPH0335018 A JP H0335018A JP 16889289 A JP16889289 A JP 16889289A JP 16889289 A JP16889289 A JP 16889289A JP H0335018 A JPH0335018 A JP H0335018A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- dds
- prepreg
- resin composition
- diaminodiphenylsulfone
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 53
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 16
- 239000011347 resin Substances 0.000 abstract description 16
- 239000011159 matrix material Substances 0.000 abstract description 13
- 239000002131 composite material Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 3
- -1 imidazole compound Chemical class 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 2
- 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 8
- 239000000463 material Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
本発明はエポキシ樹脂組成物に関し、特に高性能構造材
料用マトリックス樹脂として有用な、保存性に優れたプ
リプレグ用のエポキシ樹脂組成物に関する。The present invention relates to an epoxy resin composition, and particularly to an epoxy resin composition for prepregs that is useful as a matrix resin for high-performance structural materials and has excellent storage stability.
エポキシ樹脂は、耐熱性、弾性率、硬度及び耐薬品性に
優れており、特に炭素繊維、ガラス繊維、アラミド繊維
等の強化繊維とマトリックス樹脂からなる複合材料用の
マトリックス樹脂として、広く使用されている。ただ、
大きな強度や耐熱性、耐水性等を必要とする用途、例え
ば航空機等の構造材料としての用途などには、自ずと使
用し得るエポキシ樹脂や硬化剤は限定されてしまう。
近年、航空機用その他の高性能構造材料用マトリックス
樹脂としては、Ｎ、Ｎ、Ｎ’、Ｎ’−テトラグリシジル
ジアミノジフェニルメタンを主成分とし、ジアミノジフ
ェニルスルホンを硬化剤とするエポキシ樹脂組成物が用
いられている。即ち、Ｎ、Ｎ、Ｎ’、Ｎ′−テトラグリ
シジルジアミノジフェニルメタンは４官能乎ボキシ樹脂
であるため、その硬化物は架橋密度が高く、耐熱性に優
れた硬化物が得られるが、特に硬化剤にジアミノジフェ
ニルスルホンを用いた場合に熱変形温度の高い硬化物が
得られ、しかもその樹脂組成物は比較的長いポットライ
フを有するため、プリプレグ用樹脂組成物として使用す
ることができる。
〔発明が解決しようとする課題１
ところが、ジアミノジフェニルスルホンは、工ボキシ樹
脂に対する相溶性があまり良くないので、エポキシ樹脂
と配合後、１００℃以上に加熱溶融するか、又はアセト
ン、メチルエチルケトン等の溶媒を用いて溶解し均一組
成物とすることが推奨されている（特開昭５６〜１２０
７２７号公報）、従って、プリプレグ用エポキシ樹脂組
成物は、通常、エポキシ樹脂成分とジアミノジフェニル
スルホンとを、アセトン、メチルエチルケトン等に溶解
させて液状組成物として、あるいは６０℃又はそれ以上
の温度で充分混合して固体状組成物として、調製されて
いる。
ジアミノジフェニルスルホンは、アミン系硬化剤として
は比較的長いシェルフライフを有するとはいうものの、
これを完全に溶解した液状樹脂組成物からプリプレグを
製造する場合には、どうしても該組成物中において硬化
反応が一部進行するため、プリプレグとしてのポットラ
イフが短くなることは避けられない。一方、ジアミノジ
フェニルスルホンを溶解させずに混合しただけの固体状
樹脂組成物からプリプレグを製造する場合には、通常ジ
アミノジフェニルスルホン粒子は、その粒径が大きく且
つ不揃いであるため、均一なマトリックス組成を得るこ
とが困難であったり、また粒径の大きいジアミノジフェ
ニルスルホン粒子は、プリプレグ製造時に補強用ｙＡ＃
４１（特に炭素繊維）のフィラメント内に均一に分散す
ることができず、そのため硬化度が均一にならなかった
りする危険性がある。以上例れの場合にも、マトリック
スの機能が低下し、充分なＣＦＲＰ物性を発現すること
ができない。
従って、本発明は、高性能構造材料用の、ライフが著し
く改善されたプリプレグを製造し得るエポキシ樹脂組成
物を提供することを目的とする。Epoxy resin has excellent heat resistance, elastic modulus, hardness, and chemical resistance, and is widely used as a matrix resin for composite materials made of matrix resin and reinforcing fibers such as carbon fiber, glass fiber, and aramid fiber. There is. just,
Epoxy resins and curing agents that can be used are naturally limited to applications that require high strength, heat resistance, water resistance, etc., such as applications as structural materials for aircraft and the like. In recent years, epoxy resin compositions containing N,N,N',N'-tetraglycidyldiaminodiphenylmethane as a main component and diaminodiphenylsulfone as a curing agent have been used as matrix resins for aircraft and other high-performance structural materials. ing. That is, since N,N,N',N'-tetraglycidyldiaminodiphenylmethane is a tetrafunctional boxy resin, its cured product has a high crosslinking density and excellent heat resistance, but especially when the curing agent When diaminodiphenylsulfone is used, a cured product with a high heat distortion temperature can be obtained, and the resin composition has a relatively long pot life, so it can be used as a prepreg resin composition. [Problem to be Solved by the Invention 1] However, diaminodiphenylsulfone does not have very good compatibility with engineered boxy resins, so after blending with epoxy resins, it must be melted by heating to 100°C or higher, or it must be heated to a temperature of 100°C or higher, or treated with a solvent such as acetone or methyl ethyl ketone. It is recommended that a homogeneous composition be obtained by dissolving the composition using
Therefore, the epoxy resin composition for prepregs is usually prepared as a liquid composition by dissolving the epoxy resin component and diaminodiphenylsulfone in acetone, methyl ethyl ketone, etc., or at a temperature of 60°C or higher. A solid composition is prepared by mixing. Although diaminodiphenylsulfone has a relatively long shelf life as an amine curing agent,
When a prepreg is manufactured from a liquid resin composition in which this resin is completely dissolved, the curing reaction inevitably proceeds partially in the composition, so it is inevitable that the pot life of the prepreg will be shortened. On the other hand, when manufacturing a prepreg from a solid resin composition in which diaminodiphenylsulfone is simply mixed without dissolving it, the diaminodiphenylsulfone particles usually have a large and irregular particle size, so that a uniform matrix composition cannot be obtained. Diaminodiphenylsulfone particles that are difficult to obtain or have a large particle size are used as reinforcing yA# during prepreg production.
41 (particularly carbon fiber), and therefore there is a risk that the degree of curing may not be uniform. In any of the above cases, the functionality of the matrix deteriorates, making it impossible to exhibit sufficient CFRP physical properties. It is therefore an object of the present invention to provide an epoxy resin composition with which prepregs for high-performance structural materials can be produced with significantly improved life.
本発明によれば、４官能エポキシ樹脂を主成分とし、硬
化剤としてジアミノジフェニルスルホンを含有するエポ
キシ樹脂組成物において、該ジアミノジフェニルスルホ
ンが粒子状で分散して存在し、しかも該粒子は粒径１３
−以下のものが５０重量２以上占めるものであることを
特徴とするエポキシ樹脂組成物が提供される。
即ち、本発明のエポキシ樹脂組成物は、４官能エポキシ
樹脂を主成分とし、硬化剤として粒径１３−以下のもの
が５０重量２以上占めるジアミノジフェニルスルホンが
粒子状で分散配合されていることを特徴とする。
通常の市販されているジアミノシフエシルスルホン（以
下ＤＤＳと略記する）は、粒径がかなり大きく、また粒
度分布もかなり広く、不揃いであるが、本発明において
は、粒径１３−以下の粒子が全ＤＤＳ粒子の５０重量２
以上含まれるように調製したものを使用する。特に粒径
＋ａ４以下の粒子が７０重量２以上含まれるものを使用
するのが好ましい１粒径１３−以下の粒子が全ＤＤＳ粒
子の５０重量１未満しか含まれていないＤＤＳを使用す
ると、前記したように均一なマトリックス組成を得るこ
とが困難になる上に、プリプレグ製造時に炭素繊維フィ
ラメント内に均一に分散することができず、従って硬化
度が不均一な複合体を生じる危険性がある。
また、本発明のエポキシ樹脂組成物においては、前記粒
度分布を有するＤＤＳは、粒子状で分散した状態で存在
している。ＤＤＳが溶解した状態で存在すると、保存中
に一部の硬化反応が進行するためポットライフが短くな
り、ライフの長いプリプレグを得ようとする本発明の目
的が達成されなくなる。
従って、本発明におけるエポキシ樹脂成分とＤＤＳとの
混合は、溶媒を使用してはならず、加熱、混合時間を短
時間にする必要がある。例えば、エポキシ樹脂を１００
℃に加熱し、＋３／ｌａ以下の粒子７０重重量風上含む
ＤＤＳを添加し、撹拌、混合し均一に分散したところで
ただちに冷却する。
ＤＤＳには、４．４’−１３，３’−１３，４′−等の
異性体やそれらの混合物があるが、本発明においてはこ
れらの何れも使用することができる。４．４’−ＤＤＳ
は他の異性体に比べ耐熱性は高いが吸水率が大きいとか
、３．３’−ＤＤＳは弾性率は高いがガラス転移温度が
低いと−かいう特徴があるので、目的とする複合材料の
重視される物性に応じて、適宜選択使用することができ
る。
ＤＤＳはアミンの活性水素がエポキシ樹脂のエポキシ基
に対して０．４〜１．５当量、好ましくは０．６〜１．
２当量の割合でエポキシ樹脂に配合される。この配合範
囲より多くなると、硬化速度は早くなるが、シェルフラ
イフが短くなり、また硬化物の耐熱性が低下する。逆に
この配合範囲よりも少なくなると、硬化速度が非常に遅
くなると共に硬化物の耐熱性が低下する。
なお、本発明においては、三弗化硼素・アミン錯体、イ
ミダゾール化合物、ジシアンジアミドなどを硬化促進剤
として使用することもできる。
本発明のエポキシ樹脂組成物においては、樹脂の主成分
は４官能エポキシ樹脂である０本発明で用いられる４官
能エポキシ樹脂としては、Ｎ、Ｎ、Ｎ’。
Ｎ′−テトラグリシジルジアミノジフェニルメタン（丁
ＧＤＤＭ）が代表的なものであるが、その他にテトラグ
リシジルメタキシレンジアミン（ＴＧＭＸ＾）、テトラ
グリシジルビスアミノメチルシクロヘキサン、テトラグ
リシジルベンゾフェノン、ビスレゾルシノールテトラグ
リシジルエーテル等が挙げられる。
これらの内、Ｎ、Ｎ、Ｎ’、Ｎ’−テトラグリシジルジ
アミノジフェニルメタンは、アラルダイトＭＹ７２０（
チバ・ガイギー社製）、ＥＬＭ４３４ （住友化学工業
■製）、エポトートＹＨ４３４（東部化成社製）、ＥＰ
６０４ （油化シェル■！り等の商品名で市販されてい
る。
これらの４官能エポキシ樹脂は架橋密度が高く、高耐熱
性且つ高弾性率の硬化物が得られるという大きな特徴を
有し、高性能構造材料用マトリックス樹脂として非常に
重要な樹脂であるが、硬化物の伸度が小さく脆いとか、
プリプレグにしたときのタック・ドレープ性が悪いとか
いう欠点もある。
従って、本発明のエポキシ樹脂組成物においては、硬化
物の靭性、伸度等やプリプレグとしたときのタック・ド
レープ性を改善するために、エポキシ樹脂成分として５
０重量１未満の他のエポキシ樹脂、例えばビスフェノー
ル＾系エポキシ樹脂、ビスフェノールＦ系エポキシ樹脂
、ブロム化エポキシ樹脂、ノボラック系エポキシ樹脂、
トリグリシジル型エポキシ樹脂などを配合することがで
きるし、また靭性向上のためにポリエーテルスルホン等
の熱可塑性樹脂を配合することもできる。ただ、この場
合、これらの配合量はエポキシ樹脂混合物中５０重量％
未満、好ましくは４０重電気未満とすべきであり、５０
重電気以上配合すると、複合材料としたときの耐熱性、
靭性、耐吸水性等が低下したり、あるいはプリプレグと
してのタック性、ドレープ性が低下する。
更に、上記記載の緒特性を失わない程度の範囲に充填剤
、希釈剤等の添加剤も用いることができる。
以上のことから明らかなように、本発明のエポキシ樹脂
組成物は、特定の粒径分布を有するＤＤＳを、４官能エ
ポキシ樹脂を主成分とする樹脂中に、殆ど溶解させずに
粒子状で分散させているので、該樹脂組成物からプリプ
レグを製造すると、プリプレグマトリックス内において
ＤＤＳ粒子は均一に分散されており、プリプレグを硬化
させ−ると、ＤＤＳ粒子は完全に溶解して均一なマトリ
ックス相を形成し、しかもプリプレグ硬化前に実質的に
重合反応が起きていないので、プリプレグのライフは長
いものとなる。
なお、本発明のエポキシ樹脂組成物は、複合材料とした
ときに優れた耐熱性、弾性率、耐吸水性を有するので、
高性能複合材料用マトリックス樹脂として使用され、航
空、宇宙、車両、船舶等の構造材料用として利用される
。もちろん、本発明のエポキシ樹脂組成物は、土木建築
用材料、塗料、ランニング材、接着剤、電気機器成形材
料（機械部品、治工具）等としても使用することができ
る。
【発明の効果】
本発明のエポキシ樹脂組成物は、前記構成としたことか
ら、次のような卓越した効果を奏する。
（イ）プリプレグとしたときのライフが著しく改善され
る。
（ロ） ＤＤＳの溶解工程を省けるためプリプレグの性
状が安定し、そのためプリプレグの取扱い性や硬化物の
性能が一定化する。
（ハ） ＤＤＳを溶解しないため系の粘度が低く、その
ためプリプレグの製造作業が容易である。
また、系の粘度が低いため高粘度の樹脂の添加も可能と
なる。
〔実施例Ｊ
次に、実施例及び比較例により本発明を更に詳細に説明
する。
実施例１〜２
本実施例では、４官能エポキシ樹脂（ＴＧＤＤＭ）とし
てエピコート６０４（油化シェル■製）を、ビスフェノ
ール＾系エポキシ樹脂として、エピコート１００４（油
化シェルｎ製）を、硬化剤としては１粒径の異なる二種
類のジアミノジフェニルスルホン（ＤＤＳ。
商品名：スミキュアーＳ；住友化学工業■製）を使用し
、プリプレグ用のマトリックス樹脂を調製した。
各実施例において、表−１に示すエポキシ樹脂成分を１
５０℃で加熱混合した。この混合物を８０℃まで冷却し
、エポキシ樹脂硬化剤（ＤＤＳ）を化学量論量添加し、
混合撹拌ののちただちに冷却し、ＤＤＳをエポキシ樹脂
に溶解させないようにエポキシ樹脂組成物を調製した。
上記で得たエポキシ樹脂を一方向に揃えた炭素繊維（強
度３５０ｋｇ／ｍｍ 、弾性率３２ｔ／ａｍ″）に含浸
させ、プリプレグを得た。このプリプレグのタック値を
タック測定機（東洋精機■製ビクマタツク）を用いて測
定した。その結果を表−１に示す。
また、実施例１．２に示すエポキシ樹脂組成物は粘度が
低く、プリプレグ製造時の作業性が良好であった。また
、これらのプリプレグは製造時の作業性もよく、且つタ
ック性、ドレープ性、樹脂フロー性、ハンドリング性、
保存安定性（表−１のタック値）等のプリプレグとして
の特性も良好であった。
比較例１〜５
表−１に示す配合割合で、上記実施例と同様にしてエポ
キシ樹脂組成物及びプリプレグを作製し試験を行なった
。その結果を表−１に示す。
表−１からこの比較例のプリプレグは本発明品に比較し
て、タック性保持率が悪いことが分る。According to the present invention, in an epoxy resin composition containing a tetrafunctional epoxy resin as a main component and diaminodiphenylsulfone as a curing agent, the diaminodiphenylsulfone is present in a dispersed form in the form of particles, and the particles have a particle size of 13
- An epoxy resin composition is provided, characterized in that the following constitutes 50% or more by weight. That is, the epoxy resin composition of the present invention has a tetrafunctional epoxy resin as its main component, and diaminodiphenylsulfone, which has a particle size of 13 or less and accounts for 50% or more by weight, is dispersed in the form of particles as a curing agent. Features. Ordinary commercially available diaminociphecylsulfone (hereinafter abbreviated as DDS) has a fairly large particle size and a fairly wide and uneven particle size distribution, but in the present invention, particles with a particle size of 13- or less are used. is 50 weight of total DDS particles2
Use a product prepared to contain the above. In particular, it is preferable to use a DDS containing 70 weight 2 or more of particles with a particle size of +A4 or less.If a DDS containing less than 50 weight 1 of particles with a particle size of 13- or less of the total DDS particles is used, as described above. Not only is it difficult to obtain a uniform matrix composition, but also it cannot be uniformly dispersed within the carbon fiber filaments during prepreg production, and there is therefore a risk of producing a composite with a non-uniform degree of hardening. Furthermore, in the epoxy resin composition of the present invention, the DDS having the above particle size distribution is present in a particulate and dispersed state. If DDS exists in a dissolved state, a part of the curing reaction will proceed during storage, resulting in a shortened pot life, making it impossible to achieve the objective of the present invention, which is to obtain a prepreg with a long life. Therefore, when mixing the epoxy resin component and DDS in the present invention, a solvent must not be used, and heating and mixing times must be shortened. For example, 100% epoxy resin
The mixture is heated to 0.degree. C., and DDS containing 70 gw of particles of not more than +3/la is added, stirred and mixed until uniformly dispersed, and immediately cooled. DDS includes isomers such as 4,4'-13, 3'-13,4' and mixtures thereof, and any of these can be used in the present invention. 4.4'-DDS
Compared to other isomers, 3.3'-DDS has high heat resistance but high water absorption, and 3.3'-DDS has high elastic modulus but low glass transition temperature. They can be appropriately selected and used depending on the physical properties that are important. In DDS, the active hydrogen of the amine is 0.4 to 1.5 equivalents, preferably 0.6 to 1.5 equivalents, preferably 0.6 to 1.5 equivalents, relative to the epoxy group of the epoxy resin.
It is blended into the epoxy resin at a ratio of 2 equivalents. When the amount exceeds this range, the curing speed becomes faster, but the shelf life becomes shorter and the heat resistance of the cured product decreases. On the other hand, if the amount is less than this range, the curing speed becomes extremely slow and the heat resistance of the cured product decreases. In the present invention, boron trifluoride/amine complexes, imidazole compounds, dicyandiamide, etc. can also be used as curing accelerators. In the epoxy resin composition of the present invention, the main component of the resin is a tetrafunctional epoxy resin. Examples of the tetrafunctional epoxy resin used in the present invention include N, N, and N'. N'-tetraglycidyldiaminodiphenylmethane (GDDM) is a typical example, but other examples include tetraglycidyl metaxylene diamine (TGMX^), tetraglycidyl bisaminomethylcyclohexane, tetraglycidyl benzophenone, and bisresorcinol tetraglycidyl ether. Can be mentioned. Among these, N,N,N',N'-tetraglycidyldiaminodiphenylmethane is Araldite MY720 (
(manufactured by Ciba Geigy), ELM434 (manufactured by Sumitomo Chemical), Epotote YH434 (manufactured by Tobu Kasei), EP
604 (commercially available under trade names such as Yuka Shell ■!ri). These tetrafunctional epoxy resins have a high crosslinking density, and have the major characteristics of being able to obtain cured products with high heat resistance and high modulus of elasticity. Although it is a very important resin as a matrix resin for high-performance structural materials, it has a low elongation of the cured product and is brittle.
It also has drawbacks such as poor tuck and drape properties when made into prepreg. Therefore, in the epoxy resin composition of the present invention, in order to improve the toughness, elongation, etc. of the cured product and the tack/drape properties when made into a prepreg, 5
0 weight less than 1 other epoxy resins, such as bisphenol^-based epoxy resins, bisphenol F-based epoxy resins, brominated epoxy resins, novolac-based epoxy resins,
A triglycidyl type epoxy resin can be blended, and a thermoplastic resin such as polyether sulfone can also be blended to improve toughness. However, in this case, the amount of these compounds is 50% by weight in the epoxy resin mixture.
should be less than 40, preferably less than 50
When combined with heavy electricity or more, the heat resistance when made into a composite material,
Toughness, water absorption resistance, etc. may be reduced, or the tackiness and drapability of the prepreg may be reduced. Furthermore, additives such as fillers and diluents can be used within the range that does not impair the properties described above. As is clear from the above, the epoxy resin composition of the present invention disperses DDS having a specific particle size distribution in the form of particles without dissolving it in a resin whose main component is a tetrafunctional epoxy resin. Therefore, when a prepreg is manufactured from the resin composition, the DDS particles are uniformly dispersed within the prepreg matrix, and when the prepreg is cured, the DDS particles are completely dissolved to form a uniform matrix phase. Moreover, since substantially no polymerization reaction occurs before the prepreg is cured, the prepreg has a long life. The epoxy resin composition of the present invention has excellent heat resistance, elastic modulus, and water absorption resistance when used as a composite material, so
It is used as a matrix resin for high-performance composite materials, and as a structural material for aviation, space, vehicles, ships, etc. Of course, the epoxy resin composition of the present invention can also be used as a civil engineering and construction material, a paint, a running material, an adhesive, an electrical equipment molding material (mechanical parts, jigs and tools), and the like. Effects of the Invention Since the epoxy resin composition of the present invention has the above-mentioned structure, it exhibits the following outstanding effects. (a) The life of the prepreg is significantly improved. (b) Since the process of dissolving DDS can be omitted, the properties of the prepreg are stabilized, and therefore the handleability of the prepreg and the performance of the cured product are made constant. (c) Since DDS is not dissolved, the viscosity of the system is low, and therefore prepreg manufacturing work is easy. Furthermore, since the viscosity of the system is low, it is also possible to add high viscosity resins. [Example J Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Examples 1 to 2 In this example, Epicoat 604 (manufactured by Yuka Shell ■) was used as a tetrafunctional epoxy resin (TGDDM), Epicoat 1004 (manufactured by Yuka Shell N) was used as a bisphenol epoxy resin, and as a curing agent. A matrix resin for a prepreg was prepared using two types of diaminodiphenylsulfone (DDS, trade name: Sumicure S, manufactured by Sumitomo Chemical Co., Ltd.) with different particle sizes. In each example, 1 epoxy resin component shown in Table 1 was added.
The mixture was heated and mixed at 50°C. The mixture was cooled to 80°C, stoichiometric amount of epoxy resin hardener (DDS) was added,
After mixing and stirring, the mixture was immediately cooled to prepare an epoxy resin composition so as not to dissolve DDS in the epoxy resin. The epoxy resin obtained above was impregnated into carbon fibers aligned in one direction (strength: 350 kg/mm, elastic modulus: 32 t/am") to obtain a prepreg. The tack value of this prepreg was measured using a tack measuring device (manufactured by Toyo Seiki). The results are shown in Table 1. In addition, the epoxy resin composition shown in Example 1.2 had a low viscosity and had good workability during prepreg production. The prepreg has good workability during manufacturing, and has excellent tackiness, drapeability, resin flowability, handling properties, and
The properties as a prepreg such as storage stability (tack value in Table 1) were also good. Comparative Examples 1 to 5 Epoxy resin compositions and prepregs were prepared and tested in the same manner as in the above Examples at the blending ratios shown in Table 1. The results are shown in Table-1. From Table 1, it can be seen that the prepreg of this comparative example has a lower tackiness retention rate than the product of the present invention.
Claims (1)
ジアミノジフェニルスルホンを含有するエポキシ樹脂組
成物において、該ジアミノジフェニルスルホンが粒子状
で分散して存在し、しかも該粒子は粒径１３μｍ以下の
ものが５０重量％以上占めるものであることを特徴とす
るエポキシ樹脂組成物。(1) In an epoxy resin composition containing a tetrafunctional epoxy resin as a main component and diaminodiphenylsulfone as a curing agent, the diaminodiphenylsulfone exists in the form of particles, and the particles have a particle size of 13 μm or less. An epoxy resin composition characterized by comprising 50% by weight or more of epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16889289A JPH0335018A (en) | 1989-06-30 | 1989-06-30 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16889289A JPH0335018A (en) | 1989-06-30 | 1989-06-30 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0335018A true JPH0335018A (en) | 1991-02-15 |
Family
ID=15876505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16889289A Pending JPH0335018A (en) | 1989-06-30 | 1989-06-30 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0335018A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2734832A1 (en) * | 1995-06-01 | 1996-12-06 | Inst Francais Du Petrole | Thermo-hardenable compsns. used for the impregnation of reinforcing fibres |
| JP2007320587A (en) * | 2006-05-30 | 2007-12-13 | Tokyo Container Kogyo Co Ltd | Bumper member and storage box using the same |
| JP2015028140A (en) * | 2013-06-26 | 2015-02-12 | 本田技研工業株式会社 | Matrix material |
-
1989
- 1989-06-30 JP JP16889289A patent/JPH0335018A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2734832A1 (en) * | 1995-06-01 | 1996-12-06 | Inst Francais Du Petrole | Thermo-hardenable compsns. used for the impregnation of reinforcing fibres |
| JP2007320587A (en) * | 2006-05-30 | 2007-12-13 | Tokyo Container Kogyo Co Ltd | Bumper member and storage box using the same |
| JP2015028140A (en) * | 2013-06-26 | 2015-02-12 | 本田技研工業株式会社 | Matrix material |
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