JPS621409B2 - - Google Patents
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- Publication number
- JPS621409B2 JPS621409B2 JP54015987A JP1598779A JPS621409B2 JP S621409 B2 JPS621409 B2 JP S621409B2 JP 54015987 A JP54015987 A JP 54015987A JP 1598779 A JP1598779 A JP 1598779A JP S621409 B2 JPS621409 B2 JP S621409B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- present
- resin composition
- epoxy
- resins
- 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
Links
- 239000011342 resin composition Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 4
- 238000007348 radical reaction Methods 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000003733 fiber-reinforced composite Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000003822 epoxy resin Substances 0.000 description 15
- 229920000647 polyepoxide Polymers 0.000 description 15
- 238000010526 radical polymerization reaction Methods 0.000 description 11
- 238000009730 filament winding Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 238000000034 method Methods 0.000 description 6
- 229920006337 unsaturated polyester resin Polymers 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- -1 acrylic ester Chemical class 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 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
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 239000003677 Sheet moulding compound Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation 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
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】
本発明は、すぐれたコンポジツト物性を有する
繊維強化プラスチツク（以下FRPと略称）を製
造するための低粘度の硬化性樹脂組成物に関す
る。
さらに詳しくは、短時間で硬化し耐熱性の高い
FRPをフイラメントワインデイング法によつて
製造するための低粘度でかつポツトライフの長い
硬化性樹脂組成物に関する。
フイラメントワインデイング法は、強化材に液
体樹脂を含浸させながらマンドレルに巻きつける
成形法で、従来よりパイプやタンクの製造に利用
されている。この成形法は、補強材に連続的に樹
脂を含浸させる必要があるため、低粘度の液体樹
脂を使うことと、大型の成形品を製造するために
は樹脂組成物のポツトライフが長くなければなら
ないという制約があり、現在樹脂としては主にエ
ポキシ樹脂と不飽和ポリエステル樹脂が使われて
いる。エポキシ樹脂は、硬化物物性および耐熱性
にすぐれているが、一般に粘度が高くフイラメン
トワインデイングに適した樹脂が少なく、低粘度
のエポキシ樹脂に反応性希釈剤を添加したり、硬
化剤に低粘度の酸無水物を用いたエポキシ系樹脂
が用いられている。しかしながら、このエポキシ
系樹脂に反応性希釈剤を添加したものは耐熱性が
低下するし、酸無水物硬化剤を用いたものは、フ
イラメントワインデイング中の硬化剤の吸湿によ
り硬化特性に影響を受け性能低下を起しやすい。
さらに両者とも、硬化に長時間を有する。一方、
不飽和ポリエステル樹脂は低粘度でポツトライフ
も長く短時間で硬化するが耐熱性が低い。さらに
不飽和ポリエステル樹脂は炭素繊維強化プラスチ
ツクにおいて、炭素繊維に対する接着性が悪く、
樹脂の伸びも小さいために層間セン断強度の低い
ものになつている。
そこで、エポキシ樹脂と不飽和ポリエステル樹
脂の欠点を補うために、エポキシ樹脂にα，β不
飽和カルボン酸であるアクリル酸やメタクリル酸
を付加させた硬化性不飽和エステルすなわちビニ
ルエステルが開発された。この樹脂は、エポキシ
樹脂のすぐれた硬化物物性と不飽和ポリエステル
樹脂の硬化性をかね備え、上記の両者の欠点をか
なり克服されたが、耐熱性の良いものが得られて
いない。
このように、エポキシ樹脂、不飽和ポリエステ
ル樹脂、ビニルエステル樹脂には、各々欠点があ
り、近い将来フイラメントワインデイング法によ
り作られるドライブシヤフトのような産業資材
FRPのマトリツクス樹脂に要求されている機械
的特性が良く、耐熱性が高く、低粘度でポツトラ
イフが長く、さらに、硬化時間が短いという特性
を完全に満足しているものがない。
そこで、本発明者らは、上記の要求項目を満足
するフイラメントワインデイング用マトリツクス
樹脂を開発すべく研究した結果、本発明に到つ
た。
即ち、本発明は、従来のビニルエステル樹脂の
ように、エポキシ樹脂とアクリル酸やメタクリル
酸のようなα，β不飽和カルボン酸をあらかじめ
反応させたものにスチレンのような架橋性モノマ
を加え、ラジカル重合により硬化させるのではな
く、エポキシ樹脂、不飽和カルボン酸、架橋性モ
ノマおよびラジカル反応開始剤からなる樹脂組成
物であつて、加熱によつてラジカル重合と同時に
エポキシ基とカルボン酸との反応により硬化する
樹脂組成物に関するものである。
本発明の樹脂組成物において、エポキシ樹脂は
ラジカル重合と同時にエポキシ基がカルボン酸と
反応する、すなわち無触媒で加熱だけで反応する
ことが必要である。このようなエポキシ樹脂とし
てはポリグリシジルアミンがあり、さらに具体的
には、ポリグリシジルアミンとしてＮ，Ｎ，
N′，N′テトラグリシジルジアミノジフエニルメ
タン、Ｎ，Ｎ，N′，N′−テトラグリシジル−ｍ
−キシレンジアミン、Ｎ，Ｎ−ジグリシジルアニ
リン、トリグリシジルイソシアヌレート等を例示
することができる。
本発明に用いられるカルボン酸としては、エポ
キシ基と反応すると共にラジカル重合するもの、
すなわち、一般式CH2＝CR（CH2）o−COOHで
表わせるカルボン酸であり、たとえばアクリル
酸、メタクリル酸、ビニル酢酸、アリル酢酸、Δ
〓−ｎ−ヘキセノイツク酸等を挙げることができ
る。また、これらの不飽和カルボン酸としてその
無水物を用いることができる。しかし、機械的特
性、耐熱性の面から、アクリル酸、メタクリル酸
が好ましい。
次に、本発明に用いられるエポキシ樹脂とカル
ボン酸の混合割合は、エポキシ樹脂のエポキシ基
１当量に対して１当量のカルボン酸になるように
すればよい。しかし、必要に応じて、硬化物物性
やポツトライフの調節等でこの割合を変えてもさ
しつかえないが、本発明を有効に実施するために
は、エポキシ樹脂のエポキシ基１当量に対して、
カルボン酸1.4〜0.6当量の割合になるように混合
するのが望ましい。
さらに、本発明に用いられる架橋性モノマとし
ては、スチレン、ジアリルフタレート、ジアリル
イソフタレート、アクリル酸エステル、メタクリ
ル酸エステルのようにラジカル重合をするモノマ
であればよいが、耐熱性の面から、スチレン、ジ
アリルフタレート、ジアリルイソフタレートが好
ましい。この架橋性モノマの混合割合は、0.1〜
60部であるが、耐熱性の面から1.0〜40部の範囲
が望ましい。
本発明を有効に実施するための硬化温度は80〜
160℃の範囲が好ましい。この理由から、本発明
に用いられるラジカル開始剤としては、ベンゾイ
ルパーオキサイド、ｔ−ブチルパーベンゾエイ
ト、ジクミルパーオキサイド、ジ−ｔ−ブチルパ
ーオキサイドのように、80〜160℃の温度範囲で
ラジカル重合を起すラジカル反応開始剤ならどれ
でもよく、特に限定するものではない。さらに、
機械的特性、耐熱性を向上するには、160〜170℃
で30〜60分間後硬化するのが望ましい。このよう
に、硬化した本発明の樹脂硬化物の熱変形温度は
170℃以上あり、また、本発明の樹脂組成物と炭
素繊維からなるFRPの層間セン断強度は11〜12
Kg／mm2あり、すぐれたコンポジツト物性を有して
いる。
本発明は補強材として、ガラス繊維、有機繊維
炭素繊維など、通常FRPの補強材として用いら
れるものはすべて使用できるし、炭素繊維とガラ
ス繊維等との混合使用の場合にも適用出来る。さ
らに、本発明による樹脂組成物はフイラメントワ
インデイング用に適しているばかりでなく、樹脂
組成物が低粘度でかつポツトライフが長いことを
活かして、キヤステイングモールデイング、レジ
ンインジエクシヨンモールデイグ、シートモール
デイングコンパウド用樹脂組成物としても適して
おり、必要により無水シリカ、顔料などの充填剤
を添加して使用してもさしつかえない。
本発明になる硬化性樹脂組成物の特徴を列挙す
ると、
(1) 硬化時間は不飽和ポリエステルと同様に極め
て短時間である。
(2) 室温では反応性の低いモノマを配合してお
り、低粘度で、かつポツトライフが非常に長く
フイラメントワインデイング成形時の含浸性、
作業性、大型成形性にすぐれている。
(3) 使用時にモノマの配合割合をコントロールす
ることができ、不飽和ポリエステルやビニルエ
ステル樹脂の欠点である濃度、組成の経時変化
や変性のおそれがない。
(4) エポキシ樹脂成分を含有するため、特に炭素
繊維に対する接着力が大きい。
以下、実施例によつて本発明の内容をさらに詳
細に説明する。
実施例 １
Ｎ，Ｎ，N′，N′−テトラグリシジルジアミノ
ジフエニルメタン40ｇとスチレン36ｇとアクリル
酸24ｇとｔ−ブチルパーベンゾエイト１ｇを均一
に混合し樹脂液を調整し実施例１と同様な実験を
行なつた。その結果、25℃における粘度は３ポイ
ズ、ポツトライフは20時間以上あつた。また、
ILSS並びに曲げ特性は表の通りであり、優れた
コンポジツト物性を有している。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a low-viscosity curable resin composition for producing fiber-reinforced plastics (hereinafter abbreviated as FRP) having excellent composite physical properties. More specifically, it cures in a short time and has high heat resistance.
This invention relates to a curable resin composition with low viscosity and long pot life for producing FRP by filament winding method. The filament winding method is a molding method in which reinforcing material is impregnated with liquid resin and wound around a mandrel, and has traditionally been used to manufacture pipes and tanks. This molding method requires the reinforcing material to be continuously impregnated with resin, so a low-viscosity liquid resin must be used, and the resin composition must have a long pot life in order to produce large molded products. Due to these restrictions, currently epoxy resins and unsaturated polyester resins are mainly used as resins. Epoxy resins have excellent physical properties and heat resistance of cured products, but they generally have high viscosity and there are few resins that are suitable for filament winding. Epoxy resins using acid anhydrides are used. However, when a reactive diluent is added to this epoxy resin, the heat resistance decreases, and when an acid anhydride curing agent is used, the curing characteristics are affected by moisture absorption of the curing agent during filament winding. Performance is likely to deteriorate.
Furthermore, both have long curing times. on the other hand,
Unsaturated polyester resin has a low viscosity, a long pot life, and cures in a short time, but has low heat resistance. Furthermore, unsaturated polyester resin has poor adhesion to carbon fibers in carbon fiber reinforced plastics.
Since the elongation of the resin is also small, the interlaminar shear strength is low. Therefore, in order to compensate for the drawbacks of epoxy resins and unsaturated polyester resins, curable unsaturated esters, that is, vinyl esters, were developed by adding α,β unsaturated carboxylic acids such as acrylic acid and methacrylic acid to epoxy resins. This resin has both the excellent physical properties of an epoxy resin and the curability of an unsaturated polyester resin, and has largely overcome the drawbacks of both of the above, but a resin with good heat resistance has not yet been obtained. In this way, epoxy resin, unsaturated polyester resin, and vinyl ester resin each have their own drawbacks, and in the near future industrial materials such as drive shafts made using the filament winding method will be used.
There is no material that completely satisfies the requirements of FRP matrix resins: good mechanical properties, high heat resistance, low viscosity, long pot life, and short curing time. Therefore, the present inventors conducted research to develop a matrix resin for filament winding that satisfies the above-mentioned requirements, and as a result, they arrived at the present invention. That is, in the present invention, like conventional vinyl ester resins, an epoxy resin and an α,β unsaturated carboxylic acid such as acrylic acid or methacrylic acid are reacted in advance, and a crosslinking monomer such as styrene is added thereto. Rather than being cured by radical polymerization, the resin composition consists of an epoxy resin, an unsaturated carboxylic acid, a crosslinking monomer, and a radical reaction initiator, and the reaction between the epoxy group and the carboxylic acid is carried out simultaneously with radical polymerization by heating. This invention relates to a resin composition that is cured by. In the resin composition of the present invention, it is necessary that the epoxy group of the epoxy resin reacts with the carboxylic acid at the same time as radical polymerization, that is, the reaction occurs without a catalyst and only by heating. Such epoxy resins include polyglycidylamines, and more specifically, polyglycidylamines include N, N,
N',N'tetraglycidyldiaminodiphenylmethane, N,N,N',N'-tetraglycidyl-m
Examples include -xylene diamine, N,N-diglycidylaniline, and triglycidyl isocyanurate. The carboxylic acids used in the present invention include those that react with epoxy groups and undergo radical polymerization;
That is, it is a carboxylic acid represented by the general formula CH 2 = CR (CH 2 ) o -COOH, such as acrylic acid, methacrylic acid, vinyl acetic acid, allyl acetic acid, Δ
〓-n-hexenoitsic acid and the like can be mentioned. Furthermore, anhydrides thereof can be used as these unsaturated carboxylic acids. However, from the viewpoint of mechanical properties and heat resistance, acrylic acid and methacrylic acid are preferred. Next, the mixing ratio of the epoxy resin and carboxylic acid used in the present invention may be such that 1 equivalent of carboxylic acid per 1 equivalent of epoxy group in the epoxy resin. However, if necessary, this ratio may be changed to adjust the physical properties of the cured product or the pot life, but in order to effectively carry out the present invention, it is necessary to
It is desirable to mix the carboxylic acids in a proportion of 1.4 to 0.6 equivalents. Further, as the crosslinking monomer used in the present invention, any monomer that undergoes radical polymerization such as styrene, diallyl phthalate, diallyl isophthalate, acrylic ester, and methacrylic ester may be used. , diallyl phthalate, and diallyl isophthalate are preferred. The mixing ratio of this crosslinking monomer is 0.1~
The amount is 60 parts, but from the viewpoint of heat resistance, a range of 1.0 to 40 parts is desirable. The curing temperature for effectively implementing the present invention is 80~
A range of 160°C is preferred. For this reason, the radical initiators used in the present invention, such as benzoyl peroxide, t-butyl perbenzoate, dicumyl peroxide, and di-t-butyl peroxide, are suitable for use in the temperature range of 80 to 160°C. Any radical reaction initiator that causes radical polymerization may be used, and is not particularly limited. moreover,
160-170℃ to improve mechanical properties and heat resistance
It is desirable to post-cure for 30 to 60 minutes. In this way, the heat distortion temperature of the cured resin of the present invention is
170℃ or higher, and the interlaminar shear strength of FRP made of the resin composition of the present invention and carbon fibers is 11 to 12.
Kg/mm 2 and has excellent composite properties. The present invention can use any reinforcing material that is normally used as a reinforcing material for FRP, such as glass fibers and organic fibers and carbon fibers, and can also be applied to the case where carbon fibers, glass fibers, etc. are used in combination. Further, the resin composition according to the present invention is not only suitable for filament winding, but also for casting molding, resin injection molding, etc., by taking advantage of the resin composition's low viscosity and long pot life. It is also suitable as a resin composition for sheet molding compounds, and if necessary, fillers such as anhydrous silica and pigments may be added thereto. The characteristics of the curable resin composition of the present invention are listed below: (1) The curing time is extremely short, similar to unsaturated polyester. (2) Contains monomers that have low reactivity at room temperature, resulting in low viscosity and a very long pot life.
Excellent workability and large-scale moldability. (3) The mixing ratio of monomers can be controlled during use, and there is no risk of changes in concentration or composition over time or denaturation, which are disadvantages of unsaturated polyester and vinyl ester resins. (4) Because it contains an epoxy resin component, it has particularly strong adhesion to carbon fibers. Hereinafter, the content of the present invention will be explained in more detail with reference to Examples. Example 1 40 g of N,N,N',N'-tetraglycidyldiaminodiphenylmethane, 36 g of styrene, 24 g of acrylic acid, and 1 g of t-butyl perbenzoate were mixed uniformly to prepare a resin liquid, and the same procedure as in Example 1 was carried out. I conducted an experiment. As a result, the viscosity at 25°C was 3 poise and the pot life was over 20 hours. Also,
The ILSS and bending properties are shown in the table, indicating that the composite has excellent physical properties. 【table】
Claims (1)
る不飽和カルボン酸、架橋性モノマおよびラジカ
ル反応開始剤ととからなる繊維強化複合材料用硬
化性樹脂組成物。 H2C＝CR（CH2）−COOH （ただし上式中、ＲはＨ又はCH3、ｎは０〜５
の整数を示す。）[Scope of Claims] 1. A curable resin composition for fiber-reinforced composite materials, comprising a polyglycidylamine, an unsaturated carboxylic acid represented by the following general formula, a crosslinking monomer, and a radical reaction initiator. H 2 C=CR(CH 2 )-COOH (in the above formula, R is H or CH 3 and n is 0 to 5
indicates an integer. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1598779A JPS55110115A (en) | 1979-02-16 | 1979-02-16 | Curable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1598779A JPS55110115A (en) | 1979-02-16 | 1979-02-16 | Curable resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55110115A JPS55110115A (en) | 1980-08-25 |
| JPS621409B2 true JPS621409B2 (en) | 1987-01-13 |
Family
ID=11904007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1598779A Granted JPS55110115A (en) | 1979-02-16 | 1979-02-16 | Curable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55110115A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02127804A (en) * | 1988-11-08 | 1990-05-16 | Nippon Telegr & Teleph Corp <Ntt> | Helical antenna |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4486350B2 (en) * | 2003-11-28 | 2010-06-23 | 日本ユピカ株式会社 | Nitrogen-containing epoxy (meth) acrylate and method for producing the same, and composition and cured product thereof |
| EP2468793B1 (en) | 2009-08-17 | 2015-02-25 | DIC Corporation | Resin composition for fiber-reinforced composite materials, cured product thereof, fiber-reinforced composite materials, moldings of fiber-reinforced resin, and process for production thereof |
| WO2011034042A1 (en) * | 2009-09-18 | 2011-03-24 | Dic株式会社 | Resin composition for fiber-reinforced composite material, cured object obtained therefrom, fiber-reinforced composite material, fiber-reinforced molded resin, and process for producing same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4948774A (en) * | 1972-09-12 | 1974-05-11 | ||
| JPS5074000A (en) * | 1973-10-18 | 1975-06-18 | ||
| JPS51125200A (en) * | 1974-09-13 | 1976-11-01 | Hitachi Chem Co Ltd | Curable resin composition |
| JPS5247086A (en) * | 1975-10-14 | 1977-04-14 | Nippon Shokubai Kagaku Kogyo Co Ltd | Method for curing thermosetting resin compositions |
-
1979
- 1979-02-16 JP JP1598779A patent/JPS55110115A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4948774A (en) * | 1972-09-12 | 1974-05-11 | ||
| JPS5074000A (en) * | 1973-10-18 | 1975-06-18 | ||
| JPS51125200A (en) * | 1974-09-13 | 1976-11-01 | Hitachi Chem Co Ltd | Curable resin composition |
| JPS5247086A (en) * | 1975-10-14 | 1977-04-14 | Nippon Shokubai Kagaku Kogyo Co Ltd | Method for curing thermosetting resin compositions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02127804A (en) * | 1988-11-08 | 1990-05-16 | Nippon Telegr & Teleph Corp <Ntt> | Helical antenna |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55110115A (en) | 1980-08-25 |
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