JPS6020925A - Novel epoxy resin and its composition - Google Patents
Novel epoxy resin and its compositionInfo
- Publication number
- JPS6020925A JPS6020925A JP12693583A JP12693583A JPS6020925A JP S6020925 A JPS6020925 A JP S6020925A JP 12693583 A JP12693583 A JP 12693583A JP 12693583 A JP12693583 A JP 12693583A JP S6020925 A JPS6020925 A JP S6020925A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- epoxy
- molecular weight
- curing agent
- average molecular
- 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.)
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Links
Abstract
Description
【発明の詳細な説明】
本発明は、酬熱団の硬化物の製造に有用な新規なエポキ
シ樹脂及びその組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel epoxy resin and a composition thereof useful for producing a cured product of sulfuric acid.
エポキシ樹脂に硬化剤を配合してなる熱硬化性樹脂組成
物は、電気、電子部品の注型、回路基板利料等の絶縁材
料、接着剤、繊維強化複合材料等に広く用いられている
。近年、電子部品の高密度集積化や航空機等への繊維強
化複合材料の利用等の進展に伴って、耐熱性の高い熱硬
化性樹脂組成物の開発が強く望〜まれでいる。Thermosetting resin compositions made by blending epoxy resin with a curing agent are widely used for casting of electric and electronic parts, insulating materials such as circuit board materials, adhesives, fiber-reinforced composite materials, and the like. In recent years, with the development of high-density integration of electronic components and the use of fiber-reinforced composite materials for aircraft, etc., there is a strong desire to develop thermosetting resin compositions with high heat resistance.
かかる観点から種々の耐熱性を有するエポキシ樹脂の開
発が試みられており、トリグリシジルイソシアヌレート
もその一つとして期待されている。From this point of view, attempts have been made to develop various epoxy resins having heat resistance, and triglycidyl isocyanurate is also expected to be one of them.
しかし乍ら、トリグリシジルイソシアヌレートは、結晶
性でかつ分子量が小さい為にプリプレグ化か困難であり
、且つ硬化時に結晶が急激にとけて粘度が著しく低下し
成型が困難となるため、実用化が難しくせいぜい改質剤
として使用される程７度であった。However, since triglycidyl isocyanurate is crystalline and has a small molecular weight, it is difficult to make into prepregs, and the crystals rapidly melt during curing, resulting in a significant drop in viscosity and difficulty in molding, making it difficult to put into practical use. The temperature was 7 degrees, which was difficult enough to be used as a modifier at most.
本発明者等はトリグリシジルイソシアヌレ−１・の従来
の欠点を解決する為に鋭意検削した結果、酸性触媒を加
えてオリゴマー化することにより成型や含浸が可能な新
規なエポキシ樹脂及びその組成物となし得ることを見出
して本発明に到達した。The inventors of the present invention have conducted extensive research to solve the conventional drawbacks of triglycidyl isocyanurate-1. As a result, the inventors have developed a new epoxy resin that can be molded and impregnated by adding an acidic catalyst and oligomerizing it, and its composition. The present invention was achieved by discovering that it can be made into a material.
すなわち、本発明はトリグリシジルイソシアヌレートに
酸性触媒を加えてオリゴマー化してえられるエポキシ価
０２当量／１００ｆ以上で、且つ分子量が４００〜１５
００である新規なエボキ・ノ樹脂であり、又該エポキシ
樹脂にグリシジル基と反応する硬化剤を配合してなる熱
硬化性樹脂組成物である。トリグリシジルイソシアヌレ
ートは、インシアヌル酸トエビロルヒドリンとの反応に
よって三官能型エポキシ樹脂であシ、純品の分子量は２
９７、エポキシ価１．０１当量／１００７の白色結晶で
あるが、通常はクロルヒドリン基の残存、未反応Ｎ Ｈ
基の残存等の影響でエポキシ価０．８０〜０．９５当量
／１００７、融点９０〜１２０℃、平均分子量３００〜
３５０の白色結晶粉末として市販されている。That is, the present invention is directed to oligomerizing triglycidyl isocyanurate with an acidic catalyst, which has an epoxy value of 02 equivalents/100f or more and a molecular weight of 400 to 15
00, and a thermosetting resin composition made by blending the epoxy resin with a curing agent that reacts with glycidyl groups. Triglycidyl isocyanurate is a trifunctional epoxy resin produced by reaction with incyanuric acid toebrohydrin, and the molecular weight of the pure product is 2.
97, is a white crystal with an epoxy value of 1.01 equivalent/1007, but it usually contains residual chlorohydrin groups and unreacted N H
Due to the influence of residual groups, etc., the epoxy value is 0.80-0.95 equivalent/1007, the melting point is 90-120°C, and the average molecular weight is 300-
It is commercially available as 350 white crystalline powder.
本発明に用いるトリグリシジルイノシアヌレ＝１・は、
勿論純品であってもよいが、不純物を含んでいても何ら
差し支えない。The triglycidyl inocyanuride used in the present invention = 1.
Of course, it may be a pure product, but there is no problem even if it contains impurities.
−」−記のトリグリシフルイノシアヌレ−１−を加熱溶
融させ、酸性触媒を加えるとグリシジル基同志が反応し
、ｌ−リグリシプルインシアヌレートをユニットとする
オリゴマーを生成し、更に反応を継続すると三次元化し
て固化する。本発明の新規なエポキシ樹脂は、上記のオ
リゴマ一段階において反応を中断することによって得ら
れる。When the triglycyfluinocyanurate-1- described in "-"- is melted by heating and an acidic catalyst is added, the glycidyl groups react with each other to produce an oligomer containing l-liglycyfluinocyanurate as a unit, and the reaction is continued. Then it becomes three-dimensional and solidifies. The novel epoxy resins of the present invention are obtained by interrupting the reaction at one stage of the oligomers described above.
本発明に用いられる酸性触媒としては、例えばフェノー
ル、クレゾール、キシレノール、ターシャリ−ブチルフ
ェノール、ハイドロキノン、カブコール、ヒスフェノー
ルＡ１ ビスフェノールＳ１パラオキシ安息香酸、メタ
オキシ安息香酸等のフェノール性化合物類、三弗化Ｊｌ
ｌｌｌ素、五弗化燐、五弗化砒素等の弗化物又は弗化物
の配位錯体類、アルキルベンゼンスルフオ、ン酸、トリ
フルオロメチルスルフォン酸、パラトルエンスルフォン
酸等のスルフォン酸類、塩化アルミ、塩化第２鉄、四塩
化チタン等の固体酸類、陽イオン交換樹脂等が用いられ
る。而して本発明のエポキシ樹脂を製造するには、反応
の中間段階において反応を停止」−シ触媒を除去する必
要があることから、触媒自体がトリグリシツルイソシア
ヌレートと反応し触媒活性を失うフェノール性化合物が
好適であシ、又固体酸や陽イオン交換樹脂の如くｆ過に
よって容易に除去出来る触媒も好適である。Examples of the acidic catalyst used in the present invention include phenolic compounds such as phenol, cresol, xylenol, tertiary-butylphenol, hydroquinone, cabucol, hisphenol A1, bisphenol S1, paraoxybenzoic acid, metaoxybenzoic acid, trifluoride Jl
Fluorides or coordination complexes of fluorides such as phosphorus pentafluoride, arsenic pentafluoride, sulfonic acids such as alkylbenzene sulfuric acid, trifluoromethylsulfonic acid, paratoluenesulfonic acid, aluminum chloride, Solid acids such as ferric chloride and titanium tetrachloride, cation exchange resins, etc. are used. Therefore, in order to produce the epoxy resin of the present invention, it is necessary to stop the reaction at an intermediate stage of the reaction and remove the catalyst. Suitable are chemical compounds, and catalysts that can be easily removed by filtration, such as solid acids and cation exchange resins, are also suitable.
フェノール性化合物類は、触媒除去の工程も不要なので
特に好めである。上記フェノール性化合物類の添加量は
、トリグリシジルイソシアヌレートのグリシジル基のモ
ル数に対しフェノール性ＯＨ基又はカルボキシル基（潜
在性カルボキシル基を含む）のモル数が０．０２〜０．
２５の比率、更には００５〜０．１５の比率であること
が安定に本発明のエポキシ価及び平均分子量を制御しか
つ貯蔵時に反応の進行がないよう制御する観点から望寸
しい。Phenolic compounds are particularly preferred because they do not require a catalyst removal step. The amount of the phenolic compounds added is such that the number of moles of phenolic OH groups or carboxyl groups (including latent carboxyl groups) is 0.02 to 0.02 to the number of moles of glycidyl groups in triglycidyl isocyanurate.
From the viewpoint of stably controlling the epoxy value and average molecular weight of the present invention and preventing the reaction from proceeding during storage, a ratio of 0.25 to 0.15 is desirable.
すなわちフェノール性ＯＨ基がグリ／ノル基同志の反応
の触媒として作用する一方、グリシジル基と反応して減
少し、触媒としての機能を消失する。That is, while the phenolic OH group acts as a catalyst for the reaction between glycidyl and nor groups, it is reduced by reacting with the glycidyl group and loses its catalytic function.
反応温度は、通常ｉｏｏ〜１８０℃が好捷しく、反応は
塊状でも、不活性な有機溶媒中であっても差し支えない
が、有機溶媒を用いない場合にばトリグリシジルイノシ
アヌレートの融点以上の温度で行うことが均一に反応を
進める上で好ましい。The preferred reaction temperature is usually ioo to 180°C, and the reaction can be carried out in bulk or in an inert organic solvent, but if no organic solvent is used, the reaction temperature is above the melting point of triglycidyl inocyanurate. It is preferable to carry out the reaction at a high temperature in order to proceed with the reaction uniformly.
又、グリシジル基とフェノール性ＯＨとの反応を促進さ
せる為に第６級アミン類等の助触媒を用いてもよい。Further, a co-catalyst such as 6th class amines may be used to promote the reaction between the glycidyl group and the phenolic OH.
本発明のエポキシ樹脂は、エポキシ価が０２当量／１０
０！ｉ’以上であることが必要であり、０２当量／１０
０Ｐ未満では耐熱性が低下するために不適当であり、特
に０６〜０７尚酎−／１００７であることが好ましい。The epoxy resin of the present invention has an epoxy value of 02 equivalents/10
0! i' or more is required, and 02 equivalents/10
If it is less than 0P, it is unsuitable because the heat resistance decreases, and 06 to 07 Shochu-/1007 is particularly preferable.
又、本発明のエポキシ樹脂の数平均分子湖は、４００〜
１５００であることが必要であり、１５００以上では、
溶融状態の粘度が高く又硬化剤を加えた際のゲルタイム
が短い為に、硬化剤配合時又は貯蔵時の可使時間が短く
、実用性が低下して好捷しくなく、一方４００未満では
多量のトリグリ／ジルイノシアヌレートが残存する為に
冷却時に結晶が析出し、繊維等に含浸した際に繊維表面
に結晶を析出し、不均質な状態となって好捷しくない。Further, the number average molecular lake of the epoxy resin of the present invention is 400 to
It must be 1500, and above 1500,
Because the viscosity in the molten state is high and the gel time is short when a hardening agent is added, the pot life is short when adding the hardening agent or during storage, reducing practicality and making it undesirable. Since triglyceride/dylinocyanurate remains, crystals precipitate during cooling, and when impregnated into fibers, crystals precipitate on the surface of the fibers, resulting in a non-uniform state, which is not favorable.
従って特に平均分子量は６００〜１０００が好ましい。Therefore, the average molecular weight is preferably 600 to 1000.
上記の新規なエポキシ樹脂は、実用に際し硬化剤を配合
し常温又は加熱して架橋せしめ絶縁耐相、接着剤、繊維
強化、複合材料のマトリックス材料等に用いられる。In practical use, the above-mentioned novel epoxy resin is mixed with a curing agent and cross-linked at room temperature or by heating, and is used for insulation-resistant phases, adhesives, fiber reinforcement, matrix materials for composite materials, and the like.
硬化剤は従来エポキシ樹脂の硬化剤として用いられてき
た各種の硬化剤のいずれも用いることが出来、例えば脂
肪族ポリアミン、芳香族ポリアミン、脂環族ポリアミン
等のポリアミン化合物及びポリアミンのアダクト類、酸
無水物類、ジシアンジアミド、グアニジン等のイミノ化
合物類、カルボン酸ジヒドラジド類、イミダゾール類、
多価フ・エノール類等が挙げられる。The curing agent can be any of the various curing agents conventionally used as curing agents for epoxy resins, such as polyamine compounds such as aliphatic polyamines, aromatic polyamines, and alicyclic polyamines, adducts of polyamines, and acids. Anhydrides, imino compounds such as dicyandiamide and guanidine, carboxylic acid dihydrazides, imidazoles,
Examples include polyhydric phenols and enols.
本発明の新規なエポキシ樹脂の特徴である耐熱性の向上
の観点からは、特に芳香族ポリサミン類、酸無水物類、
イミダゾール類等が好適であるが、他の硬化剤を用いて
も従来のエポキシ樹脂に較べ著しく高い耐熱性を付与す
ることが出来る。From the viewpoint of improving heat resistance, which is a feature of the novel epoxy resin of the present invention, aromatic polysamines, acid anhydrides,
Although imidazoles and the like are preferred, other curing agents can also be used to impart significantly higher heat resistance than conventional epoxy resins.
実用に際しては本発明のエポキシ樹脂及び硬イビ剤を有
機溶媒に溶解して用いても、エポキシ樹脂の溶融状態に
硬化剤を添加混合して用いても良い。In practical use, the epoxy resin and hardening agent of the present invention may be used by dissolving them in an organic solvent, or by adding and mixing a curing agent to the molten state of the epoxy resin.
又、他の一般に公知のエポキシ樹脂を本発明の目的を阻
害しない範囲において併用してもよい。Further, other generally known epoxy resins may be used in combination as long as they do not impede the object of the present invention.
実用に際しては、目的に応じレベリング剤、消泡剤、滑
剤、可塑剤等の助剤類や顔料、染料等の着色剤、例えば
ンリカ、タルク、炭酸力ルシーウ、マイカ、アルミナ、
炭化硅素、金属粉、ガラスセンイ、炭素センイ、ホイス
カー類等の充填剤を混合使用してもよい。In practical use, depending on the purpose, auxiliary agents such as leveling agents, antifoaming agents, lubricants, and plasticizers, and coloring agents such as pigments and dyes, such as alcoholic acid, talc, carbonic acid, mica, alumina,
Fillers such as silicon carbide, metal powder, glass fiber, carbon fiber, and whiskers may be used in combination.
上記の如く、本発明の新規なエポキシ樹脂は、硬化剤を
配合して得られる硬化物の耐熱性が著しくすぐれており
、又非晶質であることから成形−や含浸等の作業が容易
であった。As mentioned above, the novel epoxy resin of the present invention has extremely excellent heat resistance of the cured product obtained by adding a curing agent, and is amorphous, making it easy to perform operations such as molding and impregnation. there were.
以下実施例を示し本発明を具体的に説明する。The present invention will be specifically explained below with reference to Examples.
実施例１
粗トリグリシジルイソシアヌレート（エポキシ価０９６
当量／１００ｆｒ、融点１１０℃）ろ００７を、撹拌器
つき反応器に入れ、加熱溶融させ、１４０℃にて溶融し
たフェノール、１８Ｊ３Ｓ’を２時間に亘って滴下し更
に６時間加熱して本発明のエポキシ樹脂（１）を得た。Example 1 Crude triglycidyl isocyanurate (epoxy value 096
equivalent weight/100fr, melting point 110°C) filter 007 was placed in a reactor equipped with a stirrer, heated and melted, phenol 18J3S' melted at 140°C was added dropwise over 2 hours, and further heated for 6 hours to produce the present invention. Epoxy resin (1) was obtained.
エポキシ価は０５５当量／１０Ｑｆ数平均分子量（ＧＰ
Ｃ法にて測定）は７１０であった。The epoxy value is 055 equivalent/10Qf number average molecular weight (GP
(measured by method C) was 710.
実施例２
実施例１で用いた粗トリグリシジルインシアヌレート３
００グを同様に融解させ１６０℃に加熱しなから５４４
グのメタヒドロキシ安息香酸を５分割し２０分毎に添加
し、更に２時間１６０℃にて加熱混合し、本発明のエポ
キシ樹脂（２）を得た。エポキシ価は０．２８当量／１
００グ、数平均分子量は９６０であった。Example 2 Crude triglycidyl in cyanurate 3 used in Example 1
544 by melting 00g in the same way and heating it to 160℃.
The metahydroxybenzoic acid was added in 5 portions every 20 minutes, and the mixture was further heated and mixed at 160° C. for 2 hours to obtain an epoxy resin (2) of the present invention. Epoxy value is 0.28 equivalent/1
The number average molecular weight was 960.
実施例６
実施例１で用いた粗トリグリシジルイソシアヌレ−）
３００ Ｆに７００２のジメチルホルムアミドを加え、
１２０℃にて溶解した後、６７の塩化第２鉄粉末を加え
、１２０℃にて２時間加熱混合し加熱溶液を力〜トリノ
ジ型フィルターにてｔ過し、塩化第２鉄粉末を除去した
後、エバポレータ〜に沢液を移し、１２０℃で加熱しな
からジメチルホルムアミドを蒸発除去して本発明のエポ
キシ樹脂（ロ）を得た。このエポキシ価は０５５当！／
１ｏｏｒ、数平均分子量は５８０であった。Example 6 Crude triglycidyl isocyanurate used in Example 1)
Add 7002 dimethylformamide to 300F,
After melting at 120°C, add ferric chloride powder of No. 67, heat and mix at 120°C for 2 hours, and pass the heated solution through a Torinoji type filter to remove the ferric chloride powder. The sludge was transferred to an evaporator and heated at 120°C to remove dimethylformamide by evaporation to obtain an epoxy resin (b) of the present invention. This epoxy value is 055! /
1 oor, and the number average molecular weight was 580.
実施例４
実施例１で用いた粗トリグリシジルイソシアヌレートを
メタノールで再結晶し純度の高いトリグリシジルインシ
アヌレートを得た。そのエポキシ価は１．０当量／１０
０７、融点は１４８℃であった。Example 4 The crude triglycidyl isocyanurate used in Example 1 was recrystallized from methanol to obtain highly pure triglycidyl in cyanurate. Its epoxy value is 1.0 equivalent/10
07, the melting point was 148°C.
上記の高純度トリグリシジルイソシアヌレート３００１
にジメチルホルムアミド７００２を加え１２０℃で溶解
した後、ビスフェノールＡ ２２Ｂ Ｙを加え、１２０
℃で５時間加熱混合した後、エバポレーターにてジメチ
ルホルムアミドを蒸発除去して本発明のエポキシ樹脂（
４）を得た。エポキシ価は０．５２当量／１００７、数
平均分子量は８８０であった。The above high purity triglycidyl isocyanurate 3001
Add dimethylformamide 7002 to the solution and dissolve at 120°C, then add bisphenol A 22B Y to 120°C.
After heating and mixing at ℃ for 5 hours, dimethylformamide was removed by evaporation using an evaporator to obtain the epoxy resin of the present invention (
4) was obtained. The epoxy value was 0.52 equivalent/1007, and the number average molecular weight was 880.
比較例１
実施例１に用いた粗トリグリシジルイソシアヌレ〜）
３００ ｆｌを実施例１と同様にして溶融し、１４０℃
にて６．１７の溶融したフェノールを２時間に亘って滴
下し更に５時間加熱した。このエポキシ樹脂（５）のエ
ポキシ価は０ｊ３５当量／１［］ＯＳ’、数平均分子量
は６８０であった。Comparative Example 1 Crude triglycidyl isocyanuride used in Example 1
300 fl was melted in the same manner as in Example 1 and heated to 140°C.
6.17 of molten phenol was added dropwise over 2 hours, and the mixture was further heated for 5 hours. This epoxy resin (5) had an epoxy value of 0j35 equivalent/1[]OS' and a number average molecular weight of 680.
比較例２
実施例１に用いた粗トリグリシジルイソシアヌレ−）
３００ ｆを実施例１と同様にして溶融し、１４０℃に
て９４１の溶融したフェノールを２時間に亘って滴下し
更に１時間加熱した時点で１部を抜きだした。このエポ
キシ樹脂（６）のエポキシ価はＯ１６当用／′１ｏｏｙ
、数平均分子量は１８００であった。Comparative Example 2 Crude triglycidyl isocyanuride used in Example 1)
300 f was melted in the same manner as in Example 1, molten phenol of 941 was added dropwise at 140° C. over 2 hours, and after further heating for 1 hour, 1 part was taken out. The epoxy value of this epoxy resin (6) is O16/'1ooy
, the number average molecular weight was 1800.
更に残余の部分を１４０℃で加熱混合し／こところ４０
分後にゲル化１〜だ。Furthermore, heat and mix the remaining portion at 140℃/Kotokoro 40
After a few minutes, it becomes gelatinous.
実施例５
実施例（１）〜（４）において製造した各エポキシ樹脂
（１）〜（４）を表１に記載する硬化剤と表１記載の重
量割合で配合し、表面温度８０℃に設定したホノ）・ロ
ールで練合し、プレスを用いてソート化した。Example 5 Each of the epoxy resins (1) to (4) produced in Examples (1) to (4) was blended with the curing agent listed in Table 1 at the weight ratio listed in Table 1, and the surface temperature was set at 80°C. The mixture was kneaded using a hono roll and sorted using a press.
プレス圧ば１ Ｄｏ Ｋｇ ／ ｃｎｆて、１５０℃、
６０分間保持し、その後１８０°Ｃに２ｎＳ間保って後
加熱して試験１’＋をえ、その試験片を用いて、Ｔ Ｍ
Ａ法でガラス転移点を測定し、表１に併せで記載した
。Press pressure 1 Do Kg/cnf, 150℃,
It was held for 60 minutes, then heated at 180°C for 2 nS to obtain test 1'+, and using that test piece, T M
The glass transition points were measured using Method A and are also listed in Table 1.
又、表１記載の各エポキシ樹脂及び硬化剤を／メチルホ
ルムアミドに２０係になるように含浸し、炭素繊維ロー
ビングに含浸した後真空で乾燥し、樹脂含浸炭素繊維を
１００℃に加熱したトラムに甘きつけ、冷却離型して一
方向性プリプレグを製造し、」二記条件にてプレスして
１．一方向性炭素繊組−強化／−トを製造した。各温度
における曲げ強さ及び層間せん断強さを測定した。結果
は表１に併せて記載する。尚、上言己炭素繊維強化ソー
トの炭素繊維含有量は６０±２容債％の範囲にあった。In addition, each epoxy resin and curing agent listed in Table 1 was impregnated in /methylformamide to a ratio of 20%, impregnated into a carbon fiber roving, dried in a vacuum, and the resin-impregnated carbon fiber was placed in a tram heated to 100°C. A unidirectional prepreg is produced by sweetening, cooling and releasing the mold, and pressing under the conditions described in 1. A unidirectional carbon fiber composite-reinforced/-t was manufactured. The bending strength and interlaminar shear strength at each temperature were measured. The results are also listed in Table 1. Incidentally, the carbon fiber content of the carbon fiber reinforced sort was in the range of 60±2%.
比較例ろ
比較例１及び２に記載したエポキシ樹脂（５）及び（６
）、更に一般的エポキシ樹脂であるビスフェノールＡ型
エボギシ樹脂（油化ンエルエボキシ社製、商品名工ピコ
−１−８３４）を表１記載の割合で硬化剤と配合し、実
施例５と全く同様にして各々のプレスンート及び一方向
性炭素繊組１強化ンーｉ・の試験片を作成することを試
みた。エポキシ樹脂（５）を用いたものは、ホソｈａ−
ル混合後冷却時に結晶の析出１）福忍められ、混合物の
均一性が外観からみて不良であった。又炭素センイロー
ビングに含浸し乾燥した段階で、炭素繊維表面に結晶が
１７４着した状態がみられ、ロービングのドラムへの゛
まきつけの際、一部脱離を生じた。Comparative Example Epoxy resins (5) and (6) described in Comparative Examples 1 and 2
), and a general epoxy resin, bisphenol A type epoxy resin (manufactured by Yuka NEL Eboxy Co., Ltd., trade name: Pico-1-834), was mixed with a curing agent in the proportions shown in Table 1, and the process was carried out in exactly the same manner as in Example 5. An attempt was made to create test pieces of each presunto and unidirectional carbon fiber 1-i reinforcement. The one using epoxy resin (5) is Hosoha-
1) Precipitation of crystals was observed during cooling after mixing, and the uniformity of the mixture was poor in appearance. In addition, when the carbon fiber roving was impregnated and dried, 174 crystals were observed to be attached to the surface of the carbon fiber, and some of the crystals were detached when the roving was wrapped around the drum.
又、エポキシ樹脂（６）を用いたものは、ホットロール
混合中に半ゲル化状態になり、プレス時のフローが不完
全であった。In addition, the product using epoxy resin (6) became semi-gelled during hot roll mixing, and the flow during pressing was incomplete.
しかし、いずれも試験片を作成し、実施例５と同様な評
価を行い、その結果を併せて表１に記載した。However, test pieces were prepared in each case and evaluated in the same manner as in Example 5, and the results are also listed in Table 1.
尚、上記比較例の炭素繊維強化ソートの炭素繊維含有量
Ｓはいずれも６ｏ±２容積係の範囲にあった。Incidentally, the carbon fiber content S of the carbon fiber-reinforced sorts of the above-mentioned comparative examples were all in the range of 6o±2 volume ratio.
Claims (2)
加えてオリゴマー化して得られるエポキシ価０２当量７
１ｏｏｙ以上で且つ平均分子量が４００〜１５００であ
る新規なエポキシ樹脂。(1) Epoxy value obtained by adding an acidic catalyst to oligomerize trigly/dylycine cyanurate and having an epoxy value of 02 and an equivalent of 7
A novel epoxy resin having an average molecular weight of 1 oooy or more and an average molecular weight of 400 to 1,500.
えてオリゴマー化して得られるエポキシ価０２当量／１
００７以上で且つ平均分子量が４００〜１５００である
エポキシ樹脂にグリシジル基と反応する硬化剤を配合し
てなる熱硬化性樹脂組成物。(2) Epoxy value obtained by adding an acidic catalyst to triglycidyl isocyanurate and oligomerizing it, with an epoxy value of 02 equivalents/1
A thermosetting resin composition comprising an epoxy resin having a molecular weight of 007 or more and an average molecular weight of 400 to 1,500 and a curing agent that reacts with glycidyl groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58126935A JPH0643483B2 (en) | 1983-07-14 | 1983-07-14 | Novel epoxy resin and composition thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58126935A JPH0643483B2 (en) | 1983-07-14 | 1983-07-14 | Novel epoxy resin and composition thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6020925A true JPS6020925A (en) | 1985-02-02 |
| JPH0643483B2 JPH0643483B2 (en) | 1994-06-08 |
Family
ID=14947539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58126935A Expired - Lifetime JPH0643483B2 (en) | 1983-07-14 | 1983-07-14 | Novel epoxy resin and composition thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643483B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250826A (en) * | 2020-11-05 | 2021-01-22 | 南京大学 | Dai serge production wastewater recycling treatment method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54107882A (en) * | 1978-02-13 | 1979-08-24 | Toray Ind Inc | Semipermeable membrane |
-
1983
- 1983-07-14 JP JP58126935A patent/JPH0643483B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54107882A (en) * | 1978-02-13 | 1979-08-24 | Toray Ind Inc | Semipermeable membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250826A (en) * | 2020-11-05 | 2021-01-22 | 南京大学 | Dai serge production wastewater recycling treatment method |
| CN112250826B (en) * | 2020-11-05 | 2021-10-26 | 南京大学 | Dai serge production wastewater recycling treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0643483B2 (en) | 1994-06-08 |
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