JPS60202116A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPS60202116A JPS60202116A JP5833884A JP5833884A JPS60202116A JP S60202116 A JPS60202116 A JP S60202116A JP 5833884 A JP5833884 A JP 5833884A JP 5833884 A JP5833884 A JP 5833884A JP S60202116 A JPS60202116 A JP S60202116A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- parts
- compound
- formula
- 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.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 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 claims abstract description 12
- -1 urea compound Chemical class 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 8
- 229920003986 novolac Polymers 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 230000002787 reinforcement Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 7
- 239000004917 carbon fiber Substances 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000012783 reinforcing fiber Substances 0.000 abstract description 5
- 238000005452 bending Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004843 novolac epoxy resin Substances 0.000 abstract description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- 238000000465 moulding Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 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 5
- 229920003319 Araldite® Polymers 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 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
- 150000003672 ureas Chemical class 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- ALEBYBVYXQTORU-UHFFFAOYSA-N 6-hydrazinyl-6-oxohexanoic acid Chemical compound NNC(=O)CCCCC(O)=O ALEBYBVYXQTORU-UHFFFAOYSA-N 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
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は低温速硬化性を有し、しかも貯蔵安定性に優れ
るプリプレグ用−液性エボギシ樹脂組成物に関Ｊるもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid epoxy resin composition for prepregs, which has quick curing properties at low temperatures and excellent storage stability.
近年、ゴルフシャフトや釣竿等のスポーツ用品に炭素繊
維を中心とする繊維強化複合材料が広く使用されている
。In recent years, fiber-reinforced composite materials mainly made of carbon fibers have been widely used in sports equipment such as golf shafts and fishing rods.
これら複合月利はプリプレグを成形して製造される場合
が多いが、プリプレグに使用されるマトリックス樹脂と
しては、機械的強度向上の点から、エポキシ樹脂が主と
して使用されている。These composite monthly products are often manufactured by molding prepregs, and epoxy resins are mainly used as matrix resins for prepregs from the viewpoint of improving mechanical strength.
従来よりプリプレグ用エポキシ樹脂組成物として、硬化
剤にジシアンジアミドを用い、且つ硬化促進剤にジクロ
ロフェニル−１，−１ジメチル尿素等の尿素誘導体を用
いることが公知である。It has been conventionally known to use dicyandiamide as a curing agent and a urea derivative such as dichlorophenyl-1,-1 dimethylurea as a curing accelerator in epoxy resin compositions for prepregs.
このものはシェルライフが室温で１力月以上あり且つ、
１３０℃で硬化可能で、現在一般的に使われている。This product has a shell life of more than 1 month at room temperature, and
It can be cured at 130°C and is commonly used today.
一方、炭素繊維のような熱収縮率の小さい繊維で強化す
る場合、成形温痩が高ければ高いほど成形物中の残留応
力が大きくなりクラック発生等の問題が起こる。このよ
うな問題を解消し、加えて省エネルギー、作業効率を高
める立場から、最近ではより低温で完全硬化可能で、且
つ長いシェルライフを有する一液性エボキシ樹脂組成物
の出現が望まれていた。On the other hand, when reinforcing fibers with a low thermal shrinkage rate such as carbon fibers, the higher the molding temperature, the greater the residual stress in the molded product, causing problems such as cracking. In order to solve these problems and to improve energy saving and work efficiency, there has recently been a desire for a one-component epoxy resin composition that can be completely cured at lower temperatures and has a long shell life.
しかるにａｉで硬化性の高い硬化剤、例えば２−エチル
−４−メチルイミダゾール等のイミダゾール化合物やポ
リアミン類を使用した場合、反応性が高いゆえに長時間
の保存が困汁どなる。However, when a curing agent with high curing properties is used, such as imidazole compounds such as 2-ethyl-4-methylimidazole or polyamines, long-term storage becomes difficult due to high reactivity.
本発明者らは、これらの事情を踏まえ、長期保存性に優
れ、且つ１００℃以下で低温速硬化性を有し、しかも炭
素繊維との組合せにおいて優れたコンポジット物性を提
供Ｊるプリプレグ用エポキシ樹脂組成物について検討し
た結果、本発明に到達した。In view of these circumstances, the present inventors have developed an epoxy resin for prepregs that has excellent long-term storage stability, fast curing at low temperatures below 100°C, and provides excellent composite physical properties when combined with carbon fibers. As a result of studying the composition, we have arrived at the present invention.
すなわち、本発明は
（Ａ）エポキシ樹脂
＜、Ｂ）融点１６０℃以下のヒドラジド化合物（Ｃ）下
式で示される尿素化合物
（但、ＸＳＹは同−又は異なりで、１−１、ＣＱ、０Ｃ
Ｈ１を表わす）
を含むことを特徴とするエポキシ樹脂組成物である。That is, the present invention provides (A) an epoxy resin <, B) a hydrazide compound with a melting point of 160°C or less, (C) a urea compound represented by the following formula (where XSY is the same or different, and 1-1, CQ, 0C
H1) is an epoxy resin composition characterized by containing the following.
更に上記エポキシ樹脂組成物に強化材！Ｉ雑を含むエポ
キシ樹脂組成物である。Furthermore, a reinforcing material is added to the above epoxy resin composition! This is an epoxy resin composition containing I.
本組成物を用いることにより、１００℃以下、２時間で
完全硬化可能であり、且つ室温で２１間以上保存するこ
とが可能である。By using this composition, it can be completely cured in 2 hours at 100° C. or lower, and can be stored at room temperature for 21 hours or more.
本発明において用いられるエポキシ樹脂はその種類に制
限がなく、ビスフェノールＡ型エポキシ樹脂、フェノー
ルノボラック型エポキシ樹脂、タレゾールノボラック型
エポキシ樹脂、グリシジルアミン型エポキシ樹脂、脂環
式エポキシ樹脂、ウレタン変性エポキシ樹脂、臭素化ご
スフ１ノールΔ型エポキシ樹脂等である。The types of epoxy resins used in the present invention are not limited, and include bisphenol A epoxy resins, phenol novolac epoxy resins, Talesol novolak epoxy resins, glycidylamine epoxy resins, alicyclic epoxy resins, and urethane-modified epoxy resins. , brominated sulfur 1-nol Δ type epoxy resin, etc.
コンポジット特性、特に層間剪断強度及び曲げ強度の観
点から、ノボラック型エポキシ樹脂若しくはビスフェノ
ールＡ型エポキシ樹脂又はこれらの合泪母が、全エポキ
シ樹脂１００重石部に対し、５０重量部以上であること
が望ましい。From the viewpoint of composite properties, especially interlaminar shear strength and bending strength, it is desirable that the amount of novolac type epoxy resin, bisphenol A type epoxy resin, or a combination thereof is 50 parts by weight or more based on 100 parts by weight of the total epoxy resin. .
ノボラック型エポキシ樹脂のうら、ノ１ノールノボラッ
ク型エボシ樹脂としては、具体的には例えばエピコート
１５２．１ビコート １５４、（シェル化学社製）、
アラルダイトＥ Ｐ Ｎ １１３８、Ｅ Ｐ Ｎ １１
３９ （チバ・ガイキー社製）ダウエポキシＤＥＮ４３
１、ＤＥＮ４３８、ＤＥＮ４３９、ＸＤ７８５５ （ダ
ウケミカル社＠） 、ＥＰＰＮ ２０１（日本化薬社製
）、エビクロンＮ７４０（大日木インキ化学工業社製）
等が挙げられる。 クレゾールノボラック型エポキシ樹
脂としては、チバガイギーＥ ＣＮ １２３５、Ｅ Ｃ
Ｎ １２７３、Ｅ ＣＮ １２８０、Ｅ ＣＮ １２９
９ （ヂバ・ガイキー社製） 、ＥＯＣＮ１０２、ＥＯ
ＣＮ１０３、ＥＯＣＮ １０４（日本化薬社製）などが
ある。Specifically, examples of the novolac type epoxy resin include Epicoat 152.1 Bicoat 154 (manufactured by Shell Chemical Co., Ltd.),
Araldite E P N 1138, E P N 11
39 (manufactured by Ciba Geikie) Dowepoxy DEN43
1,DEN438, DEN439,
etc. As cresol novolak type epoxy resin, Ciba Geigy E CN 1235, E C
N 1273, E CN 1280, E CN 129
9 (manufactured by Jiba Geikie), EOCN102, EO
Examples include CN103 and EOCN 104 (manufactured by Nippon Kayaku Co., Ltd.).
ビスフェノールＡ型エポキシ樹脂としては、エピコート
８２８、エピコート８１５、エピコート８３４、エピコ
ート１００１、エピコート１００２ （シェル化学社製
）等が挙げられる。Examples of bisphenol A epoxy resins include Epicote 828, Epicote 815, Epicote 834, Epicote 1001, and Epicote 1002 (manufactured by Shell Chemical Co., Ltd.).
（Ｂ）成分の融点１６０℃以下のヒドラジド化合物は、
硬化剤であって具体的には次式で示される各種ヒドラジ
ド化合物である。The hydrazide compound having a melting point of 160°C or lower as component (B) is
The curing agent is specifically a variety of hydrazide compounds represented by the following formulas.
融点：１３８〜１４０℃
（但し、Ｘはフェニレン基
又は
Ｏ
融点：１４２〜１４３℃
ＣＨ３５ＣＨ２ＣＨ２ＣＨ−Ｃ＝０
１
Ｑ ＣＲＯ
１
融点＝１５０〜１５１℃
（但し、Ｒ１，ｔＨ，ＣＨｓを示寸）
１
融点：１２３〜１２５℃
融点：１４６°Ｃ
（ＮＨ２ＮＨＣＣ’Ｈｅ ＣＨ２’）２ Ｎ （ＣＨ２
）１２ Ｎ（ＣＨ２ＣＨ２ＣＮＩ州Ｈ２）、 “〔■〕
ＩＩ ＩＩ
ｏ ０
融点＝１２９℃
ＮＨ２ＮＨＣＣＨ２ＣＮＨＮＨ２［■］１１１
０
融点：１５２〜１５４℃
エポキシ樹脂の硬化剤として融点１６０℃超のヒドラジ
ド化合物、例えばアジピン酸ジヒドラジド、セパチン酸
ジヒドラジド、イソフタル酸ジヒドラジド等を使用する
場合は硬化に１５０℃以上の高温を必要とし好ましくな
い。Melting point: 138-140°C (However, X is a phenylene group or O Melting point: 142-143°C CH35CH2CH2CH-C=0 1 Q CRO 1 Melting point = 150-151°C (However, R1, tH, CHs are indicated) 1 Melting point :123~125℃ Melting point: 146℃ (NH2NHCC'He CH2')2N (CH2
)12 N (CH2CH2CNI state H2), “[■]
II II o 0 Melting point = 129°C NH2NHCCH2CNHNH2 [■] 111 0 Melting point: 152-154°C A hydrazide compound with a melting point of over 160°C, such as adipic acid dihydrazide, sepatic acid dihydrazide, isophthalic acid dihydrazide, etc., is used as a curing agent for epoxy resin. In this case, curing requires a high temperature of 150° C. or higher, which is not preferable.
融点１６０℃以下のヒドラジド化合物と（Ｃ）成分であ
る下式の尿素化合物
〈但、ｘ、ｙは同−又は異なりてＨｌＣＱ。A hydrazide compound with a melting point of 160° C. or lower and a urea compound of the following formula as component (C), where x and y are the same or different and are HlCQ.
ＯＣ＋−１３を表わす）
例えば３ （３，４−ジクロロフェニル） −ｉ、ｉ−
ジメチルＩＩ’Ｓ、３−１〕−クロロフェニル−１，１
−ジメチル尿素、３−Ｐ−メトキシフェニル−１，１−
ジメチル尿素等を併用した場合において初めて １００
℃以下、２時間でエポキシ樹脂を完全硬化さＶることが
可能になった。融点１６０℃超のヒドラジド化合物と（
Ｃ）成分のｇ１用では、そのような低温速硬化性を示さ
ない。OC+-13) For example, 3 (3,4-dichlorophenyl) -i, i-
Dimethyl II'S, 3-1]-chlorophenyl-1,1
-dimethylurea, 3-P-methoxyphenyl-1,1-
For the first time when using dimethylurea etc. 100
It became possible to completely cure the epoxy resin in 2 hours at temperatures below 0.5°C. A hydrazide compound with a melting point of over 160℃ and (
Component C) for g1 does not exhibit such low-temperature rapid curing properties.
本発明樹脂組成物において硬化剤である（ Ｂ ”）成
分は全エポキシ樹脂１００重用部に対し通常５〜８０重
量部、特に好ましくは１０〜５０重量部含イラさせる。In the resin composition of the present invention, component (B''), which is a curing agent, is usually 5 to 80 parts by weight, particularly preferably 10 to 50 parts by weight, based on 100 parts by weight of the total epoxy resin.
含有（３）が５部より少ないと完全硬化が不可能となり
、逆に８０部より多くなると成形物の耐熱性及び耐水性
が低下覆る。If the content (3) is less than 5 parts, complete curing will not be possible, whereas if it is more than 80 parts, the heat resistance and water resistance of the molded product will deteriorate.
硬化促進剤である（Ｃ）成分は、０．１〜２０重量部、
特に好ましくは１〜１０重石部含有させる。Component (C), which is a curing accelerator, contains 0.1 to 20 parts by weight,
Particularly preferably, the content is 1 to 10 parts.
（Ｃ）成分が０．１部より少ないとヒドラジド化合物の
促進効果が顕著に現われず、逆に２０用吊部以上含有さ
せると成形物の耐水性が低下する等好ましくない性質を
示す。If the amount of component (C) is less than 0.1 part, the promoting effect of the hydrazide compound will not be noticeable; on the other hand, if it is contained in excess of 20 parts, undesirable properties such as decreased water resistance of the molded product will be exhibited.
本発明エポキシ樹脂組成物にあっては、硬化剤成分とし
て（＋３ ）成分と（Ｃ）成分を（７１用りるため、得
られる複合材料は物性及び成形操作性に優れている。即
ち、（Ｂ）成分と（Ｃ）成分を併用することにより９０
〜１００℃、２時間あるいは１３０℃、３０分で完全硬
化μしめることか可能であるため、成形操作を単純化し
て生産性の向上を達成することができる。また成形して
得られた複合材料はボイドが無く、且つ残留応ツノの影
響が少ないため高品質のものである。In the epoxy resin composition of the present invention, the (+3) component and (C) component (71) are used as curing agent components, so the resulting composite material has excellent physical properties and molding operability. By using component B) and component (C) together, 90
Since it is possible to completely cure the resin in ~100°C for 2 hours or 130°C for 30 minutes, the molding operation can be simplified and productivity can be improved. Furthermore, the composite material obtained by molding is of high quality because it has no voids and is less affected by residual stress.
本発明樹脂組成物には、他の成分として無機充填剤、例
えばシリカ微粉末、マイクロバルーン等あるいは難燃剤
三酸化アンチモン等を加えても良い。その他可撓性を与
えるためニトリルゴム例えばカルボキシル基変性ニトリ
ルゴム等の使用もかまわない。また硬化剤系として、ジ
シアンジアミド、ポリアミド類、イミダゾール化合物、
ジアミノジフェニルス・ルホン等の併用も可能である。Inorganic fillers such as fine silica powder, microballoons, flame retardant antimony trioxide, etc. may be added to the resin composition of the present invention as other components. In addition, nitrile rubber such as carboxyl group-modified nitrile rubber may be used to provide flexibility. In addition, as curing agent systems, dicyandiamide, polyamides, imidazole compounds,
It is also possible to use diaminodiphenyls, sulfon, etc. in combination.
強化繊維としては炭素繊維、ガラス繊維、有ａｍ維、炭
化ケイ素繊維、アルミナｗ４維、金属ｔＩＡ維等がある
。強化繊維に対づる樹脂組成物の割合は、１．０〜１０
０重惧パーセントであり、強化繊維の形態はミルドファ
イバー、チョツプドファイバー、一方向長繊維状、織物
状等である。Examples of reinforcing fibers include carbon fibers, glass fibers, am fibers, silicon carbide fibers, alumina W4 fibers, and metal TIA fibers. The ratio of the resin composition to the reinforcing fibers is 1.0 to 10
The reinforcing fibers are in the form of milled fibers, chopped fibers, unidirectional long fibers, textiles, etc.
以下、本発明の実施例を比較例と共に示す。Examples of the present invention will be shown below along with comparative examples.
実施例１
アラルダイトＥＰＮ１１３８（チバ・ガイイー社製フェ
ノールノボラック型エポキシ樹脂） ７０重同郡、エピ
コート１００１ （シェル化学社製ビスフェノールＡ型
エボ′キシ樹脂）３０重量部にビスフェノールＡ型ジヒ
ドラジド（前底〔Ｉ〕、味の素社製）２０部及び各種尿
素化合物を第１表に示す量で加え、三本ロールに３回通
し均一な組成物を得た。このものについて１００℃での
硬化性（ゲルタイム）及び３０℃での貯蔵安定性を検討
した。結果を第１表に示す。Example 1 70 parts by weight of Araldite EPN1138 (phenol novolac type epoxy resin manufactured by Ciba Gaie Co., Ltd.), 30 parts by weight of Epicote 1001 (bisphenol A type epoxy resin manufactured by Shell Chemical Co., Ltd.) and bisphenol A type dihydrazide (front bottom [I ], manufactured by Ajinomoto Co., Inc.) and various urea compounds in the amounts shown in Table 1 were added, and the mixture was passed through a triple roll three times to obtain a uniform composition. Curing properties (gel time) at 100°C and storage stability at 30°C were investigated for this product. The results are shown in Table 1.
実施例２
アラルダイトＥＰＮ１１３８（ヂバ・ガイギー社製、フ
ェノールノボラック型エポキシ樹脂）７０重開部、エピ
コート１００１ （シェル化学社製、ビスフノールＡ型
エポキシ樹脂）３０重缶部、３〈３，４−ジクロロフェ
ニル） −ｉ、ｉ−ジメチル尿素５型聞部及び第２表に
示す各種ヒドラジド化合物を表示する聞で加えて樹脂組
成物を得た。このものについて１００℃での硬化性を検
討した。Example 2 Araldite EPN1138 (manufactured by Ziba Geigy, phenol novolak type epoxy resin) 70 double openings, Epicoat 1001 (manufactured by Shell Chemical Co., Ltd., bisphnol A type epoxy resin) 30 double can parts, 3<3,4-dichlorophenyl ) -i, i-dimethylurea type 5 part and various hydrazide compounds shown in Table 2 were added in the indicated parts to obtain a resin composition. The curability of this product at 100°C was investigated.
結果を第２表に示す。The results are shown in Table 2.
実施例３
アラルダイトＥＰＮ１１３８（チバ・ガイギー社製、フ
ェノールノボラック型エポキシ樹脂）１０重量部、１ビ
コート１００１ （シェル化学社製、ビスフェノールＡ
型エポキシ樹脂）３０ｍ１部に対し、前底（Ｉ）のヒド
ラジド化合物２０部及び３（３，４−ジクロロフェニル
） −１，１−ジメチル尿素５部を加えて樹脂組成物を
得Ｉこ。Example 3 10 parts by weight of Araldite EPN1138 (manufactured by Ciba Geigy, phenol novolak type epoxy resin), 1 part by weight of Bicoat 1001 (manufactured by Shell Chemical Co., Ltd., bisphenol A)
A resin composition was obtained by adding 20 parts of the hydrazide compound of front bottom (I) and 5 parts of 3(3,4-dichlorophenyl)-1,1-dimethylurea to 1 part of 30 ml of epoxy resin.
この樹脂組成物を塩化メチレン／メタノール混合溶媒系
に溶解させ樹脂液とした。This resin composition was dissolved in a methylene chloride/methanol mixed solvent system to obtain a resin liquid.
次に炭素繊維（東邦ベス１］ン社製ベスファイト■）を
１５０（］／ＩＩＩ・の目付になるように一方向に引揃
えた後、前記樹脂液を含浸後乾燥させて、樹脂含有率３
７ｍｆｉ％の一方向ブリブレグを得た。Next, carbon fibers (Besphite ■ manufactured by Toho Betheskin Co., Ltd.) were aligned in one direction to have a basis weight of 150(]/III·, and then impregnated with the resin liquid and dried to reduce the resin content. 3
A unidirectional blob leg with 7 mfi% was obtained.
このプリプレグを２０枚積層し、第３表に示す条件でホ
ットプレス成形を行った。この成形板より試験片を切り
出し、層間剪断強度（ＩＬＳＳ）及び曲げ強度の測定を
行った。結果を第３表に示す。Twenty sheets of this prepreg were laminated and hot press molded under the conditions shown in Table 3. A test piece was cut out from this molded plate, and the interlaminar shear strength (ILSS) and bending strength were measured. The results are shown in Table 3.
比較例１
実施例３の前底（Ｉ）ヒドラジド化合物２０部の代わり
に融点１８０℃のアジピン酸ヒドラジドを２０部用いる
他は全〈実施例３と同じ手法でプリプレグを得た。実施
例３と同条件でホラ（ヘブレス成形を行い、機械的強度
の測定を行った。Comparative Example 1 A prepreg was obtained in the same manner as in Example 3, except that 20 parts of adipic acid hydrazide having a melting point of 180° C. was used instead of 20 parts of the front bottom (I) hydrazide compound of Example 3. Molding was performed under the same conditions as in Example 3, and the mechanical strength was measured.
結果をＩ′ｇ３表に示す。The results are shown in Table I'g3.
比較例２
実施例３の曲成〔Ｉ゛〕ヒドラジド化合物２０部の代わ
りにジシアンジアミド３部を用いる他は実施例３と同一
条件でプリプレグ化、成形を行い、機械的強度の測定を
行った。結果を第３表に示す。Comparative Example 2 Prepreg formation and molding were carried out under the same conditions as in Example 3, except that 3 parts of dicyandiamide was used in place of 20 parts of the curved [I゛]hydrazide compound of Example 3, and the mechanical strength was measured. The results are shown in Table 3.
実施例４
実施例３と同一条件でプリプレグ化を行い、１００℃、
２時間の硬化条件でホットプレス成形を行った成形板よ
り試験片を切り出し、８０℃でのＩ １８８及び吸水率
の測定を打つｌＣ０実施例５〜１０及び比較例３〜７
エポキシ樹脂組成物の組成を変えて、実施例４と同一条
件でプリプレグ化、成形を行い、８０℃での■ＬＳＳ及
び吸水率の測定を行った。結果を第４表、第５表に示す
。同時に比較例についても示す。Example 4 Prepreg formation was carried out under the same conditions as in Example 3, at 100°C,
A test piece was cut out from a molded plate hot-press molded under 2-hour curing conditions, and the I188 and water absorption at 80°C were measured.1C0 Examples 5 to 10 and Comparative Examples 3 to 7 of the epoxy resin composition. Prepreg formation and molding were carried out under the same conditions as in Example 4, with the composition changed, and the LSS and water absorption at 80°C were measured. The results are shown in Tables 4 and 5. At the same time, comparative examples are also shown.
手続補正内
昭和５９年５月２８日
特許庁長官 殿
１、事件の表示
昭和５９年特許願第５８３３８号
２、発明の名称
エポキシ樹脂組成物
３、補正をする者 〒１０．３
事件との関係 特許出願人
居 所 東京都中央区日本橋三丁［１３番９号名 称
東邦ベスロン株式会社
代表者鐘江啓蔵
４、代理人 〒１０５
住 所 東京都港区西新橋１丁目１０番８号５、補正命
令の日４＝Ｊ 自発補正
６．７１ｉ正の対象 明細書の発明の詳細な説明の欄７
、補正の内容 別紙のとおり
（１）明ｍ書第１２頁７行を次の如く訂正する。Procedural amendment May 28, 1980 Director General of the Patent Office 1. Indication of the case Patent Application No. 58338 of 1983 2. Name of the invention Epoxy resin composition 3. Person making the amendment 10.3 Relationship to the case Patent Applicant Residence: Nihonbashi 3-chome, Chuo-ku, Tokyo [No. 13-9 Name]
Toho Bethlon Co., Ltd. Representative Keizo Kanee 4, Agent 105 Address 1-10-8-5 Nishi-Shinbashi, Minato-ku, Tokyo Date of amendment order 4 = J Voluntary amendment 6.71i Subject of correction Statement of Column 7 for detailed description of the invention
, Contents of the amendment As shown in the attached sheet, (1) Line 7 of page 12 of the Memorandum of Understanding is corrected as follows.
「す量で加え、更に溶剤として塩化メチレン３０１ ｆ
ｉ１部を加えた後、三本ロールに３回通した。次いで減
圧下で溶剤を除去し均一な組成」
以上Add 301 f of methylene chloride as a solvent.
After adding 1 part i, it was passed through a triple roll three times. Then, remove the solvent under reduced pressure to obtain a uniform composition.''
Claims (1)
組成物。 （Ａ＞エポキシ樹脂 （Ｂ）１点１６０℃以下のヒドラジド化合物（Ｃ）下式
で示される尿素化合物 （但、Ｘ、Ｙは同−又は異なり１．１−１、ＣＱ、０Ｃ
ｔｌｉを表わす） （２〉下記成分（Ａ＞（Ｂ）（Ｃ）（Ｄ）を含むエポキ
シ樹脂組成物。 （Δ）１ボキシ樹脂 （Ｂ ） 融点１６０℃以下のヒドラジド化合物（Ｃ）
下式で示される尿素化合物 Ｙ′ （但、ＸＳＹは同−又は異なりて、１」、ＣＱ、０ＣＨ
ｔを表わ１） （Ｄ＞強化材繊維 （３） （Ａ）成分のエポキシ樹脂が、ノボラック型エ
ポキシ樹脂又は／及びビスフェノールＡ型エポキシ樹脂
を含むものであるｒ１許請求の範囲（１）又は（２）の
エポキシ樹脂組成物。 （４）全エポキシ樹脂１００重量部に対し、（Ｂ）成分
が５〜８０重量部、（Ｃ）成分が０．１〜２０重量部で
あり、且つ（Ｂ）と（Ｃ）の比が１．０〜５０である特
許請求の範囲（１）又は（２）のエポキシ樹脂組成物。 （５）（Ｄ）成分が炭素繊維を含む強化材繊維である特
許請求の範囲（２）のエポキシ樹脂組成物。[Scope of Claims] (1) An epoxy resin composition containing the following components (A), (B), and (C). (A>Epoxy resin (B) 1 point hydrazide compound below 160℃ (C) Urea compound represented by the following formula (However, X and Y are the same or different 1.1-1, CQ, 0C
tli) (2> Epoxy resin composition containing the following components (A>(B)(C)(D)). (Δ) 1 boxy resin (B) Hydrazide compound with melting point of 160°C or less (C)
Urea compound Y' represented by the following formula (where XSY is the same or different, 1'', CQ, 0CH
1) (D>Reinforcement fiber (3) The epoxy resin of component (A) contains a novolac type epoxy resin or/and a bisphenol A type epoxy resin r1 Claims (1) or (2) ). (4) Component (B) is 5 to 80 parts by weight, component (C) is 0.1 to 20 parts by weight, and (B) and 100 parts by weight of the total epoxy resin. The epoxy resin composition according to claim (1) or (2), in which the ratio of (C) is 1.0 to 50. Epoxy resin composition of range (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5833884A JPS60202116A (en) | 1984-03-28 | 1984-03-28 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5833884A JPS60202116A (en) | 1984-03-28 | 1984-03-28 | Epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60202116A true JPS60202116A (en) | 1985-10-12 |
| JPH0440378B2 JPH0440378B2 (en) | 1992-07-02 |
Family
ID=13081528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5833884A Granted JPS60202116A (en) | 1984-03-28 | 1984-03-28 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60202116A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4714648A (en) * | 1984-08-01 | 1987-12-22 | Toho Rayon Co., Ltd. | Prepregs and method for production thereof |
| JPH07109405A (en) * | 1993-10-15 | 1995-04-25 | Mitsui Toatsu Chem Inc | Production of cell for liquid-crystal sealing |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5025700A (en) * | 1973-07-06 | 1975-03-18 | ||
| JPS5145161A (en) * | 1974-10-15 | 1976-04-17 | Yokohama Rubber Co Ltd | EHOKI SHEMARUJONSOSEIBUTSU |
| JPS57147513A (en) * | 1981-03-09 | 1982-09-11 | Sumitomo Chem Co Ltd | Varnish composition |
| JPS5842674A (en) * | 1981-09-09 | 1983-03-12 | Mitsui Petrochem Ind Ltd | Heat-curing polyepoxide composition |
-
1984
- 1984-03-28 JP JP5833884A patent/JPS60202116A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5025700A (en) * | 1973-07-06 | 1975-03-18 | ||
| JPS5145161A (en) * | 1974-10-15 | 1976-04-17 | Yokohama Rubber Co Ltd | EHOKI SHEMARUJONSOSEIBUTSU |
| JPS57147513A (en) * | 1981-03-09 | 1982-09-11 | Sumitomo Chem Co Ltd | Varnish composition |
| JPS5842674A (en) * | 1981-09-09 | 1983-03-12 | Mitsui Petrochem Ind Ltd | Heat-curing polyepoxide composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4714648A (en) * | 1984-08-01 | 1987-12-22 | Toho Rayon Co., Ltd. | Prepregs and method for production thereof |
| JPH07109405A (en) * | 1993-10-15 | 1995-04-25 | Mitsui Toatsu Chem Inc | Production of cell for liquid-crystal sealing |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0440378B2 (en) | 1992-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1275674B1 (en) | Epoxy resin composition and prepreg made with the epoxy resin composition | |
| US4517321A (en) | Preimpregnated reinforcements and high strength composites therefrom | |
| US4714648A (en) | Prepregs and method for production thereof | |
| JPS58120639A (en) | Prepreg for composite having high elongation and heat resistance | |
| JPH05423B2 (en) | ||
| JPS621719A (en) | Epoxy resin composition | |
| JPS621717A (en) | Epoxy resin composition | |
| JPS6143616A (en) | Epoxy resin composition | |
| JPH01215822A (en) | Epoxy resin composed of aromatic diamine curing agent | |
| JPS60202116A (en) | Epoxy resin composition | |
| US5128425A (en) | Epoxy resin composition for use in carbon fiber reinforced plastics, containing amine or amide based fortifiers | |
| JPS5817535B2 (en) | Epoxy resin composition for carbon fiber reinforcement | |
| JPS6236421A (en) | Epoxy resin composition for prepreg | |
| JPS6338049B2 (en) | ||
| JPS621720A (en) | Epoxy resin composition | |
| JPS6017288B2 (en) | Heat-resistant epoxy resin composition | |
| JPS621721A (en) | Epoxy resin composition | |
| JPS62146927A (en) | Intermediate for composite material | |
| JPS59174616A (en) | Epoxy resin composition and prepreg | |
| JPH0776616A (en) | Epoxy resin composition for prepreg and prepreg | |
| JPS6140317A (en) | Production of prepreg | |
| JPH031327B2 (en) | ||
| JPS6338048B2 (en) | ||
| JPH03243619A (en) | Epoxy resin composition | |
| JPS61250022A (en) | Matrix resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |