JPS63159424A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPS63159424A JPS63159424A JP30622386A JP30622386A JPS63159424A JP S63159424 A JPS63159424 A JP S63159424A JP 30622386 A JP30622386 A JP 30622386A JP 30622386 A JP30622386 A JP 30622386A JP S63159424 A JPS63159424 A JP S63159424A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- epichlorohydrin
- epoxy
- heat resistance
- 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 48
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 claims abstract description 7
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical group NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical class C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000004845 glycidylamine epoxy resin Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 9
- 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
- 239000004593 Epoxy Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- -1 aliphatic amines Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規な、耐熱性および耐水性の飛躍的に優れた
エポキシ樹脂組成物に関し、さらに詳細には必須のエポ
キシ樹脂成分としてノアミノナフタレンとエピクロルヒ
ドリンからなるエポキシ樹脂を用いてなる。積層品樹脂
材料、電気絶縁材料、繊維強化複合材料、塗装材料、成
型材料、接着材料などに有用な、特に炭素繊維、アラミ
ド繊維、ガラス繊維等の強化繊維用マトリクス材料とし
て有用なエポキシ樹脂組成物に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel epoxy resin composition that has significantly superior heat resistance and water resistance, and more particularly, it relates to a novel epoxy resin composition containing noaminonaphthalene as an essential epoxy resin component. It is made using an epoxy resin consisting of and epichlorohydrin. Epoxy resin composition useful for laminate resin materials, electrical insulation materials, fiber-reinforced composite materials, coating materials, molding materials, adhesive materials, etc., particularly useful as a matrix material for reinforcing fibers such as carbon fibers, aramid fibers, glass fibers, etc. Regarding.
（従来の技術および問題点）
エポキシ樹脂は、種々の硬化剤で硬化させることにより
、一般的に機械的性質、耐薬品性、電気的性質などの優
れた硬化物となり、接着剤、塗料、積層板、成型材料、
注型材料等、幅広い分野に使用されている。(Prior art and problems) By curing epoxy resin with various curing agents, it generally becomes a cured product with excellent mechanical properties, chemical resistance, electrical properties, etc., and is used in adhesives, paints, and laminated materials. Boards, molding materials,
It is used in a wide range of fields such as casting materials.
最も汎用的なエポキシ樹脂は、ビスフェノールＡにエピ
クロルヒドリンを反応させて得られる液状又は固型のビ
スフェノールＡ型エポキシ樹脂であるが、これらは１分
子あ友りのグリシジル基が２個より多くはない几めに硬
化時の架橋密度が低く、耐熱性および耐水性に劣る傾向
にある。The most commonly used epoxy resin is liquid or solid bisphenol A type epoxy resin obtained by reacting bisphenol A with epichlorohydrin, but these resins contain no more than two glycidyl groups per molecule. Therefore, the crosslinking density during curing is low, and the heat resistance and water resistance tend to be poor.
この様な欠点を改良するために、いわゆるノブラック型
エポキシ樹脂が使用されており、確かに耐熱性は向上す
るが、その向上の程度は未だ不十分である。また同様に
耐熱性向上の目的で使用されているジアミノジフェニル
メタン等をベースとするグリシジルアミン型エポキシ樹
脂やアミノフェノール等をベースとするグリシジルアミ
ンエーテル型エポキシ樹脂は、ノボラック型エポキシ樹
脂を更に上回る耐熱性を示すものの、満足し得る耐熱性
にはいま一歩到らず、逆に耐水性の点で劣るという欠点
がある。In order to improve these drawbacks, so-called Noblak type epoxy resins have been used, and although they do improve heat resistance, the degree of improvement is still insufficient. Similarly, glycidylamine epoxy resins based on diaminodiphenylmethane and glycidylamine ether epoxy resins based on aminophenol, which are also used for the purpose of improving heat resistance, have heat resistance that is even higher than novolac epoxy resins. However, it still has the drawback of not achieving satisfactory heat resistance and, conversely, being inferior in water resistance.
（問題点を解決する友めの手段）
本発明者等は、こうし次実情に鑑みて、ノボラック型エ
ポキシ樹脂や、従来のグリシジルアミン型およびグリシ
ジルアミンエーテル型エポキシ樹脂をはるかに凌ぐ擾れ
友耐熱性および耐水性を有する新規なエポキシ樹脂組成
物を求めて鋭意研究し次結果、ジアミノナフタレンにエ
ピクロルヒドリンを反応させて得られるエポキシ樹脂を
必須成分として用い次樹脂組成物が、前述した如き優れ
次耐熱性と耐水性とを有することを見い出して。(Friendly Means for Solving Problems) In view of the current situation, the present inventors have developed a solution that far exceeds novolac type epoxy resins and conventional glycidylamine type and glycidylamine ether type epoxy resins. As a result of intensive research in search of a new epoxy resin composition having heat resistance and water resistance, the following resin composition using an epoxy resin obtained by reacting diamino naphthalene with epichlorohydrin as an essential component was found to have the excellent properties described above. It was discovered that it has heat resistance and water resistance.
本発明に到り友。My friend who came up with this invention.
すなわち１本発明は、エポキシ樹脂および硬化剤、さら
に必要により硬化促進剤から構成される工４キシ樹脂組
成物において、該エポキシ樹脂成分として、＊造式（１
）
で示されるジアミノナフタレンにエピクロルヒドリンを
反応させて得られるグリジノルアミン型エポキシ樹脂を
含有することを特徴とする硬化性エポキシ樹脂組成物を
提供するものである。That is, 1 the present invention provides a polyurethane resin composition composed of an epoxy resin, a curing agent, and, if necessary, a curing accelerator, in which the epoxy resin component has the formula (1)
) A curable epoxy resin composition is provided, which contains a glycinolamine type epoxy resin obtained by reacting diamino naphthalene with epichlorohydrin.
本発明で使用されるジアミノナフタレンとしては、上記
の構造式（Ｉ）で示されるものがいずれも使用できるが
、なかでも市販されており、入手が容易な点で１，４−
１１，５−１１，６−又は１，８−ジアミノナフタレン
が好ましい。As the diaminonaphthalene used in the present invention, any of those represented by the above structural formula (I) can be used, but among them, 1,4-
11,5-11,6- or 1,8-diaminonaphthalene is preferred.
本発明で用いるグリジノルアミン型エポキシ樹脂は、前
記構造式（１）のジアミノナフタレンにアルカリの存在
下にエピクロルヒドリンを反応させることＫよシ得られ
る。The glycinolamine type epoxy resin used in the present invention can be obtained by reacting diamino naphthalene of the structural formula (1) with epichlorohydrin in the presence of an alkali.
この場合の反応条件は、従来より行なわれているエポキ
シ樹脂の製造条件と同じであり、特に制限される本ので
はない。The reaction conditions in this case are the same as those conventionally used for producing epoxy resins, and are not particularly limited.
即ち、ジアミノナフタレンのアミン性活性水素１個に対
し、エピクロルヒドリンを１〜１０モル添加し、水酸化
ナトリウムのようなアルカリの存在下に２０〜１２０℃
でエポキシ化反応を行なうことにより得られる。この時
アミン性活性水素に対するエピクロルヒドリンの過剰率
を調節することにより、得られるエポキシ化物の分子量
、エポキシ当量、軟化点を調整することができる。エピ
クロルヒドリンの過剰率を下げるとエポキシ樹脂の分子
量が高くなり、靭性の高い硬化物となり。That is, 1 to 10 mol of epichlorohydrin is added to one amine active hydrogen of diaminonaphthalene, and the mixture is heated at 20 to 120°C in the presence of an alkali such as sodium hydroxide.
It can be obtained by carrying out an epoxidation reaction. At this time, by adjusting the excess ratio of epichlorohydrin to aminic active hydrogen, the molecular weight, epoxy equivalent, and softening point of the obtained epoxide can be adjusted. Lowering the excess ratio of epichlorohydrin increases the molecular weight of the epoxy resin, resulting in a cured product with high toughness.
逆に上げると分子量が低くなり、耐熱性の高い硬化物と
なる傾向がある。ただし、一般的にはエピクロルヒドリ
ンの過剰率が４倍を越えるとあまり変化しなくなるので
、過剰率は５倍以下にすることが望ましい。On the other hand, if the molecular weight is increased, the molecular weight tends to decrease, resulting in a cured product with high heat resistance. However, in general, if the excess ratio of epichlorohydrin exceeds 4 times, it will not change much, so it is desirable that the excess ratio is 5 times or less.
なぜに本発明のエポキシ樹脂組放物の硬化物が飛躍的に
優れた耐熱性および耐水性を有するかは。Why does the cured product of the epoxy resin assembly of the present invention have dramatically superior heat resistance and water resistance?
該エポキシ樹脂が４官能性であることに加えて。In addition to the fact that the epoxy resin is tetrafunctional.
ナフタレン骨格が剛直かつ優れた耐水性を有し。The naphthalene skeleton is rigid and has excellent water resistance.
更にナフタレン骨格間に働く凝集力が大きいためである
と推測される。Furthermore, it is presumed that this is due to the large cohesive force acting between the naphthalene skeletons.
本発明で用いる硬化剤としては１通常エポキシ樹脂の硬
化剤として常用されている化合物はすべて使用すること
ができ、例えばジエチレントリアミン、トリエチレンテ
トラミンなどの脂肪族アミン類；メタフェニレンジアミ
ン、ジアミノジフェニルメタン、ジアミノジフェニルス
ルホンなどの芳香族アミン類；プリアミド樹脂およびこ
れらの変性物；無水マレイン酸、無水フタル酸、無水へ
キサヒドロフタル酸、無水ピロメリット酸などの酸無水
物系硬化剤；ジシアンジアミｒ、イミダゾール、ＢＦ３
−アミン錯体、グアニジン誘導体などの潜在性硬化剤な
どがあげられる。As the curing agent used in the present invention, all compounds commonly used as curing agents for epoxy resins can be used, such as aliphatic amines such as diethylenetriamine and triethylenetetramine; metaphenylenediamine, diaminodiphenylmethane, and diamino Aromatic amines such as diphenyl sulfone; preamide resins and modified products thereof; acid anhydride curing agents such as maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and pyromellitic anhydride; dicyandiamyl, imidazole, BF3
- Latent curing agents such as amine complexes and guanidine derivatives are included.
上掲された如き各化合物を硬化剤として用いる際は、多
くの場合さらに硬化促進剤をも併用することが必要とな
るが、そうした場合にはジメチルベンジルアミンなどの
如き三級アミン類：イミダゾール類；ま念は各種金属化
合物などをはじめ、公知慣用の硬化促進剤ならすべて使
用できることは勿論である。本発明の組成物には、さら
に必要に応じて充填剤、着色剤などの公知慣用の各種添
加剤をも添加配合せしめることができ、またタール、ピ
ッチ、アミノ樹脂、アルキッド樹脂、フェノール樹脂な
ども併用することができる。When using each of the compounds listed above as a curing agent, it is often necessary to also use a curing accelerator, but in such cases, tertiary amines such as dimethylbenzylamine, imidazoles, etc. Of course, all known and commonly used curing accelerators can be used, including various metal compounds. The composition of the present invention may further contain various known and commonly used additives such as fillers and colorants, as well as tar, pitch, amino resins, alkyd resins, phenolic resins, etc. Can be used together.
（発明の効果）
本発明のエポキシ樹脂組成物から得られた硬化物は、飛
躍的に優れた耐熱性および耐水性ｆ、有するという特徴
がある。(Effects of the Invention) The cured product obtained from the epoxy resin composition of the present invention is characterized by dramatically superior heat resistance and water resistance f.
従って、本発明のエポキシ樹脂組成物は、成型材料、注
型材料、積層材料、塗料、接着剤などの広範囲の用途に
極めて有用であり、特に炭素繊維、アラミド繊維、ガラ
ス繊維等の強化繊維のマトリクスの如き、優れ念耐熱性
を求められる材料に適している。Therefore, the epoxy resin composition of the present invention is extremely useful for a wide range of applications such as molding materials, casting materials, laminated materials, paints, and adhesives, and is especially useful for reinforcing fibers such as carbon fibers, aramid fibers, and glass fibers. Suitable for materials that require excellent heat resistance, such as matrices.
（実施例）
次に本発明を製造例、実施例および比較例により具体的
に説明するが、以下において部および憾は特に断りのな
い限りすべて重量基準である（ただし、引張り伸び率を
除く）。(Example) Next, the present invention will be specifically explained using production examples, working examples, and comparative examples. In the following, parts and numbers are all based on weight unless otherwise specified (excluding tensile elongation percentage). .
製造例１
１．５−ジアミノナフタレン１５８９（１モル）をエピ
クロルヒドリン７４０９Ｃ８モル）に溶解させ念後、攪
拌しながら５０〜６０℃で２０４水酸化ナトリウム水溶
液８０（１（４モル）を５時間かけて滴下し、更に１時
間反応させ１次いで水層ｔ−集却しｔ後、過剰のエピク
ロルヒドリンを蒸留回収して反応粗生放物を得次。この
反応粗生成物にトルエン３５０Ｉを加えて均一に溶解さ
せ。Production Example 1 1.5-Diaminonaphthalene 1589 (1 mol) was dissolved in epichlorohydrin 7409C (8 mol), and after stirring, 204 sodium hydroxide aqueous solution 80 (1 (4 mol)) was dissolved at 50 to 60°C over 5 hours. It was added dropwise and reacted for an additional hour, and then the aqueous layer was collected. After that, excess epichlorohydrin was recovered by distillation to obtain a reaction crude product. To this reaction crude product, 350 I of toluene was added and the mixture was homogenized. Let it dissolve.
水１００ｇを加えて水洗した後、油水分離し、油層から
トルエンを留去させることによって、半固型でエポキシ
当量が１０８なるエポキシ樹脂（ａ）３６２１を得友。After washing with 100 g of water, oil and water were separated, and toluene was distilled off from the oil layer to obtain semi-solid epoxy resin (a) 3621 with an epoxy equivalent of 108.
製造例２
エピクロルヒドリンの使用量を５５５，１ｉｔ（６％ル
）とした以外は製造例１と同様にして、軟化点が６０℃
でかつエポキシ当量が１２５なるエポキシ樹脂（ｂ）
３５１ ｇを得た。Production Example 2 The softening point was 60° C. in the same manner as Production Example 1 except that the amount of epichlorohydrin used was 555.1 it (6% L).
Epoxy resin (b) which is large and has an epoxy equivalent of 125
351 g was obtained.
製造例３
１．５−ジアミノナフタレンの代りに１，８−ジアミノ
ナフタレンを用いた以外は製造例１と同様にして、半固
型でエポキシ当ｉ：１０９なるエポキシ樹脂（ｅ） ３
５９９を得た。Production Example 3 A semi-solid epoxy resin (e) 3 having an epoxy ratio of 109 was produced in the same manner as Production Example 1 except that 1,8-diaminonaphthalene was used instead of 1,5-diaminonaphthalene.
I got 599.
製造例４
１．５−ジアミノナフタレンの代りに１，８−ジアミノ
ナフタレンを用いた以外は製造例２と同様にして、軟化
点が６３℃で、かつエポキシ当量が１３０なるエポキシ
樹脂（ａ） ３４７ ｇを得た。Production Example 4 Epoxy resin (a) having a softening point of 63°C and an epoxy equivalent of 130 in the same manner as Production Example 2 except that 1,8-diaminonaphthalene was used instead of 1,5-diaminonaphthalene 347 I got g.
実施例１〜５および比較例１〜２
エポキシ樹脂として製造例１〜４で得られたエポキシ樹
脂（、）〜（ｄ）、フェノールノブラック型工？キシ樹
脂エビクロンＮ−７３８（大日本インキ化学工業■裂、
エポキシ当量１８０、半固型〕又は。Examples 1 to 5 and Comparative Examples 1 to 2 Epoxy resins (,) to (d) obtained in Production Examples 1 to 4 as epoxy resins, phenol black mold processing? Kishiresin Ebikuron N-738 (Dainippon Ink Chemical Co., Ltd.)
Epoxy equivalent: 180, semi-solid] or.
ジアミノジフェニルメタン型グリシジルアミンエボキシ
樹脂エビクロン４３０［同社製、エポキシ当量１２０．
半固型］を用い、硬化剤としてエビクロンＢ−５７０（
同社製、メチルテトラヒドロフタル酸無水物〕又はパー
カムＴＤ −２１３１（同社製、フェノールノボラック
樹脂〕を用い、更に硬化促進剤として２−エチル−４−
メチルイミダゾール又はベンジルジメチルアミンを用い
て、エポキシ樹脂のエポキシ１１個に対して硬化剤の酸
無水物基が１個になる様に表−１に示す組成で配合して
１本発明および比較対照用のエポキシ樹脂組成物を得た
。Diaminodiphenylmethane type glycidylamine epoxy resin Evicron 430 [manufactured by the same company, epoxy equivalent: 120.
Semi-solid] was used, and Evicron B-570 (
2-ethyl-4-
Using methylimidazole or benzyldimethylamine, the compositions shown in Table 1 were blended so that the number of acid anhydride groups in the curing agent was one for every 11 epoxy groups in the epoxy resin, and one sample was used for the present invention and for comparison. An epoxy resin composition was obtained.
これらのエポキシ樹脂組成物を、１００℃で２時間、次
いで１６０℃で２時間、更に１８０℃で２時間の条件で
硬化せしめて試験片を得、ＪＩＳＫ−６９１１に準拠し
て熱変形温度１曲げ強度１曲げ弾性率、引張り強度、引
張り伸び率および煮沸吸水率を測定し友。結果を表−１
に示す。These epoxy resin compositions were cured at 100°C for 2 hours, then at 160°C for 2 hours, and then at 180°C for 2 hours to obtain test pieces. Strength 1 Measuring flexural modulus, tensile strength, tensile elongation and boiling water absorption. Table 1 shows the results.
Shown below.
、′丁′, 'Ding'
Claims (1)
剤から構成されるエポキシ樹脂組成物において、該エポ
キシ樹脂成分として、構造式〔 I 〕▲数式、化学式、
表等があります▼〔 I 〕 で示されるジアミノナフタレンにエピクロルヒドリンを
反応させて得られるグリシジルアミン型エポキシ樹脂を
含有することを特徴とする硬化性エポキシ樹脂組成物。[Scope of Claims] In an epoxy resin composition comprising an epoxy resin, a curing agent, and, if necessary, a curing accelerator, the epoxy resin component includes a structural formula [I]▲mathematical formula, chemical formula,
▼ A curable epoxy resin composition characterized by containing a glycidylamine type epoxy resin obtained by reacting diamino naphthalene represented by [I] with epichlorohydrin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30622386A JPS63159424A (en) | 1986-12-24 | 1986-12-24 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30622386A JPS63159424A (en) | 1986-12-24 | 1986-12-24 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63159424A true JPS63159424A (en) | 1988-07-02 |
Family
ID=17954474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30622386A Pending JPS63159424A (en) | 1986-12-24 | 1986-12-24 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63159424A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2460050A (en) * | 2008-05-14 | 2009-11-18 | Hexcel Composites Ltd | Epoxy composite |
| WO2016017371A1 (en) * | 2014-07-31 | 2016-02-04 | 東レ株式会社 | Two-pack type epoxy resin composition for fiber-reinforced composite material, and fiber-reinforced composite material |
-
1986
- 1986-12-24 JP JP30622386A patent/JPS63159424A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2460050A (en) * | 2008-05-14 | 2009-11-18 | Hexcel Composites Ltd | Epoxy composite |
| US20110049426A1 (en) * | 2008-05-14 | 2011-03-03 | Hexcel Composites, Ltd. | Moulding processes |
| WO2016017371A1 (en) * | 2014-07-31 | 2016-02-04 | 東レ株式会社 | Two-pack type epoxy resin composition for fiber-reinforced composite material, and fiber-reinforced composite material |
| CN106574039A (en) * | 2014-07-31 | 2017-04-19 | 东丽株式会社 | Two-pack type epoxy resin composition for fiber-reinforced composite material, and fiber-reinforced composite material |
| JPWO2016017371A1 (en) * | 2014-07-31 | 2017-04-27 | 東レ株式会社 | Two-component epoxy resin composition for fiber reinforced composite material and fiber reinforced composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0127198B1 (en) | Preimpregnated reinforcements and high strength composites therefrom | |
| US4608404A (en) | Epoxy compositions containing oligomeric diamine hardeners and high strength composites therefrom | |
| US5599856A (en) | Epoxy resin systems containing modifiers | |
| RU2574054C2 (en) | Epoxy resin-based curable compositions and composite materials obtained therefrom | |
| US4661559A (en) | Impact resistant matrix resins for advanced composites | |
| US4746718A (en) | Novel oligomeric diamine hardeners and their use for curing epoxy resin systems | |
| US5091474A (en) | Epoxy resin curing agent based on blends containing disecondary aromatic diamines | |
| US4760106A (en) | Impact resistant matrix resins for advanced composites | |
| JPS6173719A (en) | Novel epoxy resin composition | |
| EP0130270A1 (en) | Epoxy compositions containing oligomeric diamine hardeners and high strength composites therefrom | |
| EP0133281A2 (en) | Curable fibre reinforced epoxy resin composition | |
| US5218061A (en) | Partially post-glycidylated epoxy resin, epoxy resin composition and cured product thereof | |
| JPS60181121A (en) | Epoxy resin composition | |
| JP2709731B2 (en) | Epoxy resin composed of aromatic diamine curing agent | |
| JPH0519567B2 (en) | ||
| JPS61188413A (en) | Epoxy resin composition | |
| JP2715512B2 (en) | Epoxy resin composition and molded article obtained by curing the same | |
| JPH06184131A (en) | Epoxy resin, its production, epoxy resin composition and semiconductor sealing material | |
| JPS63159424A (en) | Epoxy resin composition | |
| JP2587739B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| JPH01268714A (en) | Novel epoxy resin composition | |
| JPH01268712A (en) | Epoxy resin composition | |
| JPH01268715A (en) | Novel epoxy resin composition | |
| JPS62124110A (en) | Epoxy resin composition | |
| JP2774345B2 (en) | Novel epoxy resin and its production method |