JPH02135217A - Epoxy resin - Google Patents
Epoxy resinInfo
- Publication number
- JPH02135217A JPH02135217A JP28760788A JP28760788A JPH02135217A JP H02135217 A JPH02135217 A JP H02135217A JP 28760788 A JP28760788 A JP 28760788A JP 28760788 A JP28760788 A JP 28760788A JP H02135217 A JPH02135217 A JP H02135217A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- epoxy
- structural formula
- curing agent
- phenylenediamine
- 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 31
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000004760 aramid Substances 0.000 claims abstract description 13
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 13
- 150000004985 diamines Chemical class 0.000 claims abstract description 7
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 5
- 239000004593 Epoxy Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract 4
- 239000012744 reinforcing agent Substances 0.000 claims description 4
- 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 abstract description 11
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 abstract description 5
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 abstract description 5
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract 2
- 239000012046 mixed solvent Substances 0.000 abstract 2
- 239000003607 modifier Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-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
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は機械的性能の優れたエポキシ樹脂に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to an epoxy resin with excellent mechanical performance.
エポキシ樹脂用硬化剤として従来、主にアミン系、酸無
水物系が用いられている。アミン系硬化剤のうち、従来
より用いられている芳香族ジアミン類としてはｍ−フェ
ニレンジアミン、４．４’−ジアミノジフェニルスルホ
ン、４．４’−ジアミノジフェニルメタンなどが知られ
、広く用いられている。Conventionally, amine-based and acid anhydride-based curing agents have been mainly used as curing agents for epoxy resins. Among amine-based curing agents, m-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, etc. are known and widely used as aromatic diamines that have been used conventionally. .
また本発明者等は、エポキシ樹脂の機械的性能を向上さ
せるエポキシ樹脂用硬化剤として別途出願している。こ
れは、強化機能を有するアラミド系の剛直な骨格を持つ
ジアミンを硬化剤として用い、一般のエポキシプレポリ
マーに混合、硬化させてエポキシ樹脂中に剛直な骨格を
導入するもので、従来の芳香族ジアミンを用いて硬化さ
せたエポキシ樹脂に較べて優れた機械的性能を得ること
ができるものである。The present inventors have also filed a separate application as a curing agent for epoxy resins that improves the mechanical performance of epoxy resins. This uses an aramid-based diamine with a rigid skeleton that has a reinforcing function as a hardening agent, and mixes it with a general epoxy prepolymer and cures it to introduce a rigid skeleton into the epoxy resin. It is possible to obtain superior mechanical performance compared to epoxy resins cured using diamines.
ところで、前述の従来から用いられている芳香族ジアミ
ンを硬化剤として得られるエポキシ樹脂は機械的強度に
限界があり、近年、エポキシ樹脂の機械的性能を向上さ
せる技術が強く求められている。By the way, the epoxy resins obtained by using the conventionally used aromatic diamine as a curing agent have a limited mechanical strength, and in recent years, there has been a strong demand for technology to improve the mechanical performance of epoxy resins.
一方、前述の本発明者等により別途出願された末端にア
ミノ基を持つアラミド系剛直分子単独でからなるエポキ
シ樹脂用硬化剤においてはアラミド系ジアミンの分子量
が多くなる程、硬化に必要な量が多くなり、また粘度が
高くなること等が懸念される。On the other hand, in the case of the curing agent for epoxy resins consisting solely of aramid-based rigid molecules having an amino group at the end, which was separately filed by the inventors of the present invention, the larger the molecular weight of the aramid-based diamine, the more the amount required for curing. There are concerns that the amount will increase and the viscosity will increase.
本発明は、この別途出願の硬化剤を少量使用し、かつ粘
度の上昇のない、しかも従来のアミン系硬化剤を用いた
ものよりも優れた機械的性能を有するエポキシ樹脂を提
案することを目的とする。The purpose of the present invention is to propose an epoxy resin that uses a small amount of the curing agent of this separately filed application, does not increase viscosity, and has better mechanical performance than those using conventional amine-based curing agents. shall be.
上記目的を達成するために、本発明は、下記構造式を有
するアラミド系剛直分子を主鎖とすルシアミンを強化剤
として、市販のエポキシ樹脂用の芳香族アミン系硬化剤
と共にエポキシプレポリマーに添加して硬化させてなる
ことを特徴とする。In order to achieve the above object, the present invention has an aramid-based rigid molecule having the following structural formula as the main chain and luciamine as a reinforcing agent, which is added to an epoxy prepolymer together with a commercially available aromatic amine-based curing agent for epoxy resin. It is characterized by being made by curing.
〔作用〕
本発明では、末端にアミノ基を持つアラミド系剛直分子
をエポキシ樹脂の硬化の際に、一般のエポキシ樹脂用の
芳香族アミン系硬化剤と併用し、このアラミド系剛直分
子がエポキシプレポリマーと化学結合してエポキシ樹脂
中に導入される。[Function] In the present invention, an aramid-based rigid molecule having an amino group at the end is used in combination with an aromatic amine-based curing agent for general epoxy resins when curing an epoxy resin, and this aramid-based rigid molecule It is chemically bonded to a polymer and introduced into the epoxy resin.
このアラミド系剛直分子は、エポキシ樹脂中において強
化分子として作用し、あたかもＦＲＰ（Ｆｉｂｅｒ Ｒ
ｅ１ｎｆｏｒｃｅｄ Ｐｌａｓｔｉｃｓ）における分子
レベルでの強化繊維に相当し、エポキシ樹脂の機械的性
能を向上させる作用を示す。This aramid-based rigid molecule acts as a reinforcing molecule in the epoxy resin, just like FRP (Fiber R).
It corresponds to reinforcing fibers at the molecular level in e1nforced plastics, and shows the effect of improving the mechanical performance of epoxy resins.
１、 アラミド系剛直分子の合成例
■ 構造式（１）の剛直分子の合成例
テレフタル酸クロライド（ＴＰＣ） １モルに対しｐ
−フェニレンジアミン（ＰＤＡ）が１０モルとなるよう
夫々をヘキサメチルホスホルアミド（ＨＭＰＡ）とＮ−
メチル−２−ピロリドン（ＮＭＰ）の混合溶媒に溶解し
、ＰＤＡ溶液にＴＰＣ溶液を滴下して主反応生成物（ａ
）を得た。1. Synthesis example of aramid rigid molecule ■ Synthesis example of rigid molecule of structural formula (1) Terephthalic acid chloride (TPC) p per 1 mole
- Phenyl diamine (PDA) was mixed with hexamethylphosphoramide (HMPA) and N-
The main reaction product (a
) was obtained.
逆に、ＴＰＣ溶液にＰＤＡ溶液を滴下して（ｂ）を得た
。Conversely, (b) was obtained by dropping the PDA solution into the TPC solution.
同様にして反応させる上記２つの溶液の濃度を変えて構
造式（Ｉ）で示される一連のアラミド系剛直分子を得た
■ 構造式（ｎ）の剛直分子の合成例
ｐ−フェニレンジアミン（ＰＤＡ）とｐ−ニトロ塩化ベ
ンゾイル（ＭＢＣ）のジメチルアセトアミド（ＤＭＡｃ
）溶液を混合して得た生成物をアミノ化して（Ｃ）を得
た。A series of aramid-based rigid molecules represented by structural formula (I) were obtained by changing the concentrations of the above two solutions reacted in the same manner.■ Synthesis example of rigid and rigid molecules having structural formula (n) p-phenylenediamine (PDA) dimethylacetamide (DMAc) of p-nitrobenzoyl chloride (MBC) and p-nitrobenzoyl chloride (MBC).
) The product obtained by mixing the solutions was aminated to obtain (C).
（Ｃ）とＭＢＣから同様にして（ｄ）を得、構造式（ｎ
）で示される一連のアラミド系剛直分子を得た。(d) was obtained in the same manner from (C) and MBC, and the structural formula (n
) A series of aramid-based rigid molecules were obtained.
■ 構造式（Ｉ［Ｉ）の剛直分子の合成例ｐ−ニトロア
ニリンとテレフタル酸クロライドから■と同様にして構
造式（ＩＩＩ）を示される一連のアラミド系剛直分子を
得た。(2) Synthesis Example of Rigid and Rigid Molecules of Structural Formula (I [I) A series of aramid rigid molecules represented by Structural Formula (III) were obtained from p-nitroaniline and terephthalic acid chloride in the same manner as (2).
２、 エポキシ樹脂の調製例
エポキシ樹脂としてビスフェノールＡ系エポキシ樹脂（
平均分子１１３８０）を用い、樹脂１モルに対し、ｐ−
フェニレンジアミンを硬化剤として０．２５モル、上記
■の合成例で得た生成物（ａ）を強化剤として０．２５
モル添加し、８０°Ｃで２４ｈｒ加熱後、１６０ ’Ｃ
で２４ｈｒ加熱して硬化させた。2. Preparation example of epoxy resin Bisphenol A epoxy resin (
average molecular weight of 11380), p-
0.25 mol of phenylenediamine as a curing agent, 0.25 mol of the product (a) obtained in the synthesis example (2) above as a reinforcing agent.
mol added and heated at 80°C for 24hr, then 160'C.
It was heated and cured for 24 hours.
また、比較のために、生成物（ａ）を用いないで、樹脂
１モルに対し、ｐ−フェニレンジアミンを０．５モル添
加し、８０°Ｃで２４ｈｒ加熱後、１６０°Ｃで２４ｈ
ｒ加熱硬化したエポキシ樹脂を調製した。For comparison, 0.5 mol of p-phenylenediamine was added to 1 mol of resin without using product (a), and after heating at 80°C for 24 hours, it was heated at 160°C for 24 hours.
A heat-cured epoxy resin was prepared.
この結果、比較例のｐ−フェニレンジアミンのみを用い
て硬化したエポキシ樹脂の引張強度は３２ＭＰａを示し
たのに対し、本発明の生成物（ａ）を引張強化剤として
添加して硬化させたエポキシ樹脂の引張強度は５５ＭＰ
ａを示した。As a result, the tensile strength of the epoxy resin cured using only p-phenylenediamine in the comparative example was 32 MPa, whereas the epoxy resin cured with the product (a) of the present invention added as a tensile strength agent showed a tensile strength of 32 MPa. The tensile strength of the resin is 55MP
It showed a.
〔発明の効果〕
以上詳述したように本発明のエポキシ樹脂は、従来のア
ミン系硬化剤のみで硬化したエポキシ樹脂に比べて、優
れた機械的性能を実現する。[Effects of the Invention] As detailed above, the epoxy resin of the present invention achieves superior mechanical performance compared to epoxy resins cured only with conventional amine-based curing agents.
また、本発明エポキシ樹脂は、強化剤の使用量も少なく
て済み、粘度の上昇を招くこともない等の効果をも奏す
る。Furthermore, the epoxy resin of the present invention has the advantage that only a small amount of reinforcing agent is required and no increase in viscosity is caused.
Claims (1)
ジアミンを強化剤として、エポキシ樹脂用の芳香族アミ
ン系硬化剤と共にエポキシプレポリマーに添加して硬化
させてなることを特徴とするエポキシ樹脂。 〔構造式〕 ▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（II） ▲数式、化学式、表等があります▼（III）[Scope of Claims] A diamine whose main chain is an aramid rigid molecule having the following structural formula is added as a reinforcing agent to an epoxy prepolymer together with an aromatic amine curing agent for epoxy resin and cured. An epoxy resin characterized by [Structural formula] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28760788A JPH02135217A (en) | 1988-11-16 | 1988-11-16 | Epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28760788A JPH02135217A (en) | 1988-11-16 | 1988-11-16 | Epoxy resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02135217A true JPH02135217A (en) | 1990-05-24 |
Family
ID=17719459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28760788A Pending JPH02135217A (en) | 1988-11-16 | 1988-11-16 | Epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02135217A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160152785A1 (en) * | 2013-07-11 | 2016-06-02 | Toray Industries, Inc. | Epoxy resin composition, prepreg, and carbon fiber-reinforced composite material |
| CN105960428A (en) * | 2014-02-06 | 2016-09-21 | 赫克塞尔合成有限公司 | Amino benzoates or benzamides as curing agents for epoxy resins |
-
1988
- 1988-11-16 JP JP28760788A patent/JPH02135217A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160152785A1 (en) * | 2013-07-11 | 2016-06-02 | Toray Industries, Inc. | Epoxy resin composition, prepreg, and carbon fiber-reinforced composite material |
| US10400076B2 (en) * | 2013-07-11 | 2019-09-03 | Toray Industries, Inc. | Epoxy resin composition, prepreg, and carbon fiber-reinforced composite material |
| CN105960428A (en) * | 2014-02-06 | 2016-09-21 | 赫克塞尔合成有限公司 | Amino benzoates or benzamides as curing agents for epoxy resins |
| EP3102621A1 (en) * | 2014-02-06 | 2016-12-14 | Hexcel Composites Limited | Amino benzoates or benzamides as curing agents for epoxy resins |
| US10040897B2 (en) | 2014-02-06 | 2018-08-07 | Hexcel Composites | Amino benzoates or benzamides as curing agents for epoxy resins |
| EP3102621B1 (en) * | 2014-02-06 | 2021-06-09 | Hexcel Composites Limited | Amino benzoates or benzamides as curing agents for epoxy resins |
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