JP4765053B2 - Heat resistant and high strength epoxy resin - Google Patents
Heat resistant and high strength epoxy resin Download PDFInfo
- Publication number
- JP4765053B2 JP4765053B2 JP2004148422A JP2004148422A JP4765053B2 JP 4765053 B2 JP4765053 B2 JP 4765053B2 JP 2004148422 A JP2004148422 A JP 2004148422A JP 2004148422 A JP2004148422 A JP 2004148422A JP 4765053 B2 JP4765053 B2 JP 4765053B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- amino
- quinoxaline
- curing agent
- aminophenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003822 epoxy resin Substances 0.000 title claims description 33
- 229920000647 polyepoxide Polymers 0.000 title claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 9
- 150000004982 aromatic amines Chemical class 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- -1 6-amino-2,3-bis (aminophenyl) quinoxaline Chemical compound 0.000 claims description 4
- QMSQNWKFGPPRIJ-UHFFFAOYSA-N 2,3-bis(4-aminophenyl)quinoxalin-6-amine Chemical group C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N=C1C1=CC=C(N)C=C1 QMSQNWKFGPPRIJ-UHFFFAOYSA-N 0.000 claims description 3
- FTKCJWKPAZRHTL-UHFFFAOYSA-N 3-quinoxalin-2-ylaniline Chemical compound NC1=CC=CC(C=2N=C3C=CC=CC3=NC=2)=C1 FTKCJWKPAZRHTL-UHFFFAOYSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 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 8
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 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 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 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 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- QFVXVCVHHDVGIP-UHFFFAOYSA-N 2,3-bis(3-aminophenyl)quinoxalin-6-amine Chemical compound NC1=CC=CC(C=2C(=NC3=CC(N)=CC=C3N=2)C=2C=C(N)C=CC=2)=C1 QFVXVCVHHDVGIP-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- KBFRYWNQGIWTIB-UHFFFAOYSA-N 2-[3-(2-aminophenyl)quinoxalin-2-yl]aniline Chemical compound NC1=CC=CC=C1C1=NC2=CC=CC=C2N=C1C1=CC=CC=C1N KBFRYWNQGIWTIB-UHFFFAOYSA-N 0.000 description 1
- IRIGZAPSCHSJAQ-UHFFFAOYSA-N 4-[3-(4-aminophenyl)quinoxalin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=CC=C2N=C1C1=CC=C(N)C=C1 IRIGZAPSCHSJAQ-UHFFFAOYSA-N 0.000 description 1
- JLBSVDZUWJLOCF-GTWSWNCMSA-N DDM-838 Chemical compound C1CCCNC(=O)C1NC(=O)CC(C)OC(=O)C(CCCCNC(=O)\C=C/CCCCCCCCCCCCCCCCC)NC(=O)C(N=1)(C)COC=1C1=CC=CC=C1O JLBSVDZUWJLOCF-GTWSWNCMSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003252 quinoxalines Chemical group 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
本発明は，耐熱性・高強度エポキシ樹脂に関するものである。 The present invention relates to a heat resistant and high strength epoxy resin.
エポキシ樹脂は接着性、接着強度、非収縮性、電気特性など優れているため、航空機、宇宙機器、自動車、スポーツ用品、レジャー用品などの用途で広く用いられている。 Epoxy resins are widely used in applications such as aircraft, space equipment, automobiles, sporting goods, and leisure goods because of their excellent adhesiveness, adhesive strength, non-shrinkage, and electrical properties.
一般的に、エポキシ樹脂の耐熱性を向上させるためには、硬化剤の構造中に芳香環を導入すれば効果があることがわかっている。従来、汎用のエポキシ樹脂の耐熱性硬化剤としては、４，４‘−ジアミノジフェニルスルホン（ＤＤＳ）や４，４’−ジアミノジフェニルメタン（ＤＤＭ）が知られている（たとえば特許文献１参照）。これらの硬化剤を用いて製造されたエポキシ樹脂硬化物は熱変形温度が１９６℃および１５６℃で室温では十分な接着強度を示す。しかし、従来のエポキシ樹脂硬化物を高温にさらすと、その接着強度は１２０℃付近から急速に低下し、１８０℃においてはＤＤＭ効果の場合で室温の６７％、ＤＤＳ効果の場合で室温の５４％にまで低下する。このように従来のエポキシ樹脂硬化物では熱変形温度、接着力ともに耐熱性が十分でないという問題があった。
本発明の目的は、高い耐熱性または、および接着強度を示すエポキシ樹脂硬化物を提供することである。 The objective of this invention is providing the epoxy resin hardened | cured material which shows high heat resistance or adhesive strength.
本発明は、（１）エポキシ樹脂（Ａ）と芳香族アミン系硬化剤（Ｂ）をエポキシ基とアミノ基をモル比２：１で配合したエポキシ樹脂組成物。（２）芳香族アミン系硬化剤（Ｂ）がポリアミノフェニルキノキサリンを１〜１００モル％含有している（１）のエポキシ樹脂組成物。（３）前記ポリアミノフェニルキノキサリンが、６−アミノ−２，３−ビス（ｐ−アミノフェニル）キノキサリン、６−アミノ−２，３−ビス（ｍ−アミノフェニル）キノキサリンまたは６−アミノ−２，３−ビス（アミノフェニル）キノキサリンであることを特徴とする（２）のエポキシ樹脂組成物。（４）（１）〜（３）のエポキシ樹脂組成物を硬化したエポキシ樹脂硬化物に関する。 The present invention is (1) an epoxy resin composition in which an epoxy resin (A) and an aromatic amine curing agent (B) are blended with an epoxy group and an amino group in a molar ratio of 2: 1. (2) The epoxy resin composition according to (1), wherein the aromatic amine-based curing agent (B) contains 1 to 100 mol% of polyaminophenylquinoxaline. (3) The polyaminophenylquinoxaline is 6-amino-2,3-bis (p-aminophenyl) quinoxaline, 6-amino-2,3-bis (m-aminophenyl) quinoxaline or 6-amino-2,3 -The epoxy resin composition according to (2), which is bis (aminophenyl) quinoxaline. (4) It relates to a cured epoxy resin obtained by curing the epoxy resin composition of (1) to (3).
本発明に係るエポキシ樹脂硬化剤は、キノキサリン環を有するポリアミンであって、アミノ基として６−アミノおよびｐ−アミノまたはおよびｍ−アミノまたはおよびアミノフェニル基を有するか、キノキサリン環を含むポリアミンと芳香族アミン系硬化剤（ＤＤＳ、ＤＤＭおよびエーテル変性芳香族アミンおよびこれらの誘導体など）と混合したものである。芳香族アミン系硬化剤としては、例えば、フェニレンジアミン、ジアミノジフェニルメタン、２，２’−ビス−（アミノフェニル）プロパン、ジアミノジフェニルスルホン、トルエンジアミン等およびこれらの誘導体が挙げられ、単独または数種混合して使用することが出来る。 The epoxy resin curing agent according to the present invention is a polyamine having a quinoxaline ring, which has a 6-amino and p-amino or m-amino or and aminophenyl group as an amino group, or a polyamine containing a quinoxaline ring. Mixed with an aromatic amine-based curing agent (such as DDS, DDM and ether-modified aromatic amines and derivatives thereof). Examples of the aromatic amine-based curing agent include phenylenediamine, diaminodiphenylmethane, 2,2′-bis- (aminophenyl) propane, diaminodiphenylsulfone, toluenediamine, and the like, and derivatives thereof. Can be used.
本発明に係るエポキシ樹脂硬化物は、ポリアミノフェニルキノキサリンまたはポリアミノフェニルキノキサリンを含有する芳香族ポリアミンを硬化剤としエポキシ樹脂を硬化した硬化物であって、樹脂中に３置換キノキサリン構造を有することを特徴とする。３置換キノキサリン構造を下記に示す。
本発明のエポキシ樹脂硬化剤は複素環を含み３置換構造を有しているため架橋密度が高くなり、高い熱変形温度およびまたは高い接着強度を達成することが出来る。 Since the epoxy resin curing agent of the present invention contains a heterocyclic ring and has a trisubstituted structure, the crosslinking density is increased, and a high heat distortion temperature and / or a high adhesive strength can be achieved.
以下、本発明を実施例に基づいて説明する。
エポキシ樹脂として旭電化工業製ＥＰ−４１００（ビスフェノールＡのジグリシジルエーテル）を用意した。また、硬化剤として下記のものを用意した。
ＡＢＡＰＱ：６−アミノ−２，３−ビス（４−アミノフェニル）キノキサリン
ｐ−ＢＡＰＱ：２，３−ビス（４−アミノフェニル）キノキサリン
ＤＤＳ：４，４’−ジアミノジフェニルスルホン
これらの硬化剤の化学式を下記に示す。
As an epoxy resin, EP-4100 (diglycidyl ether of bisphenol A) manufactured by Asahi Denka Kogyo was prepared. Moreover, the following were prepared as a hardening | curing agent.
ABAPQ: 6-amino-2,3-bis (4-aminophenyl) quinoxaline p-BAPQ: 2,3-bis (4-aminophenyl) quinoxaline DDS: 4,4′-diaminodiphenylsulfone Chemical formula of these curing agents Is shown below.
上記エポキシ樹脂と各々の硬化剤をエポキシ基とアミノ基のモル比が２：１になるように混合し、加熱硬化してエポキシ樹脂硬化物を得た。
それぞれのエポキシ樹脂硬化物の熱変形温度を求めた。
熱変形温度は、ＪＩＳ Ｋ−７１９６に従い、針入法によるＴＭＡ（Ｔｈｅｒｍａｏｍｅｃｈａｎｉｃａｌａｎａｌｙｓｉｓ）を行うことによって測定した。The epoxy resin and each curing agent were mixed so that the molar ratio of epoxy group to amino group was 2: 1 and cured by heating to obtain a cured epoxy resin.
The thermal deformation temperature of each cured epoxy resin was determined.
The heat distortion temperature was measured by performing TMA (Thermomechanical analysis) according to the penetration method according to JIS K-7196.
また、上記のエポキシ樹脂とＡＢＡＰＱとＤＤＳをモル比で２５：７５、５０：５０、７５：２５の割合で混合した硬化剤を調整し、エポキシ基とアミノ基のモル比が２：１になるように混合し、加熱硬化しエポキシ硬化物を得た。
それぞれのエポキシ硬化物の熱変形温度をＴＭＡで測定した。In addition, a curing agent prepared by mixing the above epoxy resin, ABAPQ, and DDS in a molar ratio of 25:75, 50:50, and 75:25 is adjusted so that the molar ratio of epoxy group to amino group is 2: 1. The resulting mixture was cured by heating to obtain an epoxy cured product.
The thermal deformation temperature of each epoxy cured product was measured by TMA.
さらに、上記のエポキシ樹脂と各々の硬化剤をエポキシ基とアミノ基がモル比２：１になるように混合し、ステンレススチール製試験片に塗布した後、もう１枚のステンレススチール製試験片を圧着して加熱することにより接着した。これらの試料について引張試験を行うことにより、接着強度を測定した。
これらの結果を表１に示す。
These results are shown in Table 1.
表１の実施例１〜４から、ＡＢＡＰＱの含有率の増加に伴い熱変形温度が著しく向上していることがわかる。また実施例２〜４では熱変形温度が上昇しかつ接着強度が著しく改善されたことがわかる。本発明のエポキシ樹脂硬化物では３−置換キノキサリン構造を有するＡＢＡＰＱを用いて架橋密度を上げたことによって、上記のような高い耐熱性・高い接着力が得られた。 From Examples 1 to 4 in Table 1, it can be seen that the heat distortion temperature is remarkably improved as the ABAPQ content increases. In Examples 2 to 4, it can be seen that the heat distortion temperature increased and the adhesive strength was remarkably improved. In the cured epoxy resin of the present invention, the high heat resistance and high adhesive strength as described above were obtained by increasing the crosslinking density using ABAPQ having a 3-substituted quinoxaline structure.
本発明のエポキシ樹脂硬化物は、他の特性を維持しつつ、熱変形温度または、および接着強度が改善されているので、航空機、宇宙機器、自動車、スポーツ用品、レジャー用品などで耐熱性、接着強度が要求される用途で使用されることが期待される。 The epoxy resin cured product of the present invention has improved heat distortion temperature or adhesive strength while maintaining other properties, so that it has heat resistance and adhesion in aircraft, space equipment, automobiles, sports equipment, leisure goods, etc. It is expected to be used in applications where strength is required.
Claims (3)
前記芳香族アミン系硬化剤（Ｂ）はポリアミノフェニルキノキサリンであって、前記ポリアミノフェニルキノキサリンが、６−アミノ−２，３−ビス（ｐ−アミノフェニル）キノキサリン、６−アミノ−２，３−ビス（ｍ−アミノフェニル）キノキサリンまたは６−アミノ−２，３−ビス（アミノフェニル）キノキサリンであるエポキシ樹脂組成物。 An epoxy resin composition in which an epoxy resin (A) having two or more epoxy groups in one molecule and an aromatic amine curing agent (B) are blended with an epoxy group and an amino group in a molar ratio of 2: 1,
The aromatic amine curing agent (B) is polyaminophenylquinoxaline, and the polyaminophenylquinoxaline is 6-amino-2,3-bis (p-aminophenyl) quinoxaline, 6-amino-2,3-bis. An epoxy resin composition which is (m-aminophenyl) quinoxaline or 6-amino-2,3-bis (aminophenyl) quinoxaline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004148422A JP4765053B2 (en) | 2004-04-15 | 2004-04-15 | Heat resistant and high strength epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004148422A JP4765053B2 (en) | 2004-04-15 | 2004-04-15 | Heat resistant and high strength epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005298788A JP2005298788A (en) | 2005-10-27 |
| JP4765053B2 true JP4765053B2 (en) | 2011-09-07 |
Family
ID=35330717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004148422A Expired - Lifetime JP4765053B2 (en) | 2004-04-15 | 2004-04-15 | Heat resistant and high strength epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4765053B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005314624A (en) * | 2004-04-28 | 2005-11-10 | Chiba Univ | High-strength epoxy resin |
| JP5243151B2 (en) * | 2008-09-01 | 2013-07-24 | 旭化成イーマテリアルズ株式会社 | Epoxy resin curable composition, resin varnish, prepreg, metal-clad laminate and cured product |
| DE102011121133A1 (en) * | 2011-12-13 | 2013-06-13 | Kostal Kontakt Systeme Gmbh | Fluid-tight contact feedthrough |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4568940B2 (en) * | 1999-04-13 | 2010-10-27 | 日立化成工業株式会社 | Epoxy resin composition for sealing and electronic component device |
| JP2002080693A (en) * | 2000-06-28 | 2002-03-19 | Nippon Kayaku Co Ltd | Epoxy resin composition and its cured product |
| JP2005060481A (en) * | 2003-08-08 | 2005-03-10 | Chiba Univ | Heat resistant epoxy hardener |
-
2004
- 2004-04-15 JP JP2004148422A patent/JP4765053B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005298788A (en) | 2005-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2005508436A (en) | Heat resistant epoxy adhesive film | |
| DE19845607A1 (en) | Impact-resistant epoxy resin compositions | |
| JP2016501922A (en) | Toughened curable epoxy compositions for high temperature applications | |
| KR102341570B1 (en) | Epoxy resin compositions for pre-gel ovens | |
| KR20170088896A (en) | Epoxy adhesive, automotive member, and method for manufacturing same | |
| JP2021006633A (en) | Thermosetting resin composition, prepreg, and fiber-reinforced composite material and production method therefor | |
| JP2017527645A (en) | Adhesive composition | |
| KR102155006B1 (en) | Two part adhesive composition and cured product thereof and vehicle material adhesive method | |
| TW201012869A (en) | Epoxy resin composition and prepreg using the same, fiber-reinforced tubular composite made of prepreg and method of manufacturing the same, and fiber-reinforced composite plastic product | |
| EP2828860A2 (en) | Wash-off resistant epoxy adhesive composition and pre-gelled adhesive | |
| CN108699419A (en) | Including the composition of epobond epoxyn and aluminum slice and the method for preparing it | |
| WO2001029109A1 (en) | Hardener for epoxy resin and epoxy resin composition | |
| CN108291129A (en) | Can second rank adhesive composition | |
| JP4765053B2 (en) | Heat resistant and high strength epoxy resin | |
| JP2023538895A (en) | thermosetting resin composition | |
| JPH01158038A (en) | Latent curable accelerating agent for cyanate esters | |
| WO2019031576A1 (en) | Thermosetting resin composition and resin cured product | |
| JP2006131661A (en) | Epoxy resin composition and epoxy resin-cured material | |
| Bakar et al. | Effect of poly (amic acid) and polyimide on the adhesive strength and fracture toughness of epoxy resin | |
| Abbasi et al. | Synthesis, structure, and mechanical properties of castor oil‐based polyamidoamines toughened epoxy coatings | |
| JP2005314624A (en) | High-strength epoxy resin | |
| KR20180083662A (en) | Modified epoxy resin, preparation method thereof and thermosetting resin composition comprising the same | |
| Strzelec | Studies on the properties of epoxy resins cured with polythiourethanes | |
| JP4779112B2 (en) | Epoxy resin composition and cured epoxy resin | |
| JP2005060481A (en) | Heat resistant epoxy hardener |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070302 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20091118 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091215 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091228 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100511 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100515 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100707 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110517 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4765053 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| EXPY | Cancellation because of completion of term |