JPH05163474A - Epoxy resin composition suitable as structural adhesive - Google Patents

Epoxy resin composition suitable as structural adhesive

Info

Publication number
JPH05163474A
JPH05163474A JP33210691A JP33210691A JPH05163474A JP H05163474 A JPH05163474 A JP H05163474A JP 33210691 A JP33210691 A JP 33210691A JP 33210691 A JP33210691 A JP 33210691A JP H05163474 A JPH05163474 A JP H05163474A
Authority
JP
Japan
Prior art keywords
epoxy resin
composition
weight
parts
pts
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.)
Withdrawn
Application number
JP33210691A
Other languages
Japanese (ja)
Inventor
Yoshinobu Ohashi
橋 義 暢 大
Hideyuki Matsuda
田 秀 行 松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yokohama Rubber Co Ltd
Original Assignee
Yokohama Rubber Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Yokohama Rubber Co Ltd filed Critical Yokohama Rubber Co Ltd
Priority to JP33210691A priority Critical patent/JPH05163474A/en
Publication of JPH05163474A publication Critical patent/JPH05163474A/en
Withdrawn legal-status Critical Current

Links

Landscapes

  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

PURPOSE:To obtain an epoxy resin composition, containing specific two kinds of epoxy resins, a carboxyl group-containing butadiene-acrylonitrile liquid rubber and a curing agent and suitable as a structural adhesive excellent in heat- resistant adhesion. CONSTITUTION:The objective composition containing (A) 90-40 pts.wt. bisphenolic type epoxy resin expressed by formula I [R1 to R6 are H or lower alkyl; (n) is 0-16: (m) is 0-0.5], (B) 60-10 pts.wt. biphenyl type epoxy resin expressed by formula II [the total amount of the components (A) and (B) is 100 pts.wt.], (C) 5-30 pts. wt. carboxyl group-containing butadiene-acrylonitrile liquid rubber expressed by formula III [(x), (y) and (1) are the number of recurring units and (x/y) is (95/5) to (50/50); (1) is 0-50] and (D) a curing agent such as dicyandiamide. This composition is capable of exhibiting high adhesion even at high temperatures. Furthermore, a filter and a titanate coupling agent are preferably blended in this composition.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は自動車の車体組み立てに
おけるフード、ドアー、フェンダのヘム・フランジ部等
の接着あるいはウェルドボンド工法による車体骨格部品
の接着、複合材料の接着に用いられる構造用接着剤に適
したエポキシ樹脂組成物に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structural adhesive used for bonding hoods, doors, hem / flange parts of fenders, etc., in vehicle body assembly of automobiles, bonding vehicle body frame parts by the weld bond method, and bonding composite materials. The present invention relates to an epoxy resin composition suitable for.

【0002】[0002]

【従来の技術】従来、エポキシ樹脂をベースとする構造
用接着剤としてビスフェノール型エポキシ樹脂、ゴム変
性エポキシ樹脂、合成ゴム、ウレタン変性エポキシ樹
脂、充填剤および硬化剤からなる各種のエポキシ樹脂組
成物が知られている。
Conventionally, various epoxy resin compositions comprising bisphenol type epoxy resin, rubber modified epoxy resin, synthetic rubber, urethane modified epoxy resin, filler and curing agent have been used as structural adhesives based on epoxy resin. Are known.

【0003】構造物の使用形態から接着部に熱が加わり
高温にさらされるので、耐熱接着性に於いて高度のもの
が要求される。従来公知の構造用接着剤に用いられるエ
ポキシ樹脂組成物は必ずしもこの様な要求を完全に満た
すものでは無く改良の余地があった。
Since the bonded portion is exposed to high temperature due to heat applied to the structure depending on the usage pattern, a high degree of heat resistant adhesive property is required. Conventionally known epoxy resin compositions used for structural adhesives do not always completely meet such requirements, and there is room for improvement.

【0004】[0004]

【発明が解決しようとする課題】本発明は上記の様な高
温にさらされる構造部材の接着に用いても接着力を保持
する耐熱接着性に優れたエポキシ樹脂組成物を提供する
ことを目的とする。
SUMMARY OF THE INVENTION It is an object of the present invention to provide an epoxy resin composition having excellent heat resistant adhesiveness that retains adhesive strength even when used for bonding structural members exposed to high temperatures as described above. To do.

【0005】本発明者は上記目的を達成すべく研究を行
った結果、後記式(1)のビスフェノール型エポキシ樹
脂に後記式(2)のビフェニル型エポキシ樹脂を併用し
かつカルボキシル基含有ブタジエン・アクリロニトリル
液状ゴムを組成物のゴム成分として用いることにより、
剪断接着強度、剥離接着強度に優れると共に耐熱接着性
に於いても優れることを見い出した。そして又、これ等
の成分に加えて充填材及びチタン系カップリング剤を配
合すると接着力が更に向上すると共に耐水接着力も向上
することが明らかとなった。
As a result of research to achieve the above object, the present inventor has found that a bisphenol type epoxy resin of the following formula (1) is used in combination with a bisphenol type epoxy resin of the following formula (1) and a carboxyl group-containing butadiene / acrylonitrile is used. By using liquid rubber as the rubber component of the composition,
It was found that not only the shear adhesive strength and the peel adhesive strength are excellent, but also the heat resistant adhesiveness is excellent. It has also been clarified that when a filler and a titanium-based coupling agent are blended in addition to these components, the adhesive strength is further improved and the water resistant adhesive strength is also improved.

【0006】[0006]

【課題を解決するための手段】かくして本発明の目的は
下記式(1)で示されるビスフェノール型エポキシ樹脂
(A)90〜40重量部、下記式(2)で示されるビフ
ェニル型エポキシ樹脂(B)60〜10重量部(ここで
エポキシ樹脂(A)とエポキシ樹脂(B)との合計量は
100重量部となるようにする)、カルボキシル基含有
ブタジエン・アクリロニトリル液状ゴム(C)5〜30
重量部および硬化剤(D)を含む構造用接着剤に適した
エポキシ樹脂組成物によって達成され、更に上記組成物
に充填剤及びチタネートカップリング剤を配合すること
により接着強度及び耐水接着強度が向上したエポキシ樹
脂組成物が得られる。
The object of the present invention is thus 90 to 40 parts by weight of a bisphenol type epoxy resin (A) represented by the following formula (1) and a biphenyl type epoxy resin (B) represented by the following formula (2). ) 60 to 10 parts by weight (here, the total amount of the epoxy resin (A) and the epoxy resin (B) is 100 parts by weight), carboxyl group-containing butadiene-acrylonitrile liquid rubber (C) 5 to 30
Achieved by an epoxy resin composition suitable for structural adhesives containing parts by weight and a curing agent (D), and by further adding a filler and a titanate coupling agent to the composition, the adhesive strength and the water resistant adhesive strength are improved. The obtained epoxy resin composition is obtained.

【化2】 (上記式でR1 〜R6 は各々独立に水素原子又は低級ア
ルキル基を示し、nは0〜16の数は、mは0〜0.5
の数である) 以下、本発明を詳述する。
[Chemical 2] (In the above formula, R 1 to R 6 each independently represent a hydrogen atom or a lower alkyl group, n is a number of 0 to 16, m is 0 to 0.5.
The following is a detailed description of the present invention.

【0007】ビスフェノール型エポキシ樹脂(A) ビスフェノール型エポキシ樹脂(A)は式(1)で示さ
れる構造を有し、例えば2,2−ビス(4−ヒドロキシ
フェニル)プロパン:ビスフェノールA、2,2−ビス
(4−ヒドロキシフェニル)エタン:ビスフェノールA
D、ビス(4−ヒドロキシフェニル)メタン:ビスフェ
ノールFなどで例示されるビスフェノールとエピクロル
ヒドリンから誘導されるエポキシ樹脂を例示的に挙げる
ことができるが、ビスフェノールA型エポキシ樹脂が最
も好ましい。
Bisphenol type epoxy resin (A) The bisphenol type epoxy resin (A) has a structure represented by the formula (1), for example, 2,2-bis (4-hydroxyphenyl) propane: bisphenol A, 2,2 -Bis (4-hydroxyphenyl) ethane: Bisphenol A
Epoxy resins derived from bisphenol and epichlorohydrin exemplified by D, bis (4-hydroxyphenyl) methane: bisphenol F and the like can be exemplified, but bisphenol A type epoxy resin is most preferable.

【0008】エポキシ樹脂(A)の数平均分子量は35
0〜5000、特には、350〜2000が好ましい。
あまり分子量の高いものは、エポキシ基の含量が低いの
で硬化後の架橋密度が低く、十分な剪断接着強度を得ら
れないと共に接着剤の粘度が大となり塗布作業等が困難
となる。
The number average molecular weight of the epoxy resin (A) is 35.
0-5000, especially 350-2000 are preferable.
If the molecular weight is too high, the content of epoxy groups is low and the crosslink density after curing is low, so that sufficient shear adhesive strength cannot be obtained, and the viscosity of the adhesive becomes large, which makes the coating operation difficult.

【0009】ビフェニル型エポキシ樹脂(B) ビフェニル型エポキシ樹脂(B)は前記式(2)で示さ
れる構造を有し、例えば4,4’−ジヒドロキシビフェ
ニル、4,4’- ジヒドロキシ−3,3’、5,5’−
テトラメチルビフェニルなどのジヒドロキシビフェニル
類とエピクロルヒドロリンから誘導されるものが例示さ
れ、4,4’- ジヒドロキシ−3,3’、5,5’−テ
トラメチルビフェニルから誘導されるものが好ましい。
Biphenyl type epoxy resin (B) The biphenyl type epoxy resin (B) has a structure represented by the above formula (2), and is, for example, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3. ', 5, 5'-
Examples are those derived from dihydroxybiphenyls such as tetramethylbiphenyl and epichlorohydroline, and those derived from 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl are preferred.

【0010】このビフェニル型エポキシ樹脂(B)は前
記ビスフェノール型エポキシ樹脂(A)と併用すること
により高温に於ける接着性に優れる本発明のエポキシ樹
脂組成物が得られることになる。しかしながらエポキシ
樹脂(B)の過剰の配合は組成物の粘度が上昇したり、
ビフェニル型エポキシ樹脂は結晶性が高いために、析出
することがあり、組成物の接着面への塗布作業性が低下
する。この意味に於いてエポキシ樹脂(B)の配合量
は、エポキシ樹脂(A)との重量比((A)/(B))
が90/10〜40/60、好ましくは70/30〜5
0/50となるように配合する。
When this biphenyl type epoxy resin (B) is used in combination with the bisphenol type epoxy resin (A), the epoxy resin composition of the present invention having excellent adhesiveness at high temperatures can be obtained. However, when the epoxy resin (B) is excessively compounded, the viscosity of the composition increases,
Since the biphenyl type epoxy resin has high crystallinity, it may be deposited and the workability of applying the composition to the adhesive surface is deteriorated. In this sense, the blending amount of the epoxy resin (B) is the weight ratio with the epoxy resin (A) ((A) / (B)).
Is 90/10 to 40/60, preferably 70/30 to 5
It is blended so as to be 0/50.

【0011】カルボキシル基含有ブタジエン・アクリロ
ニトリル液状ゴム(C) 好ましい液状ゴム(C)は下記構造式(3)で示される
カルボキシル基が末端に結合しているものである。
Carboxyl group-containing butadiene acrylo
Nitrile liquid rubber (C) A preferable liquid rubber (C) is one in which a carboxyl group represented by the following structural formula (3) is bonded to the terminal.

【0012】[0012]

【化3】 (ここでx,y,lは繰り返し単位数でx/yは95/
5〜50/50、lは10〜50である。)
[Chemical 3] (Where x, y and l are the number of repeating units and x / y is 95 /
5-50 / 50, 1 is 10-50. )

【0013】液状ゴム(c)はそれ自体公知の方法で製
造可能でもあるし、また、宇部興産(株)のHycar
CTBN 1300×31、CTBN 1300×
8、CTBN 1300×13、CTBN 1300×
9として市販され、容易に入手できる。液状ゴム(C)
のアクリロニトリルの含量の増大と共にエポキシ樹脂
(A)との相溶性が大きくなるが、あまり多いとゴム的
性質を失うので上記式(2)においてx/y(モル比)
は90/10〜70/30が好ましい。
The liquid rubber (c) can be produced by a method known per se, or it can be produced by Ube Industries, Ltd. Hycar.
CTBN 1300x31, CTBN 1300x
8, CTBN 1300x13, CTBN 1300x
It is marketed as 9 and is easily available. Liquid rubber (C)
The compatibility with the epoxy resin (A) increases with an increase in the content of acrylonitrile, but if it is too much, the rubber-like property is lost, so x / y (molar ratio) in the above formula (2)
Is preferably 90/10 to 70/30.

【0014】この液状ゴム(C)を適切な量配合すると
エポキシ樹脂(A)および(B)と硬化時に反応してエ
ポキシ樹脂の剛直な高分子鎖と結合し、硬化物に可撓性
を与え、剥離接着強度を大ならしめる。その意味に於い
て液状ゴム(C)の配合量はエポキシ樹脂(A)と変性
エポキシ樹脂(B)の合計100重量部に対して5〜5
0重量部、好ましくは10〜30重量部である。
When this liquid rubber (C) is blended in an appropriate amount, it reacts with the epoxy resins (A) and (B) during curing to bond with the rigid polymer chains of the epoxy resin, giving flexibility to the cured product. , Increases peel adhesion strength. In that sense, the compounding amount of the liquid rubber (C) is 5 to 5 per 100 parts by weight of the total of the epoxy resin (A) and the modified epoxy resin (B).
It is 0 part by weight, preferably 10 to 30 parts by weight.

【0015】硬化剤(D) 本発明で使用される硬化剤(D)は硬化温度100〜2
00℃の温度範囲でエポキシ樹脂の硬化反応が実質的に
開始するものであれば如何なるものであっても良いが、
具体的にはジシアンジアミド、イソフタル酸ジヒドラジ
ド、N,N’−ジアルキル尿素誘導体、N,N’−ジア
ルキルチオ尿素誘導体などの潜在性硬化剤、4,4’−
ジアミノジフェニルメタン、4,4’−ジアミノジフェ
ニルスルホンなどの芳香族ジアミン系硬化剤、その他イ
ミダゾールおよびその誘導体を挙げることができるが、
なかでもジシアンジアミド、N,N’−ジアルキル尿素
誘導体などが好ましく使用できる。硬化剤の使用量は硬
化剤の種類およびエポキシ基の組成物中に於ける存在量
を考慮して適切に定めることができるが一般的には、エ
ポキシ樹脂((A)+(B))100重量部に対して1
〜30重量部程度配合される。また、必要に応じて硬化
促進剤を併用できる。
Curing Agent (D) The curing agent (D) used in the present invention has a curing temperature of 100 to 2
Any substance may be used as long as the curing reaction of the epoxy resin substantially starts in the temperature range of 00 ° C.
Specifically, latent curing agents such as dicyandiamide, isophthalic acid dihydrazide, N, N'-dialkylurea derivatives, N, N'-dialkylthiourea derivatives, 4,4'-
Aromatic diamine-based curing agents such as diaminodiphenylmethane and 4,4′-diaminodiphenylsulfone, and other imidazoles and derivatives thereof can be mentioned.
Among them, dicyandiamide, N, N′-dialkylurea derivative and the like can be preferably used. The amount of the curing agent used can be appropriately determined in consideration of the type of the curing agent and the amount of the epoxy group present in the composition, but generally, the epoxy resin ((A) + (B)) 100 1 to parts by weight
About 30 parts by weight is blended. Further, a curing accelerator can be used in combination if necessary.

【0016】本発明の組成物に於いては上記(A)〜
(D)の成分に加えて、接着強度の向上及び耐水接着強
度の向上の目的で充填材及びチタネートカップリング材
を配合することができる。用いることのできる充填材と
しては炭酸カルシウム、水酸化アルミニウム、酸チタ
ン、硫酸バリウム、カルシウムメタシリケート、カーボ
ン繊維、ガラス繊維、などを挙げることができる。これ
等の充填剤は単独又は混合して用いることができる。こ
の様な充填材の配合により本発明の組成物の接着強度及
び耐熱性が向上するが、そのためには充填材はエポキシ
樹脂((A)+(B))100重量部に対して通常10
〜100重量部好ましくは30〜60重量部配合され
る。過剰の配合は組成物の調製、被着面への塗布などの
工程に於いて作業性が悪化する。過少の配合は当然なが
ら前記の効果が発現しない。
In the composition of the present invention, the above (A) to
In addition to the component (D), a filler and a titanate coupling material can be blended for the purpose of improving the adhesive strength and the water resistant adhesive strength. Examples of fillers that can be used include calcium carbonate, aluminum hydroxide, titanium oxide, barium sulfate, calcium metasilicate, carbon fiber, and glass fiber. These fillers can be used alone or as a mixture. By compounding such a filler, the adhesive strength and heat resistance of the composition of the present invention are improved. For that purpose, the filler is usually 10 per 100 parts by weight of the epoxy resin ((A) + (B)).
-100 parts by weight, preferably 30-60 parts by weight. If the composition is excessive, workability is deteriorated in the steps of preparing the composition, coating the surface to be adhered and the like. If the blending amount is too small, the above-mentioned effects cannot be obtained.

【0017】使用できるチタネートカップリング剤とし
ては、テトラオクチルビス(ジドデシルホスファイト)
チタネート、イソプロピル(N−アミノエチル−アミノ
エチル)チタネート、イソプロピルトリス(ジオクチル
ピロホスフェート)チタネート、イソプロピルトリイソ
ステアロイルチタネート、テトラ(2,2−ジアリルオ
キシメチル−1−ブチル)ビス(ジトリデシル)ホスフ
ァイトチタネート、ビス(ジオクチルピロホスフェー
ト)エチレンチタネート、テトライソプロピルビス(ジ
オクチルホスファイト)チタネート、イソプロピルトリ
クミルフェニルチタネート、イソプロピルトリ(ジオク
チルホスフェート)チタネート、イソプロピルイソステ
アロイルジアクリルチタネート、イソプロピルトリデシ
ルベンゼンスルホニルチタネート、イソプロピルジメタ
クリルイソステアロイルチタネート、イソプロピルトリ
オクタノイルチタネートを挙げることができる。この様
なチタネートカップリング剤が配合された本発明のエポ
キシ樹脂組成物は、その接着強度の耐水性に於いて優れ
る。即ち、水中に浸漬しても又、高温多湿の雰囲気下に
放置しても接着強度を維持する。耐水接着強度試験後の
試料の破壊状態を観察すると、本発明の組成物の硬化物
の凝集破壊が生じており、界面破壊はほとんど発生して
いない。このことは長期にわたる耐水接着強度の信頼性
を保証する。
The titanate coupling agent that can be used is tetraoctyl bis (didodecyl phosphite).
Titanate, isopropyl (N-aminoethyl-aminoethyl) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl triisostearoyl titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate , Bis (dioctyl pyrophosphate) ethylene titanate, tetraisopropyl bis (dioctyl phosphite) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tridecylbenzene sulfonyl titanate, isopropyl di Methacryl isostearoyl titanate, isopropyl trioctanoyl titanate Mention may be made of the door. The epoxy resin composition of the present invention containing such a titanate coupling agent is excellent in its adhesive strength and water resistance. That is, the adhesive strength is maintained even when immersed in water or left in a hot and humid atmosphere. When the fracture state of the sample after the water resistant adhesive strength test is observed, cohesive failure of the cured product of the composition of the present invention occurs, and interface failure hardly occurs. This guarantees long-term reliability of the water resistant bond strength.

【0018】特に充填材が炭酸カルシュウム、カルシュ
ウムメタシリケートのとき、チタネートカップリング剤
としてテトラオクチルビス(ジトリデシルホスファイ
ト)チタネートをもちいると耐水性の向上は著しい。
Especially when the filler is calcium carbonate or calcium metasilicate, the use of tetraoctyl bis (ditridecyl phosphite) titanate as a titanate coupling agent brings about a remarkable improvement in water resistance.

【0019】チタネートカップリング剤の添加量は、無
機充填材に対して通常0.1〜10重量%添加する。過
剰の添加は接着性の低下をもたらす。チタネートカップ
リング剤の混合は、他の配合剤と共にいっしょに混合す
ることもできるが、あらかじめ充填材と混合する態様も
好ましい。
The titanate coupling agent is usually added in an amount of 0.1 to 10% by weight based on the inorganic filler. Excessive addition results in poor adhesion. The titanate coupling agent can be mixed together with other compounding agents, but it is also preferable to mix it with the filler in advance.

【0020】なお、本発明の組成物には、本発明の目的
の達成を損なわない範囲で、ウレタン変性エポキシ樹脂
を少量配合することもできる。
The composition of the present invention may contain a small amount of a urethane-modified epoxy resin as long as the object of the present invention is not impaired.

【0021】[0021]

【実施例】以下、実施例を以って本発明を具体的に説明
する。表1に記載している配合比率で各成分を混合し、
3本ロールで十分に分散させて接着性を得た。この接着
剤を被着体(鋼板SCP−28C(防錆油面処理)、引
張剪断接着試験用:25×150×1.6mmT型剥離
試験用:25×200×0.8mm)に厚さ0.15m
mに塗布し180℃、20分の硬化条件にて硬化接着
し、得られた試験片につき引張剪断接着試験(ラップ長
10mm、引張速度10mm/min)および剥離強度試験
(引張速度200mm/min)を20℃雰囲気下に行った。
EXAMPLES The present invention will be specifically described below with reference to examples. Mix the components in the mixing ratios listed in Table 1,
It was sufficiently dispersed with three rolls to obtain adhesiveness. This adhesive is applied to an adherend (steel plate SCP-28C (rust-preventing oil surface treatment), tensile shear adhesion test: 25 × 150 × 1.6 mm, T-type peeling test: 25 × 200 × 0.8 mm) with a thickness of 0. .15m
m and applied and cured and adhered under the curing conditions of 180 ° C. for 20 minutes, and the resulting test pieces are subjected to a tensile shear adhesion test (lap length 10 mm, pulling speed 10 mm / min) and peel strength test (pulling speed 200 mm / min). Was performed in an atmosphere of 20 ° C.

【0022】一方耐熱接着性の試験は、引張剪断接着試
験を120℃の雰囲気下で行うことによって行った。結
果を表1に示した。
On the other hand, the heat resistance adhesion test was carried out by conducting a tensile shear adhesion test in an atmosphere of 120 ° C. The results are shown in Table 1.

【0023】実施例1〜3はビフェニル型エポキシ樹脂
の添加量を変化させた例、実施例4〜7は液状ゴムの量
を変化させた例であり、常態の接着性を損なうことな
く、120℃の剪断接着強度を100kg/cm2以上とする
ことができた。比較例1、2はビフェニル型エポキシ樹
脂を配合しないか過少の場合の例であり耐熱接着強度は
小さい。比較例3は液状ゴムの添加量が多い場合で常態
での接着性が低下し、耐熱接着強度も低下した。
Examples 1 to 3 are examples in which the addition amount of the biphenyl type epoxy resin was changed, and Examples 4 to 7 were examples in which the amount of liquid rubber was changed, and 120% without impairing the normal adhesiveness. The shear adhesive strength at 0 ° C. could be 100 kg / cm 2 or more. Comparative Examples 1 and 2 are examples in which no biphenyl type epoxy resin was blended or when the amount was too small, and the heat resistant adhesive strength was low. In Comparative Example 3, when the amount of the liquid rubber added was large, the adhesiveness in the normal state was lowered and the heat resistant adhesive strength was also lowered.

【0024】[0024]

【表1】 [Table 1]

【0025】[0025]

【発明の効果】以上詳述した本発明の(A)〜(D)成
分からなるエポキシ樹脂組成物は、120℃の高温に於
いても高接着性を示し、更に充填剤及びチタネートカッ
プリング剤を配合したエポキシ樹脂組成物は、高接着強
度で耐水性を有している。従って、本発明のエポキシ樹
脂組成物は、構造用接着剤として優れ、特には高温雰囲
気下に晒される部材の接着に適切に用いることができ
る。
The epoxy resin composition comprising the components (A) to (D) of the present invention described in detail above exhibits high adhesiveness even at a high temperature of 120 ° C., and further, a filler and a titanate coupling agent. The epoxy resin composition containing is highly adhesive and has water resistance. Therefore, the epoxy resin composition of the present invention is excellent as a structural adhesive and can be suitably used particularly for adhesion of members exposed to a high temperature atmosphere.

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】下記式(1)で示されるビスフェノール型
エポキシ樹脂(A)90〜40重量部、下記式(2)で
示されるビフェニル型エポキシ樹脂(B)60〜10重
量部(ここでエポキシ樹脂(A)とエポキシ樹脂(B)
との合計量は100重量部となるようにする)、カルボ
キシル基含有ブタジエン・アクリロニトリル液状ゴム
(C)5〜30重量部および硬化剤(D)を含む構造用
接着剤に適したエポキシ樹脂組成物。 【化1】 (上記式でR1 〜R6 は各々独立に水素原子又は低級ア
ルキル基を示し、nは0〜16の数は、mは0〜0.5
の数である)
1. A bisphenol type epoxy resin (A) represented by the following formula (1) 90 to 40 parts by weight, and a biphenyl type epoxy resin (B) represented by the following formula (2) 60 to 10 parts by weight (epoxy here). Resin (A) and epoxy resin (B)
And a total amount of 100 parts by weight), an epoxy resin composition suitable for a structural adhesive containing 5 to 30 parts by weight of a carboxyl group-containing butadiene-acrylonitrile liquid rubber (C) and a curing agent (D). .. [Chemical 1] (In the above formula, R 1 to R 6 each independently represent a hydrogen atom or a lower alkyl group, n is a number of 0 to 16, m is 0 to 0.5.
Is the number of)
【請求項2】充填剤及びチタネートカップリング剤が更
に配合されている請求項1記載のエポキシ樹脂組成物。
2. The epoxy resin composition according to claim 1, further comprising a filler and a titanate coupling agent.
JP33210691A 1991-12-16 1991-12-16 Epoxy resin composition suitable as structural adhesive Withdrawn JPH05163474A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP33210691A JPH05163474A (en) 1991-12-16 1991-12-16 Epoxy resin composition suitable as structural adhesive

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP33210691A JPH05163474A (en) 1991-12-16 1991-12-16 Epoxy resin composition suitable as structural adhesive

Publications (1)

Publication Number Publication Date
JPH05163474A true JPH05163474A (en) 1993-06-29

Family

ID=18251221

Family Applications (1)

Application Number Title Priority Date Filing Date
JP33210691A Withdrawn JPH05163474A (en) 1991-12-16 1991-12-16 Epoxy resin composition suitable as structural adhesive

Country Status (1)

Country Link
JP (1) JPH05163474A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7182381B2 (en) 2003-10-20 2007-02-27 Mitsubishi Jidosha Kogyo Kabushiki Kaisha Joint structure for vehicle body members
JP2007091797A (en) * 2005-09-27 2007-04-12 Dainippon Ink & Chem Inc Urethane-modified epoxy resin composition and cured product thereof
JP2010507709A (en) * 2006-10-24 2010-03-11 シーカ・テクノロジー・アーゲー Derivatized solid epoxy resin and use thereof
JP2010507708A (en) * 2006-10-24 2010-03-11 シーカ・テクノロジー・アーゲー Thermosetting epoxy resin composition containing block polyurethane prepolymer
JP2010507707A (en) * 2006-10-24 2010-03-11 シーカ・テクノロジー・アーゲー Thermosetting epoxy resin composition comprising one blocked and one epoxide terminated polyurethane prepolymer
JP2011105102A (en) * 2009-11-16 2011-06-02 Honda Motor Co Ltd Joint structure of vehicle-body panel
WO2015068659A1 (en) 2013-11-05 2015-05-14 旭硝子株式会社 Adhesive agent

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7182381B2 (en) 2003-10-20 2007-02-27 Mitsubishi Jidosha Kogyo Kabushiki Kaisha Joint structure for vehicle body members
CN1329236C (en) * 2003-10-20 2007-08-01 三菱自动车工业株式会社 Coupling structure of vehicle body parts
DE102004050933B4 (en) * 2003-10-20 2014-05-22 Mitsubishi Jidosha Kogyo K.K. Connection structure for vehicle body elements
JP2007091797A (en) * 2005-09-27 2007-04-12 Dainippon Ink & Chem Inc Urethane-modified epoxy resin composition and cured product thereof
JP2010507709A (en) * 2006-10-24 2010-03-11 シーカ・テクノロジー・アーゲー Derivatized solid epoxy resin and use thereof
JP2010507708A (en) * 2006-10-24 2010-03-11 シーカ・テクノロジー・アーゲー Thermosetting epoxy resin composition containing block polyurethane prepolymer
JP2010507707A (en) * 2006-10-24 2010-03-11 シーカ・テクノロジー・アーゲー Thermosetting epoxy resin composition comprising one blocked and one epoxide terminated polyurethane prepolymer
US8202920B2 (en) 2006-10-24 2012-06-19 Sika Technology Ag Heat-curable epoxy resin composition comprising a blocked polyurethane prepolymer
JP2011105102A (en) * 2009-11-16 2011-06-02 Honda Motor Co Ltd Joint structure of vehicle-body panel
WO2015068659A1 (en) 2013-11-05 2015-05-14 旭硝子株式会社 Adhesive agent
KR20160082505A (en) 2013-11-05 2016-07-08 아사히 가라스 가부시키가이샤 Adhesive agent
US10253221B2 (en) 2013-11-05 2019-04-09 AGC Inc. Adhesive

Similar Documents

Publication Publication Date Title
KR101467609B1 (en) Crash durable epoxy adhesives with very low sensitivity to temperature variations
KR101467602B1 (en) Heat-resistant structural epoxy resins
EP1155082B1 (en) Shock-resistant epoxide resin compositions
JP3294268B2 (en) Reactive hot melt adhesive
JP2002526618A (en) Impact resistant epoxy resin composition
SK282304B6 (en) One-component, in hot hardenable mixture based on liquid caoutchoucs, its production method and use
BRPI0506523B1 (en) ADHESIVE EPOXY COMPOSITION AND USE OF AN ADHESIVE EPOXY COMPOSITION
CA1255041A (en) Epoxy resin coating composition
EP0309903B1 (en) Epoxide and rubber based curable compositions having good adhesion direct to metal
JPS59108072A (en) Thermosetting adhesive sheet having cold tackiness
JPH05148337A (en) Epoxy resin composition suitable for structural adhesive
JPH05163474A (en) Epoxy resin composition suitable as structural adhesive
JP4060440B2 (en) Thermosetting pressure sensitive adhesive film
JPH05163475A (en) Epoxy resin composition suitable as structural adhesive
CA1339566C (en) Adhesive film
JPS62236879A (en) Epoxy-resin-base adhesive composition
JPH0288684A (en) Bonding and liquid adhesive used therefor
JPS5978282A (en) Thermosetting adhesive composition
JPH02189329A (en) Epoxy resin composition
JPH0231732B2 (en) EHOKISHIJUSHISOSEIBUTSU
JPH05302073A (en) Adhesive epoxy resin composition
JPH11246827A (en) Heat curing type adhesive sheet
JP3422066B2 (en) Viscoelastic resin for vibration damping material and composition thereof
JPS62201983A (en) Epoxy resin adhesive composition
JPH03167283A (en) Adhesive composition for aluminum alloy

Legal Events

Date Code Title Description
A300 Withdrawal of application because of no request for examination

Free format text: JAPANESE INTERMEDIATE CODE: A300

Effective date: 19990311