JPH0334513B2 - - Google Patents
Info
- Publication number
- JPH0334513B2 JPH0334513B2 JP58063655A JP6365583A JPH0334513B2 JP H0334513 B2 JPH0334513 B2 JP H0334513B2 JP 58063655 A JP58063655 A JP 58063655A JP 6365583 A JP6365583 A JP 6365583A JP H0334513 B2 JPH0334513 B2 JP H0334513B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- parts
- adhesive
- bisphenol
- diglycidyl ether
- 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 claims description 41
- 229920000647 polyepoxide Polymers 0.000 claims description 41
- 230000001070 adhesive effect Effects 0.000 claims description 31
- 239000000853 adhesive Substances 0.000 claims description 29
- 238000007259 addition reaction Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 9
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 6
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 claims description 5
- 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 description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims 1
- 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
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 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 4
- 238000011156 evaluation Methods 0.000 description 4
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- -1 sheet Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 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 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-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
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 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
- 210000005252 bulbus oculi Anatomy 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007527 glass casting Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Description
【発明の詳細な説明】
本発明は、低温での速硬化性及び貯蔵安定性を
有し、その硬化物の接着性、耐熱性、耐水性、機
械的強度に優れており、とくに構造用接着剤とし
て適性を有する一液型エポキシ樹脂接着剤組成物
に関するものである。
エポキシ樹脂は電気絶縁性、耐熱性、防食性、
接着性能の優れた特性を有しており、その使用形
態も液状、ペースト状、シート状、粉末状と選べ
るため各種の分野で使用されている。また各種の
配合が可能であり、使用目的に応じて硬化物特性
を種々変えるのが可能であることも、幅広く使用
されている一つの理由となつている。しかしなが
ら、一般にエポキシ樹脂は高温で長時間の硬化処
理条件を必要とするという欠点を有しており、低
温硬化のための方法が種々提案されている。例え
ば、硬化剤に、芳香族アミン化合物、イミダゾー
ル化合物などを使用する方法が提案されている
が、これら高活性の硬化剤を含むエポキシ樹脂組
成物は、130℃以下の低温でも硬化させることは
できるものの、他方金属素材に対する接着性なら
びに硬化物の機械的強度が低下し、加えて該樹脂
組成物の貯蔵安定性も数日以下と極めて劣るもの
である。
本発明の目的は貯蔵安定性があり130℃以下の
低温で速かに硬化し、かつその硬化物が良好な接
着性、耐熱性、耐水性及び機械的強度を有する一
液型エポキシ樹脂接着剤組成物を提供することに
ある。
本発明の一液型エポキシ樹脂接着剤組成物は、
(A) 少なくとも一種の芳香族ポリアミンと、エポ
キシ当量が200以下であるビスフエノールＡジ
グリシジルエーテルおよびまたはビスフエノー
ルＦジグリシジルエーテルとを１／３〜１／10
の化学量論量で反応させて得られる数平均分子
量1000〜4000を有する付加反応生成物、
(B) ゴム質ポリマー、
(C) ジシアンジアミド及び
(D) 一般式（）で示される化合物
（但し、式中X1およびX2はそれぞれ−OCH3、
−NO2、Cl又は水素原子である）を必須成分
として含有することを特徴とするものである。
本発明で用いる芳香族ポリアミンとしては、ｏ
−フエニレンジアミン、ｍ−フエニレンジアミ
ン、４，4′−メチレンジアニリン、４，4′−ジア
ミノジフエニルスルホン、３，3′−ジアミノジフ
エニルスルホン等が挙げられ、これらは単独であ
るいは混合して用いてもよい。
また、ビスフエノールＡジグリシジルエーテル
およびまたはビスフエノールＦジグリシジルエー
テルのエポキシ当量は200以下のものを使用する
必要があり、エポキシ当量が200を越えるものを
用いると、芳香族ポリアミンとの付加反応物の粘
度が極めて高くなり、接着剤としてのとりあつか
いが困難になるとともに、貯蔵安定性も著しく低
下するので好ましくない。前記付加反応物は上記
のビスフエノールＡジグリシジルエーテルおよ
び／またはビスフエノールＦジグリシジルエーテ
ルと適当な化学量論量の芳香族ポリアミンとを熱
処理し適当な粘度に到達したとき反応を停止する
ことにより得ることができる。ここでその化学量
論は極めて重要であり、芳香族ポリアミンとエポ
キシ樹脂の量論量比が１／３〜１／10の範囲にあ
る必要がある。量論比が１／３をこえると芳香族
ポリアミンが過剰となり、えられる変性エポキシ
樹脂の粘度が高くなりすぎ作業性と貯蔵安定性が
低下するので望ましくなく、また１／10未満では
芳香族ポリアミンが不足となり接着性及び硬化物
の耐熱性、強度が低下するので好ましくない。こ
こで化学量論量はエポキシ基１個がＮ−Ｈ結合１
個に相当する当量を意味する。
上記の付加反応はその反応生成物が所望の分子
量に到達する様に反応当量、処理温度、時間など
を制御することにより行われる。エポキシ樹脂過
剰の反応では熱処理温度を高くし処理時間を短か
くすることができるが、エポキシ樹脂が少過剰の
反応ではゲル化し易いため処理温度は低く設定さ
れる。
付加反応生成物はその数平均分子量が1000〜
4000の範囲にあることが望ましい。数平均分子量
が1000未満では、低温硬化性が悪化し、同時に接
着性も低下する。他方、4000を越えると極めて高
粘度となり、作業性の低下を招くばかりでなく、
貯蔵安定性が悪化するので好ましくない。
かくして得られる変性エポキシ樹脂は、通常の
エポキシ樹脂組成物と比較し、低温硬化性に優
れ、かつ硬化物の接着強度、耐水性、耐熱性も極
めて良好であるという特徴を発現するものであ
る。
本発明の第二の成分であるゴム質ポリマーとし
ては、ポリブタジエン、アクリロニトリルとブタ
ジエンとのコポリマー及びこれらの末端をカルボ
キシル化したもの等、種々あげられるが、とくに
本発明の変性エポキシ樹脂との相溶性あるいは金
属素材に対する接着性の点から分子両末端にカル
ボキシル基を有する、ブタジエン−アクリロニト
リル樹脂（以下CTBNと略称する）及び該
CTBNとエポキシ樹脂とを反応させ得られる
CTBN変性エポキシ樹脂が好適である。このゴ
ム質ポリマーの含有率としては、(A)成分と(B)成分
の合計に対して３〜30重量％が好ましく、３重量
％未満では、ゴム質ポリマー添加によるいわゆる
応力緩和効果が得られず接着力が不足し、他方30
重量％をこえると変性エポキシ樹脂との相溶性が
低下し、貯蔵安定性の低下を招き、同時に、耐熱
性等が低下する。
次に、第三の成分として用いるジシアンジアミ
ドは硬化剤的効能を発揮するばかりでなく、金属
素材に対する接着性及び硬化接着剤層の耐熱性と
機械的強度の向上に寄与する効果をも発揮する。
しかし、ジシアンジアミド単独で十分な接着力を
得るためには、150℃以上の硬化温度を必要とす
るが、本発明の第四の成分である一般式
で表わされる化合物（但し、X1及びX2は前記の
とおり）、例えばジクロロフエニル−１，１−ジ
メチルウレア、クロロフエニル−１，１−ジメチ
ルウレアなどの尿素化合物を硬化促進剤として併
用することより、130℃以下の低温硬化が可能と
なりかつ貯蔵安定性も良好な接着剤が得られる。
ここで硬化促進剤の添加量は成分ＡとＢの合計
100重量部に対し１〜８部の範囲が好ましく、ジ
シアンジアミドの添加量は成分ＡとＢの合計100
重量部に対して２〜10部の範囲が好ましい。また
成分Ｃと成分Ｄの使用割合はＣ／Ｄ重量比で10／
１〜１／１の範囲が好ましい。
本発明は該変性エポキシ樹脂を主体とする接着
剤に関するものであるが、通常のエポキシ樹脂す
なわち未変性のビスフエノールＡ型エポキシ樹
脂、ビスフエノールＦ型エポキシ樹脂、フエノー
ルノボラツク型エポキシ樹脂及びこれらの樹脂以
外のエポキシ樹脂、例えば脂肪族エポキシ樹脂、
脂環式エポキシ樹脂、ポリブタジエン変性エポキ
シ樹脂、長鎖エステル型エポキシ樹脂、芳香族ジ
カルボン酸系エポキシ樹脂、クレゾールノボラツ
ク型エポキシ樹脂等を、本発明の目的をそこなわ
ない範囲で使用しても何らさしつかえない。
なお、本発明を実施するに当たつては、本発明
の目的を害しない範囲で例えばナイロン樹脂、ア
クリル樹脂等の熱可塑樹脂、無水シリカ、アルミ
ナなどの顔料等を添加してもさしつかえない。
以下、実施例により本発明を更に説明する。な
お、実施例中「部」とあるのは重量部の意であ
る。
実施例 １
ビスフエノールＦジグリシジルエーテル（エポ
キシ当量175、エポキシ樹脂エピコート807、シエ
ル化学登録商標）100部に４，4′−ジアミノジフ
エニルスルホン７部を加えて、撹拌機つき加熱容
器に入れて、内部温度100℃で撹拌下10時間付加
反応せしめた後、冷却した。ここで得られた付加
反応生成物Ａ（数平均分子量1440）45部に対して、
エポキシ樹脂（エピコート＃825、油化シエル社
製）45部、長鎖エステル型エポキシ樹脂（ST−
2PG、岡村製油(株)製）２部、カルボキシ変性ブタ
ジエン−アクリロニトリル樹脂（CTBN1300×
13、宇部興産製）８部、ジシアンジアミド８部及
び３−（３，４−ジクロロフエニル）１，１−ジ
メチルウレア（カーメツクスＤ、デユポン製）２
部を加え均一に混合して一液型エポキシ樹脂接着
剤を得た。
この接着剤の諸性能を下記の方法で評価した：
JIS−Ｋ−6848、6850に従い25×100×２mmの
SPCC軟鋼板の、12.5mmラツプ部分をサンドペー
パー（＃240）により研摩し、アセトンで充分脱
脂する。処理した鋼板に上記の接着剤を片面に均
一に塗り、処理したもう一枚の鋼板と重ね合せ
る。
次にズレを起さぬ様にして、試料を、５cm巾の
目玉クリツプ２個で固定し、表−１の所定条件で
硬化し接着試料とした。常温（室温）放置後、引
張試験機（オートグラフ、DSS−2000）により印
張速度５mm／minで引張せん断接着強さを求め
た。
次に、熱変形温度（HDT）測定用の試料は、
あらかじめ150℃に予熱しておいたガラス注型枠
（50×150×２mmのガラス板２枚、離型紙として全
面にセロハン使用、スペーサーは厚さ３mmのシリ
コンゴムを使用）に予備加熱して粘度を下げた接
着剤を流し込み注型後、150℃×30min硬化して
脱わく後、約12.7×127×３mmのサイズに切削加
工した。HDT測定は、JIS−Ｋ−6919に基づいて
行つた。
又、貯蔵安定性試験は40℃空気オーブン中で促
進試験を行い比較検討した。評価結果を表−１に
示した。接着強度、耐熱性及び貯蔵安定性ともい
ずれもすぐれたものであつた。
比較例 １
実施例１において、エピコート807と４，4′−
ジアミノジフエニルスルホンとの反応で得られた
付加反応生成物A45部の代りにエポキシ樹脂エピ
コート＃825を用いることを除いて実施例１と全
く同一配合により接着剤を得た。この接着剤を実
施例１と同様に性能評価を行つた。評価結果を表
−１に示す。実施例１に比較し接着強度及び耐熱
性がかなり劣つている。
実施例 ２
ビスフエノールＡジグリシジルエーテル（エポ
キシ当量173、エポキシ樹脂エポトートYD−
8125、東都化成製）100部に、４，4′−ジアミノ
ジフエニルスルホン７部を加え実施例１と同様に
10時間付加反応せしめ、付加反応生成物Ｂ（数平
均分子量1520）を得た。次いでカルボキシ変性ブ
タジエン−アクリロニトリル樹脂（CTBN1300
×13）８部にビスフエノールＡジグリシジルエー
テル（エポートートYD−8125）45部を加えて撹
拌機つき加熱容器に入れて内温130℃で撹拌下３
時間付加反応せしめゴム変性エポキシ樹脂Ｃを得
た。反応付加物B45部に対し、ゴム変性エポキシ
樹脂Ｃを53部加え、さらに長鎖エステル型エポキ
シ樹脂（ST−2PG）２部、ジシアンジアミド８
部及び３−（３，４−ジクロロフエニル）１，１
−ジメチルウレア（カーメツクスＤ）２部を加え
均一に混合し一液型エポキシ樹脂接着剤を得た。
この接着剤を実施例１と全く同様に性能評価を行
つた。評価結果を表１に示す。接着強度、耐熱性
及び貯蔵安定性のいずれもすぐれたものであつ
た。
比較例 ２
実施例２に示した反応付加物B40部及びエポキ
シ樹脂エピコート＃828 38部にポリブタジエン変
性エポキシ樹脂（EPB17、日本曹達製）20部、
長鎖エステル型エポキシ樹脂（ST−2PG）２部、
ジシアンジアミド８部及び２−フエニル−４−メ
チル−５−ヒドロキシメチルイミダゾール４部を
加え均一に混合し一液型エポキシ樹脂接着剤を得
た。この接着剤を実施例１と全く同様の方法で性
能の評価を行つた。評価結果を表−１に示す。実
施例１、２に比べ接着強度、とりわけ低温（120
℃×60min硬化）での接着強度が極めて不満足な
ものであつた。
【表】Detailed Description of the Invention The present invention has fast curing properties and storage stability at low temperatures, and the cured product has excellent adhesive properties, heat resistance, water resistance, and mechanical strength, and is particularly suitable for structural adhesives. The present invention relates to a one-component epoxy resin adhesive composition suitable as an adhesive. Epoxy resin has electrical insulation, heat resistance, corrosion resistance,
It has excellent adhesive properties and can be used in liquid, paste, sheet, or powder form, so it is used in a variety of fields. Another reason why it is widely used is that it can be mixed in various ways and the properties of the cured product can be varied depending on the purpose of use. However, epoxy resins generally have the drawback of requiring curing conditions at high temperatures and for long periods of time, and various methods have been proposed for curing at low temperatures. For example, methods using aromatic amine compounds, imidazole compounds, etc. as curing agents have been proposed, but epoxy resin compositions containing these highly active curing agents can be cured even at low temperatures of 130°C or lower. However, on the other hand, the adhesion to metal materials and the mechanical strength of the cured product are reduced, and in addition, the storage stability of the resin composition is extremely poor, being only a few days or less. The object of the present invention is to provide a one-component epoxy resin adhesive that is storage stable, cures quickly at low temperatures of 130°C or less, and whose cured product has good adhesion, heat resistance, water resistance, and mechanical strength. An object of the present invention is to provide a composition. The one-component epoxy resin adhesive composition of the present invention comprises (A) at least one aromatic polyamine and bisphenol A diglycidyl ether and/or bisphenol F diglycidyl ether having an epoxy equivalent of 200 or less. 3-1/10
(B) a rubbery polymer, (C) dicyandiamide, and (D) a compound represented by the general formula (); (However, in the formula, X 1 and X 2 are respectively −OCH 3 ,
-NO2 , Cl or hydrogen atoms) as an essential component. The aromatic polyamine used in the present invention includes o
-phenylenediamine, m-phenylenediamine, 4,4'-methylenedianiline, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, etc., which may be used alone or in combination. It may also be used as In addition, it is necessary to use bisphenol A diglycidyl ether and/or bisphenol F diglycidyl ether with an epoxy equivalent of 200 or less, and if an epoxy equivalent of more than 200 is used, addition reaction products with aromatic polyamines The viscosity of the adhesive becomes extremely high, making it difficult to use as an adhesive, and the storage stability is also significantly reduced, which is undesirable. The addition reaction product is obtained by heat-treating the above-mentioned bisphenol A diglycidyl ether and/or bisphenol F diglycidyl ether and an appropriate stoichiometric amount of aromatic polyamine, and stopping the reaction when an appropriate viscosity is reached. Obtainable. Here, the stoichiometry is extremely important, and the stoichiometric ratio of the aromatic polyamine and epoxy resin must be in the range of 1/3 to 1/10. If the stoichiometric ratio exceeds 1/3, the aromatic polyamine will be in excess and the viscosity of the resulting modified epoxy resin will become too high, reducing workability and storage stability, which is undesirable.If the stoichiometric ratio is less than 1/10, the aromatic polyamine This is not preferable because the adhesiveness and heat resistance and strength of the cured product decrease due to insufficient . Here, the stoichiometric amount is 1 epoxy group and 1 N-H bond.
means the equivalent amount equivalent to 1. The above addition reaction is carried out by controlling the reaction equivalent, treatment temperature, time, etc. so that the reaction product reaches a desired molecular weight. In a reaction with an excess of epoxy resin, the heat treatment temperature can be increased to shorten the treatment time, but in a reaction with a small excess of epoxy resin, gelation tends to occur, so the treatment temperature is set low. The addition reaction product has a number average molecular weight of 1000~
Preferably in the 4000 range. When the number average molecular weight is less than 1000, low temperature curability deteriorates, and at the same time adhesiveness also deteriorates. On the other hand, if it exceeds 4000, the viscosity becomes extremely high, which not only causes a decrease in workability, but also
This is not preferred because storage stability deteriorates. The modified epoxy resin thus obtained has excellent low-temperature curability as compared to ordinary epoxy resin compositions, and the cured product exhibits extremely good adhesive strength, water resistance, and heat resistance. Various rubbery polymers, which are the second component of the present invention, include polybutadiene, copolymers of acrylonitrile and butadiene, and terminally carboxylated polymers, but in particular, rubbery polymers that are compatible with the modified epoxy resin of the present invention can be used. Alternatively, butadiene-acrylonitrile resin (hereinafter abbreviated as CTBN) and its
Obtained by reacting CTBN with epoxy resin
CTBN modified epoxy resin is preferred. The content of this rubbery polymer is preferably 3 to 30% by weight based on the total of components (A) and (B), and if it is less than 3% by weight, the so-called stress relaxation effect due to the addition of the rubbery polymer cannot be obtained. The adhesion force is insufficient, and the other 30
If it exceeds % by weight, the compatibility with the modified epoxy resin decreases, leading to a decrease in storage stability, and at the same time, heat resistance etc. decrease. Next, dicyandiamide used as the third component not only exhibits the effect of a curing agent, but also exhibits the effect of contributing to improving the adhesion to metal materials and the heat resistance and mechanical strength of the cured adhesive layer.
However, in order to obtain sufficient adhesive strength with dicyandiamide alone, a curing temperature of 150°C or higher is required. A compound represented by (however, X 1 and As a result, an adhesive can be obtained that can be cured at a low temperature of 130°C or less and has good storage stability.
Here, the amount of curing accelerator added is the sum of components A and B.
The amount of dicyandiamide added is preferably in the range of 1 to 8 parts per 100 parts by weight, and the amount of dicyandiamide added is 100 parts in total of components A and B.
A range of 2 to 10 parts by weight is preferred. In addition, the usage ratio of component C and component D is 10/ in C/D weight ratio.
The range of 1 to 1/1 is preferable. The present invention relates to an adhesive mainly composed of the modified epoxy resin, but ordinary epoxy resins, namely unmodified bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and these Epoxy resins other than resins, such as aliphatic epoxy resins,
Alicyclic epoxy resins, polybutadiene-modified epoxy resins, long-chain ester-type epoxy resins, aromatic dicarboxylic acid-based epoxy resins, cresol novolac-type epoxy resins, etc. may be used without impairing the purpose of the present invention. I can't help it. In carrying out the present invention, for example, thermoplastic resins such as nylon resin and acrylic resin, pigments such as anhydrous silica and alumina, etc. may be added as long as the purpose of the present invention is not impaired. The present invention will be further explained below with reference to Examples. In addition, "parts" in the examples means parts by weight. Example 1 7 parts of 4,4'-diaminodiphenylsulfone was added to 100 parts of bisphenol F diglycidyl ether (epoxy equivalent: 175, epoxy resin Epicote 807, Shell Chemical registered trademark), and the mixture was placed in a heating container equipped with a stirrer. The mixture was allowed to undergo an addition reaction for 10 hours with stirring at an internal temperature of 100°C, and then cooled. For 45 parts of addition reaction product A (number average molecular weight 1440) obtained here,
45 parts of epoxy resin (Epikoat #825, manufactured by Yuka Ciel Co., Ltd.), long chain ester type epoxy resin (ST-
2PG, manufactured by Okamura Oil Co., Ltd.) 2 parts, carboxy-modified butadiene-acrylonitrile resin (CTBN1300×
13, manufactured by Ube Industries) 8 parts, dicyandiamide 8 parts and 3-(3,4-dichlorophenyl)1,1-dimethylurea (Carmex D, manufactured by Dupont) 2
1 part and mixed uniformly to obtain a one-component epoxy resin adhesive. The various performances of this adhesive were evaluated using the following methods:
25 x 100 x 2 mm according to JIS-K-6848, 6850
Polish the 12.5mm lap part of the SPCC mild steel plate with sandpaper (#240) and thoroughly degrease it with acetone. Apply the above adhesive evenly to one side of the treated steel plate and overlap it with another treated steel plate. Next, the sample was fixed with two eyeball clips with a width of 5 cm so as not to shift, and was cured under the specified conditions shown in Table 1 to form an adhesive sample. After being left at normal temperature (room temperature), the tensile shear adhesive strength was determined using a tensile tester (Autograph, DSS-2000) at a printing speed of 5 mm/min. Next, the sample for heat distortion temperature (HDT) measurement is
A glass casting frame (two glass plates of 50 x 150 x 2 mm, using cellophane on the entire surface as a release paper, and a 3 mm thick silicone rubber spacer) was preheated to 150°C and the viscosity was adjusted. After pouring the lowered adhesive and casting, it was cured at 150°C for 30 minutes, unwound, and then cut to a size of approximately 12.7 x 127 x 3 mm. HDT measurement was performed based on JIS-K-6919. In addition, for storage stability testing, an accelerated test was conducted in an air oven at 40°C and a comparative study was conducted. The evaluation results are shown in Table-1. The adhesive strength, heat resistance and storage stability were all excellent. Comparative Example 1 In Example 1, Epicote 807 and 4,4'-
An adhesive was obtained using exactly the same formulation as in Example 1, except that epoxy resin Epicoat #825 was used in place of 45 parts of the addition reaction product A obtained by the reaction with diaminodiphenylsulfone. The performance of this adhesive was evaluated in the same manner as in Example 1. The evaluation results are shown in Table-1. Compared to Example 1, adhesive strength and heat resistance are considerably inferior. Example 2 Bisphenol A diglycidyl ether (epoxy equivalent weight 173, epoxy resin Epotote YD-
8125, manufactured by Toto Kasei) and 7 parts of 4,4'-diaminodiphenylsulfone were added in the same manner as in Example 1.
The addition reaction was carried out for 10 hours to obtain addition reaction product B (number average molecular weight 1520). Next, carboxy-modified butadiene-acrylonitrile resin (CTBN1300
×13) Add 45 parts of bisphenol A diglycidyl ether (Eporto YD-8125) to 8 parts, place in a heating container with a stirrer, and stir at an internal temperature of 130℃ for 3 minutes.
A rubber-modified epoxy resin C was obtained by time addition reaction. To 45 parts of reaction adduct B, 53 parts of rubber-modified epoxy resin C was added, and further 2 parts of long-chain ester type epoxy resin (ST-2PG) and 8 parts of dicyandiamide were added.
part and 3-(3,4-dichlorophenyl)1,1
- Two parts of dimethyl urea (Carmex D) were added and mixed uniformly to obtain a one-component epoxy resin adhesive.
The performance of this adhesive was evaluated in exactly the same manner as in Example 1. The evaluation results are shown in Table 1. Adhesive strength, heat resistance and storage stability were all excellent. Comparative Example 2 20 parts of polybutadiene-modified epoxy resin (EPB17, manufactured by Nippon Soda) were added to 40 parts of the reaction adduct B shown in Example 2 and 38 parts of epoxy resin Epicoat #828.
2 parts of long chain ester type epoxy resin (ST-2PG),
8 parts of dicyandiamide and 4 parts of 2-phenyl-4-methyl-5-hydroxymethylimidazole were added and mixed uniformly to obtain a one-component epoxy resin adhesive. The performance of this adhesive was evaluated in exactly the same manner as in Example 1. The evaluation results are shown in Table-1. Compared to Examples 1 and 2, the adhesive strength, especially at low temperatures (120
The adhesive strength was extremely unsatisfactory. 【table】
Claims (1)
ポキシ当量が200以下であるビスフエノールＡ
ジグリシジルエーテルおよび／又はビスフエノ
ールＦジグリシジルエーテルとを１／３〜１／
10の化学量論量で反応させて得られる数平均分
子量1000〜4000を有する付加反応生成物、 (B) ゴム質重合体、 (C) ジシアンジアミド及び (D) 次式 （式中X1及びX2はそれぞれ−OCH3、−NO2、
Cl又は水素原子である）で表わされる化合物 を必須成分として含有することを特徴とする一液
型エポキシ樹脂接着剤組成物。[Scope of Claims] 1 (A) Bisphenol A containing at least one aromatic polyamine and an epoxy equivalent of 200 or less
diglycidyl ether and/or bisphenol F diglycidyl ether from 1/3 to 1/
an addition reaction product having a number average molecular weight of 1000 to 4000 obtained by reacting in a stoichiometric amount of 10, (B) a rubbery polymer, (C) dicyandiamide, and (D) the following formula: (In the formula, X 1 and X 2 are respectively −OCH 3 , −NO 2 ,
A one-component epoxy resin adhesive composition containing as an essential component a compound represented by (Cl or hydrogen atom).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6365583A JPS59189179A (en) | 1983-04-13 | 1983-04-13 | One-pack type epoxy resin adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6365583A JPS59189179A (en) | 1983-04-13 | 1983-04-13 | One-pack type epoxy resin adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59189179A JPS59189179A (en) | 1984-10-26 |
| JPH0334513B2 true JPH0334513B2 (en) | 1991-05-22 |
Family
ID=13235574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6365583A Granted JPS59189179A (en) | 1983-04-13 | 1983-04-13 | One-pack type epoxy resin adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59189179A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2737190B2 (en) * | 1988-12-21 | 1998-04-08 | 松下電器産業株式会社 | Bicycle frame structure and manufacturing method thereof |
| JP4718666B2 (en) * | 2000-06-06 | 2011-07-06 | 三井化学株式会社 | Epoxy resin composition and adhesive sheet |
| DE60320134T3 (en) | 2002-11-28 | 2015-12-24 | Mitsubishi Rayon Co., Ltd. | METHOD OF MANUFACTURING FIBER-REINFORCED COMPOSITE MATERIAL |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5349055A (en) * | 1976-10-15 | 1978-05-04 | Matsushita Electric Works Ltd | Thermosetting composition |
| JPS57167370A (en) * | 1981-04-09 | 1982-10-15 | Mitsui Petrochem Ind Ltd | Adhesive composition |
-
1983
- 1983-04-13 JP JP6365583A patent/JPS59189179A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5349055A (en) * | 1976-10-15 | 1978-05-04 | Matsushita Electric Works Ltd | Thermosetting composition |
| JPS57167370A (en) * | 1981-04-09 | 1982-10-15 | Mitsui Petrochem Ind Ltd | Adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59189179A (en) | 1984-10-26 |
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