JPH0230327B2 - - Google Patents
Info
- Publication number
- JPH0230327B2 JPH0230327B2 JP57102606A JP10260682A JPH0230327B2 JP H0230327 B2 JPH0230327 B2 JP H0230327B2 JP 57102606 A JP57102606 A JP 57102606A JP 10260682 A JP10260682 A JP 10260682A JP H0230327 B2 JPH0230327 B2 JP H0230327B2
- Authority
- JP
- Japan
- Prior art keywords
- curing agent
- modified amine
- epoxy resin
- amine condensate
- resin curing
- 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
- 150000001412 amines Chemical class 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 239000003822 epoxy resin Substances 0.000 claims description 26
- 229920000647 polyepoxide Polymers 0.000 claims description 26
- 238000009835 boiling Methods 0.000 claims description 10
- 229920000768 polyamine Polymers 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 235000019445 benzyl alcohol Nutrition 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 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
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 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
- 229940116411 terpineol Drugs 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Description
本発明はエポキシ樹脂硬化剤に関するものであ
る。
近年、土木建設等の分野においてもエポキシ樹
脂が広く用いられるようになり、その作業性から
も、低粘度且つ低毒性のものであり、低温且つ高
湿の条件下でもエポキシ樹脂を良好且つ迅速に硬
化させうるエポキシ樹脂硬化剤の開発が望まれて
いる。
従来からも、低粘度化させるために、トリエチ
レンテトラミン等のポリアミンを添加させること
が一般に行われてはいるが、毒性を高めるばかり
でなく、硬化後の表面状態が著しく悪くなる不都
合がある。
また、低温且つ高湿の条件下において好適な硬
化剤としては、ポリアミンにフエノール類を添加
したものが知られているが、零度近くの低温条件
下では硬化反応が殆ど行われず、しかも耐薬品性
及び機械的強度等の物理的物性が劣るといつた欠
点がある。
そこで、近年、このような欠点のないものとし
て、例えばフエノール、ホルマリン及びアミンを
主成分として縮合された変性アミン縮合物を用い
た硬化剤が開発されている。
しかしながら、変性アミン縮合物は、低温、高
湿の条件下でもエポキシ樹脂を良好に硬化させう
るといつた、硬化剤として極めて優れた特性を有
する反面、粘度が高く、硬化物が非常に脆いとい
つた欠点がある。この脆さを解消するために、変
性アミン縮合物にポリアドアミン或いはノニルフ
エノール等を添加することも行われてはいるが、
低粘度化させるには至らず、しかも硬化物の物性
を良好となし得ないでいるのが実情である。
本発明は、上記した点に鑑み、硬化剤としての
変性アミン縮合物の優れた特性をそのまま活かし
ながら、しかもその欠点である高粘度性及び硬化
物の物性劣化を良好に解消したエポキシ樹脂硬化
物を提供するものである。
この課題を解決した本発明のエポキシ樹脂硬化
剤は、窒素活性水素を有するポリアミン類、フエ
ノール類及びカルボニル化合物を主成分として縮
合させて得られる変性アミン縮合物に、沸点が
130℃を超える高沸点のアルコール類を配合して
なるものである。
変性アミン縮合物は、ポリアミン類等の全成分
を１工程の反応操作によつて得ることもできる
が、２工程の反応操作によつて得ることが好まし
い。すなわち、フエノール類とポリアミン類の混
合物にカルボニル化合物を反応させるか、又はフ
エノール類とカルボニル化合物を予め反応させ、
この反応物にポリアミン類を反応させるか、若し
くはポリアミン類とカルボニル化合物を予め反応
させ、この反応物とフエノール類とを反応させる
ことによつて、変性アミン縮合物を得る。このと
き、反応温度は10〜150℃であり、好ましくは30
〜70℃である。また、反応を完結させるために、
全量添加後に昇温させるようにすればよい。反応
終了後においては、反応混合物を減圧下で加熱し
て、水分及び未反応物を除去しておく。通常、変
性アミン縮合物は液体であることが望ましい。
ポリアミン類は、１分子中に少なくとも、１個
の窒素活性水素を有するものであるが、活性水素
を有するアミノ基を２個以上有するポリアミンが
好ましい。例えば、エチレンジアミン、ジエチレ
ントリアミン、ｍ―キシリレンジアミン等が用い
られる。フエノール類は、芳香族核に置換されて
いない反応性位置を少なくとも１ケ所有するもの
で、１価のフエノール類が好ましい。例えば、フ
エノール等が用いられる。カルボニル化合物は、
分子中に少なくとも１個のカルボニル基を有する
もので、炭素数１〜３個の低級アルデヒド類が好
ましい。例えば、ホルマリン等が用いられる。
かくして得られた変性アミン縮合物に、沸点が
130℃を超える高沸点のアルコール類を配合する
ことによつて、本発明のエポキシ樹脂硬化剤が得
られる。変性アミン縮合物に対するアルコール類
の配合割合は特に限定されないが、通常100：１
〜50であり、好ましくは100：５〜30である。ま
た、変性アミン縮合物とアルコール類との配合方
法も特に限定されないが、両者の混合温度条件は
上記アルコール類を残存させるために20〜130℃
とする。この沸点が130℃を超える高沸点のアル
コール類としては、例えば、ベンジルアルコー
ル、フルフリルアルコール、ノニルアルコール、
１―ヘキサノール、ヘプタノール、オクタノー
ル、２―エチル―１―ヘキサノール、２メチル―
１―ペンタノール、２―エチル―１―ブタノー
ル、４メチル―２―ペンタノール、デカノール、
ドデカノール、シクロヘキサノール、メチルシク
ロヘキサノール、テルピネオール、ポリエチレン
グリコール、エタンジオール、プロパンジオー
ル、ブタンジオール、ヘプタンジオール、グリセ
リン等が用いられる。
以上のように、本発明のエポキシ樹脂硬化剤
は、変性アミン縮合物に沸点が130℃を超える高
沸点のアルコール類を配合させたものであるか
ら、上記高沸点のアルコール類の添加により、変
性アミン縮合物自体の有する優れた特性をそのま
ま維持しながら、その欠点である高粘度性及び硬
化物の物性劣化を除去できるものである。すなわ
ち、本発明のエポキシ樹脂硬化剤は、低粘度且つ
低毒性のものであり、エポキシ樹脂と混合させた
場合には、低温且つ高湿の条件下でも良好に且つ
短時間で硬化反応が行われ、接着作業性を極めて
向上させうるものであり、しかも表面状態が極め
てよく且つ機械的強度等の物理的物性が大巾に向
上した硬化物を得ることができるものである。し
たがつて、本発明のエポキシ樹脂硬化剤を用いる
エポキシ樹脂は、塗料用、注型用、土木建設用
（例えば、流し展ベ用、レジンモルタル用或いは
クランク補修用等）、その他接着、積層用等とし
て好適に用いられうるのである。なお、本発明の
エポキシ樹脂硬化剤によつて硬化されるエポキシ
樹脂として特に限定されるものはなく、また両者
の配合割合等の硬化条件は、従来公知のアミン系
硬化剤を用いた場合と同一である。
以下、本発明の実施例について説明する。
（実施例 １）
２モル（188ｇ）のフエノールと２モル（120
ｇ）のエチレンジアミンを、攪拌器、温度計、滴
下装置及び還流冷却器を夫々セツトした容積１
の四ツ口フラスコに入れて、フエノールをエレチ
ンジアミンに溶解させた上、これに２モル
（162.2ｇ）の37％ホルマリンを50℃以下で徐々に
滴下して、滴下後更に500℃前後の温度下で２時
間反応させ、その後80℃に昇温させて１時間攪拌
して、反応を完結させ、そして反応終了後減圧脱
水蒸留を行つて、330ｇの変性アミン縮合物（）
を得た。
かくして得られた変性アミン縮合物（）75ｇ
にベンジルアルコール25ｇを混合して、エポキシ
樹脂硬化剤（）を得た。
また、前記変性アミン縮合物（）75ｇにフル
フリルアルコール25ｇを混合して、エポキシ樹脂
硬化剤（）を得た。
そして、変性アミン縮合物（）及び硬化剤
（）（）の各粘度及びアミン価を測定したとこ
ろ、表１の如き結果が得られた。なお、粘度は25
℃の条件下で測定したものであり、アミン価は試
料１ｇ当りのKOH量（mg）に換算したものであ
る（表３、表５及び表７において同じ）。
また、エポキシ樹脂と変性アミン縮合物（）
及び硬化剤（）（）とを各々混合させて、各
場合における硬化時間及び硬化物の塗膜状態、曲
げ強度等の機械的強度を測定したところ、表２の
如き結果が得られた。なお、エポキシ樹脂として
は、ユカシエルエポキシ株式会社製のエピコート
828を用いた。また硬化時間は、表２の配合比
（重量部）のもの50ｇを試料とした25℃の温度下
での時間であり、塗膜状態は、硬化後の塗膜の光
沢、凸凹、濁りを判定したものであり、機械的強
度は、JISK−6911の試験によつたものである
（表４、表６及び表８において同じ）。
（実施例 ２）
１モル（94ｇ）のフエノールと0.5モル（40.55
ｇ）の37％ホルマリンを前記実施例１と同様のフ
ラスコに入れ、これに触媒として2.8ｇのトリエ
チルアミンを加えた上、攪拌しながら100℃に昇
温し、昇温後、この温度を維持しながら、２時間
還流反応を行わしめ、さらに1.5モル（154.5ｇ）
のジエチレントリアミンを１時間に亘つて滴下し
た後、１時間攪拌して反応を完結させ、反応終了
後、減圧脱水蒸留を行つて260ｇの変性アミン縮
合物（）を得た。
かくして得られた変性アミン縮合物（）80ｇ
にフルフリルアルコール20ｇを混合して、エポキ
シ樹脂硬化剤（）を得た。
そして、変性アミン縮合物（）と硬化剤
（）との性状及び硬化物性能を比較判定したと
ころ、表３及び表４の如き結果が得られた。
（実施例 ３）
１モル（94ｇ）のフエノール、1.2モル（163.2
ｇ）のｍ―キシリレンジアミン及び１モル（81.1
ｇ）の37％ホルマリンを前記実施例１の場合と同
様にして反応させた後、脱水蒸留後268ｇの変性
アミン縮合物（）を得た。
かくして得られた変性アミン縮合物（）90ｇ
にベンジルアルコール10ｇを混合して、エポキシ
樹脂硬化剤（）を得た。
また、変性アミン縮合物（）85ｇにベンジル
アルコール15ｇを混合して、エポキシ樹脂硬化剤
（）を得た。
また、変性アミン縮合物（）80ｇにベンジル
アルコール20ｇを混合して、エポキシ樹脂硬化剤
（）を得た。
また、変性アミン縮合物（）75ｇにベンジル
アルコール25ｇを混合して、エポキシ樹脂硬化剤
（）を得た。
そして、変性アミン縮合物（）と各硬化剤
（）〜（）との性状及び硬化物性能を比較判
定したところ、表５及び表６の如き結果が得られ
た。
（実施例 ４）
前記実施例３で得られた変性アミン縮合物
（）100ｇにノニフエノール10ｇを加え、100℃
の温度下で30分攪拌して変性アミン硬化剤（）
を得た。
かくして得られた変性アミン硬化剤（）80ｇ
にノニルアルコール20ｇを混合して、エポキシ樹
脂硬化剤（）を得た。
そして、この変性アミン硬化剤（）とエポキ
シ樹脂硬化剤（）との性状及び硬化物性能を比
較判定したところ、表７及び表８の如き結果が得
られた。
The present invention relates to an epoxy resin curing agent. In recent years, epoxy resins have come to be widely used in fields such as civil engineering and construction, and due to their workability, they have low viscosity and low toxicity, and can be processed quickly and efficiently even at low temperatures and high humidity. It is desired to develop an epoxy resin curing agent that can be cured. Conventionally, it has been common practice to add polyamines such as triethylenetetramine in order to lower the viscosity, but this has the disadvantage of not only increasing toxicity but also significantly worsening the surface condition after curing. In addition, as a curing agent suitable for low temperature and high humidity conditions, it is known that phenols are added to polyamine. It also has disadvantages such as poor physical properties such as mechanical strength. Therefore, in recent years, a curing agent using a modified amine condensate containing phenol, formalin, and amine as main components has been developed as a curing agent that does not have such drawbacks. However, although modified amine condensates have extremely excellent properties as curing agents, such as being able to cure epoxy resins well even under low temperature and high humidity conditions, they have high viscosity and the cured products are extremely brittle. There are some drawbacks. In order to eliminate this brittleness, it has been attempted to add polyadamine or nonylphenol to the modified amine condensate; however,
The reality is that the viscosity cannot be lowered, and the physical properties of the cured product cannot be improved. In view of the above-mentioned points, the present invention provides a cured epoxy resin product that takes advantage of the excellent properties of a modified amine condensate as a curing agent while satisfactorily eliminating its drawbacks of high viscosity and deterioration of the physical properties of the cured product. It provides: The epoxy resin curing agent of the present invention that solves this problem is a modified amine condensate obtained by condensing polyamines, phenols, and carbonyl compounds having nitrogen active hydrogen as main components, and has a boiling point.
It is made by blending alcohols with a high boiling point exceeding 130℃. Although the modified amine condensate can be obtained by a one-step reaction operation using all components such as polyamines, it is preferably obtained by a two-step reaction operation. That is, a mixture of phenols and polyamines is reacted with a carbonyl compound, or a phenol and a carbonyl compound are reacted in advance,
A modified amine condensate is obtained by reacting this reactant with a polyamine, or by reacting the polyamine and a carbonyl compound in advance and reacting this reactant with a phenol. At this time, the reaction temperature is 10 to 150°C, preferably 30°C.
~70℃. Also, in order to complete the reaction,
The temperature may be raised after the entire amount is added. After the reaction is completed, the reaction mixture is heated under reduced pressure to remove moisture and unreacted substances. Usually, it is desirable that the modified amine condensate is liquid. Polyamines have at least one nitrogen active hydrogen in one molecule, but polyamines having two or more amino groups having active hydrogen are preferred. For example, ethylenediamine, diethylenetriamine, m-xylylenediamine, etc. are used. The phenols have at least one reactive position that is not substituted with an aromatic nucleus, and monovalent phenols are preferred. For example, phenol etc. are used. Carbonyl compounds are
Lower aldehydes having at least one carbonyl group in the molecule and having 1 to 3 carbon atoms are preferred. For example, formalin or the like is used. The modified amine condensate thus obtained has a boiling point of
The epoxy resin curing agent of the present invention can be obtained by blending an alcohol with a high boiling point of over 130°C. The blending ratio of alcohol to modified amine condensate is not particularly limited, but is usually 100:1.
-50, preferably 100:5-30. In addition, the method of blending the modified amine condensate and the alcohol is not particularly limited, but the temperature conditions for mixing both are 20 to 130°C in order to allow the alcohol to remain.
shall be. Examples of high-boiling alcohols with boiling points exceeding 130°C include benzyl alcohol, furfuryl alcohol, nonyl alcohol,
1-hexanol, heptanol, octanol, 2-ethyl-1-hexanol, 2-methyl-
1-pentanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, decanol,
Dodecanol, cyclohexanol, methylcyclohexanol, terpineol, polyethylene glycol, ethanediol, propanediol, butanediol, heptanediol, glycerin, etc. are used. As described above, the epoxy resin curing agent of the present invention is a modified amine condensate blended with a high-boiling alcohol with a boiling point exceeding 130°C. While maintaining the excellent properties of the amine condensate itself, its disadvantages of high viscosity and deterioration in the physical properties of the cured product can be eliminated. That is, the epoxy resin curing agent of the present invention has low viscosity and low toxicity, and when mixed with an epoxy resin, the curing reaction can be performed well and in a short time even under low temperature and high humidity conditions. , it is possible to significantly improve adhesive workability, and to obtain a cured product with extremely good surface condition and greatly improved physical properties such as mechanical strength. Therefore, the epoxy resin using the epoxy resin curing agent of the present invention can be used for paints, casting, civil engineering construction (e.g., pouring, resin mortar, crank repair, etc.), and other adhesives and laminations. It can be suitably used as, etc. The epoxy resin to be cured by the epoxy resin curing agent of the present invention is not particularly limited, and the curing conditions such as the blending ratio of the two are the same as in the case of using conventionally known amine-based curing agents. It is. Examples of the present invention will be described below. (Example 1) 2 moles (188 g) of phenol and 2 moles (120 g) of phenol
g) Ethylenediamine was added to a volume 1 containing a stirrer, a thermometer, a dropping device, and a reflux condenser, respectively.
After dissolving phenol in eletin diamine, 2 mol (162.2 g) of 37% formalin was gradually added dropwise at below 50°C, and after the dropwise addition, the mixture was further heated to around 500°C. The reaction was carried out at a temperature of 2 hours, and then the temperature was raised to 80°C and stirred for 1 hour to complete the reaction.After the reaction was completed, vacuum dehydration distillation was performed to obtain 330g of modified amine condensate ().
I got it. 75 g of the thus obtained modified amine condensate ()
and 25 g of benzyl alcohol were mixed to obtain an epoxy resin curing agent (2). Further, 75 g of the modified amine condensate (2) was mixed with 25 g of furfuryl alcohol to obtain an epoxy resin curing agent (2). The viscosity and amine value of each of the modified amine condensate () and the curing agent () were measured, and the results shown in Table 1 were obtained. In addition, the viscosity is 25
It was measured under the conditions of ℃, and the amine value was converted to the amount of KOH (mg) per 1 g of sample (same in Table 3, Table 5, and Table 7). In addition, epoxy resin and modified amine condensate ()
and curing agent () and () were mixed, and the curing time, coating state of the cured product, and mechanical strength such as bending strength were measured in each case, and the results shown in Table 2 were obtained. The epoxy resin used is Epicoat manufactured by Yukashiel Epoxy Co., Ltd.
828 was used. The curing time is the time taken at a temperature of 25°C using 50g of the compounding ratio (parts by weight) shown in Table 2.The coating condition is determined by the gloss, unevenness, and turbidity of the coating after curing. The mechanical strength was determined according to the JISK-6911 test (same in Tables 4, 6, and 8). (Example 2) 1 mol (94 g) of phenol and 0.5 mol (40.55 g)
g) 37% formalin was placed in the same flask as in Example 1, 2.8 g of triethylamine was added as a catalyst, and the temperature was raised to 100°C while stirring, and after raising the temperature, this temperature was maintained. While refluxing for 2 hours, an additional 1.5 mol (154.5 g)
of diethylenetriamine was added dropwise over 1 hour, and the mixture was stirred for 1 hour to complete the reaction. After the reaction was completed, dehydration and distillation under reduced pressure was performed to obtain 260 g of a modified amine condensate (). 80 g of the thus obtained modified amine condensate ()
20 g of furfuryl alcohol was mixed with the mixture to obtain an epoxy resin curing agent (). When the properties and cured product performance of the modified amine condensate (2) and the curing agent (2) were compared, the results shown in Tables 3 and 4 were obtained. (Example 3) 1 mol (94 g) of phenol, 1.2 mol (163.2
g) of m-xylylenediamine and 1 mol (81.1
After reacting 37% formalin (g) in the same manner as in Example 1, 268 g of modified amine condensate () was obtained after dehydration and distillation. 90 g of the thus obtained modified amine condensate ()
10 g of benzyl alcohol was mixed with the mixture to obtain an epoxy resin curing agent (2). Further, 15 g of benzyl alcohol was mixed with 85 g of the modified amine condensate (2) to obtain an epoxy resin curing agent (2). Further, 20 g of benzyl alcohol was mixed with 80 g of the modified amine condensate (2) to obtain an epoxy resin curing agent (2). Further, 25 g of benzyl alcohol was mixed with 75 g of the modified amine condensate (2) to obtain an epoxy resin curing agent (2). Then, when the properties and cured product performance of the modified amine condensate () and each of the curing agents () to () were compared and judged, the results shown in Tables 5 and 6 were obtained. (Example 4) 10 g of nonyphenol was added to 100 g of the modified amine condensate () obtained in Example 3, and the mixture was heated at 100°C.
Modified amine curing agent () by stirring for 30 min at a temperature of
I got it. 80g of the thus obtained modified amine curing agent ()
and 20 g of nonyl alcohol were mixed to obtain an epoxy resin curing agent (2). Then, the properties and cured product performance of this modified amine curing agent (2) and epoxy resin curing agent (2) were compared, and the results shown in Tables 7 and 8 were obtained.
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【表】【table】
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Claims (1)
ール類及びカルボニル化合物を主成分として縮合
させて得られる変性アミン縮合物に、沸点が130
℃を超える高沸点のアルコール類を配合してなる
エポキシ樹脂硬化剤。1 A modified amine condensate obtained by condensing polyamines, phenols, and carbonyl compounds having nitrogen active hydrogen as main components has a boiling point of 130
An epoxy resin curing agent containing alcohols with a high boiling point exceeding ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10260682A JPS58219220A (en) | 1982-06-14 | 1982-06-14 | Curing agent for epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10260682A JPS58219220A (en) | 1982-06-14 | 1982-06-14 | Curing agent for epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58219220A JPS58219220A (en) | 1983-12-20 |
| JPH0230327B2 true JPH0230327B2 (en) | 1990-07-05 |
Family
ID=14331892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10260682A Granted JPS58219220A (en) | 1982-06-14 | 1982-06-14 | Curing agent for epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58219220A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0511858Y2 (en) * | 1988-11-02 | 1993-03-25 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62280216A (en) * | 1986-05-28 | 1987-12-05 | Aica Kogyo Co Ltd | Epoxy resin composition |
| JPH0625331B2 (en) * | 1988-03-18 | 1994-04-06 | ソマール株式会社 | Adhesive composition for battery case |
| JP2021004270A (en) * | 2019-06-25 | 2021-01-14 | 住友ベークライト株式会社 | Phenol resin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4948480A (en) * | 1972-09-11 | 1974-05-10 | ||
| JPS57195118A (en) * | 1981-05-25 | 1982-11-30 | Mitsubishi Gas Chem Co Inc | Preparation of curing agent for epoxy resin |
| JPS57195119A (en) * | 1981-05-25 | 1982-11-30 | Mitsubishi Gas Chem Co Inc | Preparation of curing agent for epoxy resin |
| JPS58187462A (en) * | 1982-04-27 | 1983-11-01 | Kansai Paint Co Ltd | Curing agent for epoxy resin coating compound |
-
1982
- 1982-06-14 JP JP10260682A patent/JPS58219220A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4948480A (en) * | 1972-09-11 | 1974-05-10 | ||
| JPS57195118A (en) * | 1981-05-25 | 1982-11-30 | Mitsubishi Gas Chem Co Inc | Preparation of curing agent for epoxy resin |
| JPS57195119A (en) * | 1981-05-25 | 1982-11-30 | Mitsubishi Gas Chem Co Inc | Preparation of curing agent for epoxy resin |
| JPS58187462A (en) * | 1982-04-27 | 1983-11-01 | Kansai Paint Co Ltd | Curing agent for epoxy resin coating compound |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0511858Y2 (en) * | 1988-11-02 | 1993-03-25 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58219220A (en) | 1983-12-20 |
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