JPH0710871A - Diamino-s-triazine compound having imidaziline ring and curing of epoxy resin therewith - Google Patents
Diamino-s-triazine compound having imidaziline ring and curing of epoxy resin therewithInfo
- Publication number
- JPH0710871A JPH0710871A JP17221593A JP17221593A JPH0710871A JP H0710871 A JPH0710871 A JP H0710871A JP 17221593 A JP17221593 A JP 17221593A JP 17221593 A JP17221593 A JP 17221593A JP H0710871 A JPH0710871 A JP H0710871A
- Authority
- JP
- Japan
- Prior art keywords
- diamino
- triazine
- compound
- epoxy resin
- ring
- 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.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 17
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 17
- -1 Diamino-s-triazine compound Chemical class 0.000 title claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 15
- 125000002636 imidazolinyl group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 abstract description 23
- 239000003795 chemical substances by application Substances 0.000 abstract description 15
- 238000010992 reflux Methods 0.000 abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 20
- 239000013078 crystal Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- LYWVNPSVLAFTFX-UHFFFAOYSA-N 4-methylbenzenesulfonate;morpholin-4-ium Chemical compound C1COCCN1.CC1=CC=C(S(O)(=O)=O)C=C1 LYWVNPSVLAFTFX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001879 gelation Methods 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
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical class NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002018 Aerosil® 300 Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical group C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はイミダゾリン環を有する
ジアミノ−ｓ−トリアジン化合物に関するものであり、
本発明化合物はエポキシ樹脂の硬化剤あるいは硬化促進
剤として有用である。TECHNICAL FIELD The present invention relates to a diamino-s-triazine compound having an imidazoline ring,
The compound of the present invention is useful as a curing agent or curing accelerator for epoxy resins.
【０００２】[0002]
【従来の技術】従来から多くのイミダゾール化合物がエ
ポキシ樹脂の硬化剤あるいは硬化促進剤として使用され
ている。特に、4,6-ジアミノ−1,3,5-s-トリアジンと２
−メチルイミダゾールをエチレンで連結した化合物〔商
品名：２ＭＡ，四国化成工業（株）製〕は、所謂一液性
エポキシ樹脂組成物として用いた場合に保存安定性と硬
化物の性質がよいので、電気絶縁塗料等の分野に多く使
用されている。2. Description of the Related Art Conventionally, many imidazole compounds have been used as curing agents or curing accelerators for epoxy resins. In particular, 4,6-diamino-1,3,5-s-triazine and 2
-A compound obtained by linking methylimidazole with ethylene [trade name: 2MA, manufactured by Shikoku Chemicals Co., Ltd.] has good storage stability and properties of a cured product when used as a so-called one-component epoxy resin composition. It is widely used in the field of electrical insulating paints.
【０００３】[0003]
【発明が解決しようとする課題】このように同一分子内
にトリアジン環とイミダゾ−ル環を有する化合物は、一
液性エポキシ樹脂組成物の硬化剤あるいは硬化促進剤と
して有用であると考えらている。このような観点からエ
ポキシ樹脂組成物の硬化剤あるいは硬化促進剤として有
用である同一分子内にトリアジン環とイミダゾリン環を
有する新規な化合物を提供することが、本発明の目的で
ある。The compound having a triazine ring and an imidazole ring in the same molecule is considered to be useful as a curing agent or curing accelerator for a one-pack type epoxy resin composition. There is. From this point of view, it is an object of the present invention to provide a novel compound having a triazine ring and an imidazoline ring in the same molecule, which compound is useful as a curing agent or a curing accelerator for an epoxy resin composition.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、このよう
な事情に鑑み鋭意研究を重ねた結果、サクシノニトリル
とジシアンジアミドから得られる２−シアノエチル−
（4',6'-ジアミノ-1',3',5'-s-トリアジン）−(2')、イ
ソフタロニトリルとジシアンジアミドから得られるｍ−
シアノ−フェニル−（4',6'-ジアミノ-1',3',5'-s-トリ
アジン）−(2')及びテレフタロニトリルとジシアンジア
ミドから得られるｐ−シアノ−フェニル−（4',6'-ジア
ミノ-1',3',5'-s-トリアジン）−(2')化合物を出発原料
とし、これらの化合物に単体硫黄の存在下１，２−ジア
ミンを反応させることにより、化２で示されるトリアジ
ン環とイミダゾリン環をエチレンあるいはフェニレンで
連結した新規な化合物が得られ、これらの化合物が優れ
たエポキシ樹脂の硬化作用を有することを見い出し、本
発明を完遂するに至った。Means for Solving the Problems The inventors of the present invention have made extensive studies in view of such circumstances, and as a result, 2-cyanoethyl-obtained from succinonitrile and dicyandiamide
(4 ', 6'-diamino-1', 3 ', 5'-s-triazine)-(2'), m-obtained from isophthalonitrile and dicyandiamide
Cyano-phenyl- (4 ', 6'-diamino-1', 3 ', 5'-s-triazine)-(2') and p-cyano-phenyl- (4 ', obtained from terephthalonitrile and dicyandiamide By using 6'-diamino-1 ', 3', 5'-s-triazine)-(2 ') compound as a starting material and reacting these compounds with 1,2-diamine in the presence of elemental sulfur, The novel compounds in which the triazine ring and the imidazoline ring represented by 2 are linked with ethylene or phenylene were obtained, and it was found that these compounds have an excellent curing effect for epoxy resin, and the present invention was completed.
【０００５】[0005]
【化２】 [Chemical 2]
【０００６】本発明化合物の出発原料となる２−シアノ
エチル−（4',6'-ジアミノ-1',3',5'-s-トリアジン）−
(2')化合物、ｍ−シアノ−フェニル−（4',6'-ジアミノ
-1',3',5'-s-トリアジン）−(2')あるいはｐ−シアノ−
フェニル−（4',6'-ジアミノ-1',3',5'-s-トリアジン）
−(2')化合物は、英国特許第６４２４０９号、有機合成
化学、第２４巻、１２５〜１２６頁（1966年）及びビュ
レチン・オブ・ケミカル・ソサイアティ・ジャパン（Bu
ll. Chem. Soc. Japan）、第３８巻、１８２０〜１８２
４頁（1965年）に記載の方法により得られ、その合成方
法は化３で示す反応式で表される。2-Cyanoethyl- (4 ', 6'-diamino-1', 3 ', 5'-s-triazine) -starting material for the compounds of the present invention
(2 ') compound, m-cyano-phenyl- (4', 6'-diamino
-1 ', 3', 5'-s-triazine)-(2 ') or p-cyano-
Phenyl- (4 ', 6'-diamino-1', 3 ', 5'-s-triazine)
-(2 ') compound is described in British Patent No. 642409, Synthetic Organic Chemistry, 24, 125-126 (1966) and Buretin of Chemical Society Japan (Bu.
ll. Chem. Soc. Japan), Volume 38, 1820-182.
It is obtained by the method described on page 4 (1965), and its synthetic method is represented by the reaction formula shown in Chemical formula 3.
【０００７】[0007]
【化３】 [Chemical 3]
【０００８】本発明化合物は、２−シアノエチル−
（4',6'-ジアミノ-1',3',5'-s-トリアジン）−(2')化合
物、ｍ−シアノ−フェニル−（4',6'-ジアミノ-1',3',
5'-s-トリアジン）−(2')あるいはｐ−シアノ−フェニ
ル−（4',6'-ジアミノ-1',3',5'-s-トリアジン）−(2')
化合物１モルに対して１，２−ジアミン化合物を３〜１
０モル加えた混合物を単体硫黄の存在下、加熱還流する
ことにより得られ、その反応式は化４に示すとおりであ
る。The compound of the present invention is 2-cyanoethyl-
(4 ', 6'-diamino-1', 3 ', 5'-s-triazine)-(2') compound, m-cyano-phenyl- (4 ', 6'-diamino-1', 3 ',
5'-s-triazine)-(2 ') or p-cyano-phenyl- (4', 6'-diamino-1 ', 3', 5'-s-triazine)-(2 ')
3-1 of the 1,2-diamine compound is used for 1 mol of the compound
It was obtained by heating and refluxing a mixture added with 0 mol in the presence of elemental sulfur, and its reaction formula is shown in Chemical formula 4.
【０００９】[0009]
【化４】 [Chemical 4]
【００１０】代表的な本発明のイミダゾリン環を有する
ジアミノ−ｓ−トリアジン化合物及びその物性は、次に
示すとおりである。Representative diamino-s-triazine compounds having an imidazoline ring of the present invention and their physical properties are as follows.
【００１１】２−（イミダゾリニル-2')−エチレン−
（4",6"-ジアミノ-1",3",5"-s-トリアジン）−(2")2- (imidazolinyl-2 ')-ethylene-
(4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-(2")
【００１２】[0012]
【化５】 [Chemical 5]
【００１３】塩基性無色結晶。融点：２１４．５〜２２
５℃ ＭｅＯＨ、水及びＤＭＦに熱時可溶、ＤＭＳＯ及びＡｃ
ＯＨに冷時可溶、アセトン及びクロロホルムに不溶。 ＴＬＣ（シリカ，n-BuOH/W/AcOH=4/2/1)：Ｒｆ0.１６〜
0.３５ ＩＲ(KBr):ν 3675(22.4),3650(22.2),3083( 2.7),2938
( 7.9),2863(10.6),2361(22.4),1678( 4.6),1657( 1.
5),1599( 4.0),1555( 0.6),1453( 3.4),1406( 8.3),127
9(14.9),1186(17.9),1152(17.2),1055(27.8),1022(22.
0), 994(24.7), 961(29.2), 930(33.4),897(31.2), 820
(17.1), 766(29.4), 704(30.0), 612(16.1),600(16.6),
577(23.5), 401(38.6) cm-1（透過率 ％） ＮＭＲ(d6 -DMSO): δ6.57,s,4H(トリアジン環のNH2 );
3.37,s,4H(イミダゾリン環の4,5-位);2.50,br,S,4H（エ
チレン基) Ｍａｓｓ：m/e 207( M+ ),177,163,150,138,125,97,83,
68,54,43,28Basic colorless crystals. Melting point: 214.5-22
5 ° C Soluble in MeOH, water and DMF when hot, DMSO and Ac
Soluble in cold OH, insoluble in acetone and chloroform. TLC (silica, n-BuOH / W / AcOH = 4/2/1): Rf 0.16 to
0.35 IR (KBr): ν 3675 (22.4), 3650 (22.2), 3083 (2.7), 2938
(7.9), 2863 (10.6), 2361 (22.4), 1678 (4.6), 1657 (1.
5), 1599 (4.0), 1555 (0.6), 1453 (3.4), 1406 (8.3), 127
9 (14.9), 1186 (17.9), 1152 (17.2), 1055 (27.8), 1022 (22.
0), 994 (24.7), 961 (29.2), 930 (33.4), 897 (31.2), 820
(17.1), 766 (29.4), 704 (30.0), 612 (16.1), 600 (16.6),
577 (23.5), 401 (38.6) cm -1 (transmittance%) NMR (d 6 -DMSO): δ6.57, s, 4H (NH 2 of triazine ring);
3.37, s, 4H (4,5-position of the imidazoline ring); 2.50, br, S, 4H (ethylene group) Mass: m / e 207 (M + ), 177,163,150,138,125,97,83,
68,54,43,28
【００１４】２−（4'- メチルイミダゾリニル-2')−エ
チレン−（4",6"-ジアミノ-1",3",5"-s-トリアジン）−
(2")2- (4'-methylimidazolinyl-2 ')-ethylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-
(2 ")
【００１５】[0015]
【化６】 [Chemical 6]
【００１６】塩基性無色結晶。融点：２５４〜２６４℃ ＤＭＦに熱時可溶、ＭｅＯＨ、水、ＤＭＳＯ及びＡｃＯ
Ｈに冷時可溶。 ＴＬＣ（シリカ，n-BuOH/W/AcOH=4/2/1)：Ｒｆ0.２２〜
0.４０ ＩＲ(KBr):ν 3904(29.1),3854(29.0),3841(29.3),3675
(28.7),3650(28.5),3567(27.7),3403(20.3),1734(38.
1),1717(36.5),1640(15.7),1620(21.0),1545(13.0),148
7(31.0),1458(18.2),1410(28.4),1283(37.8),1157(41.
1), 926(46.2), 837(42.2), 722(44.8),592(41.1), 569
(46.8), 521(44.4), 421(48.4) cm-1 ＮＭＲ(d6 -DMSO): δ6.52,s,4H(トリアジン環のNH2 );
3.93〜2.88,m,3H(イミダゾリン環の4,5-位);2.30,br,S,
4H（エチレン基);1.08と0.97,3H(メチル基) Ｍａｓｓ：m/e 221( M+ ),206,178,165,150,138,124,11
1,96,83,82,68,67,55,54,28Basic colorless crystals. Melting point: 254-264 ° C. Soluble in DMF when hot, MeOH, water, DMSO and AcO.
Soluble in H when cold. TLC (silica, n-BuOH / W / AcOH = 4/2/1): Rf 0.22 to
0.40 IR (KBr): ν 3904 (29.1), 3854 (29.0), 3841 (29.3), 3675
(28.7), 3650 (28.5), 3567 (27.7), 3403 (20.3), 1734 (38.
1), 1717 (36.5), 1640 (15.7), 1620 (21.0), 1545 (13.0), 148
7 (31.0), 1458 (18.2), 1410 (28.4), 1283 (37.8), 1157 (41.
1), 926 (46.2), 837 (42.2), 722 (44.8), 592 (41.1), 569
(46.8), 521 (44.4), 421 (48.4) cm -1 NMR (d 6 -DMSO): δ6.52, s, 4H (triazine ring NH 2 );
3.93-2.88, m, 3H (4,5-position of the imidazoline ring); 2.30, br, S,
4H (ethylene group); 1.08 and 0.97,3H (methyl group) Mass: m / e 221 (M + ), 206,178,165,150,138,124,11
1,96,83,82,68,67,55,54,28
【００１７】ｍ−（イミダゾリニル-2')−フェニレン−
（4",6"-ジアミノ-1",3",5"-s-トリアジン）−(2")M- (imidazolinyl-2 ')-phenylene-
(4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-(2")
【００１８】[0018]
【化７】 [Chemical 7]
【００１９】塩基性無色結晶。融点：２８５〜２９３℃ ＤＭＦ及びＤＭＳＯに熱時可溶、ＡｃＯＨ、水及びＭｅ
ＯＨに熱時も難溶。 ＴＬＣ（シリカ，n-BuOH/W/AcOH=4/2/1)：Ｒｆ0.２４〜
0.３５ ＩＲ(KBr):ν 3677(27.4),3652(27.2),3436(17.2),3414
(14.8),3330(17.8),3144(15.0),2367(33.9),1636(13.
6),1615(15.7),1539( 4.2),1512(13.7),1456(20.9),142
2(18.2),1387(12.8),1327(31.7),1283(29.0),1262(31.
3),1165(34.2),1084(36.2), 986(35.1),930(41.2), 830
(40.5), 812(27.7), 725(37.4), 704(36.5),617(38.8),
579(37.1), 550(38.0), 421(48.1) cm-1 ＮＭＲ(d6 -DMSO): δ8.83,s,1H(フェニレン基の２位);
8.45と8.2 及び8.02と7.88,2H（フェニレン基の4,6
位);7.67,7.53 及び7.39,1H(フェニレン基の５位);6.8
2,br.S,4H( トリアジン環のNH2 );3.64,s,4H Ｍａｓｓ：m/e 255( M+ ),227,226,214,187,170,142,12
9,102,43,28Basic colorless crystals. Melting point: 285-293 [deg.] C. Soluble in DMF and DMSO when hot, AcOH, water and Me.
Insoluble in OH when heated. TLC (silica, n-BuOH / W / AcOH = 4/2/1): Rf 0.24 to
0.35 IR (KBr): ν 3677 (27.4), 3652 (27.2), 3436 (17.2), 3414
(14.8), 3330 (17.8), 3144 (15.0), 2367 (33.9), 1636 (13.
6), 1615 (15.7), 1539 (4.2), 1512 (13.7), 1456 (20.9), 142
2 (18.2), 1387 (12.8), 1327 (31.7), 1283 (29.0), 1262 (31.
3), 1165 (34.2), 1084 (36.2), 986 (35.1), 930 (41.2), 830
(40.5), 812 (27.7), 725 (37.4), 704 (36.5), 617 (38.8),
579 (37.1), 550 (38.0), 421 (48.1) cm -1 NMR (d 6 -DMSO): δ8.83, s, 1H (2nd position of phenylene group);
8.45 and 8.2 and 8.02 and 7.88,2H (phenylene group 4,6
Position); 7.67,7.53 and 7.39,1H (5th position of the phenylene group); 6.8
2, br.S, 4H (NH 2 of triazine ring); 3.64, s, 4H Mass: m / e 255 (M + ), 227,226,214,187,170,142,12
9,102,43,28
【００２０】ｍ−（４'-メチルイミダゾリニル-2')−フ
ェニレン−（4",6"-ジアミノ-1",3",5"-s-トリアジン）
−(2")M- (4'-methylimidazolinyl-2 ')-phenylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)
-(2 ")
【００２１】[0021]
【化８】 [Chemical 8]
【００２２】塩基性無色結晶。融点：２８９〜２９９℃ ＤＭＦ及びＤＭＳＯに熱時可溶、熱ＡｃＯＨ、水及びＭ
ｅＯＨに難溶。 ＴＬＣ（シリカ，n-BuOH/W/AcOH=4/2/1)：Ｒｆ0.２６〜
0.４１ ＩＲ(KBr):ν 3341( 9.7),3171( 8.2),2967(22.4),2928
(23.9),2867(26.5),1647( 5.2),1615( 7.2),1538(0.8
4),1489(12.8),1449(10.0),1412(13.0),1385( 6.9),132
0(25.9),1281(25.5),1163(33.1),1119(34.1),1076(33.
1), 986(30.0), 924(40.4), 887(41.7),828(31.9), 806
(25.0), 725(32.2), 700(27.7), 619(27.6),581(27.4)
cm-1 ＮＭＲ(d6 -DMSO): δ8.78,s,1H(フェニレン基の２位);
8.38と8.25及び7.94と7.82,2H（フェニレン基の4,6
位);7.62,7.48 及び7.34,1H(フェニレン基の５位);6.7
7,br.S,4H( トリアジン環のNH2 );4.07〜3.60,m,3H(イ
ミダゾリン環の4,5 位);1.24と1.14,3H(メチル基) Ｍａｓｓ：m/e 269( M+ ),254,226,213,186,169,144,12
9,102,85,68,43,28Basic colorless crystals. Melting point: 289 to 299 ° C Soluble in DMF and DMSO when hot, hot AcOH, water and M
Hardly soluble in eOH. TLC (silica, n-BuOH / W / AcOH = 4/2/1): Rf 0.26 ~
0.41 IR (KBr): ν 3341 (9.7), 3171 (8.2), 2967 (22.4), 2928
(23.9), 2867 (26.5), 1647 (5.2), 1615 (7.2), 1538 (0.8
4), 1489 (12.8), 1449 (10.0), 1412 (13.0), 1385 (6.9), 132
0 (25.9), 1281 (25.5), 1163 (33.1), 1119 (34.1), 1076 (33.
1), 986 (30.0), 924 (40.4), 887 (41.7), 828 (31.9), 806
(25.0), 725 (32.2), 700 (27.7), 619 (27.6), 581 (27.4)
cm -1 NMR (d 6 -DMSO): δ8.78, s, 1H (position 2 of phenylene group);
8.38 and 8.25 and 7.94 and 7.82,2H (phenylene group 4,6
Position); 7.62,7.48 and 7.34,1H (5th position of the phenylene group); 6.7
7, br.S, 4H (NH 2 of triazine ring); 4.07 to 3.60, m, 3H (4,5 position of imidazoline ring); 1.24 and 1.14,3H (methyl group) Mass: m / e 269 (M + ), 254,226,213,186,169,144,12
9,102,85,68,43,28
【００２３】ｐ−（イミダゾリニル-2')−フェニレン−
（4",6"-ジアミノ-1",3",5"-s-トリアジン）−(2")P- (imidazolinyl-2 ')-phenylene-
(4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-(2")
【００２４】[0024]
【化９】 [Chemical 9]
【００２５】塩基性無色結晶。融点：２９７〜３０７℃ ＤＭＦ及びＡｃＯＨに熱時可溶、ＤＭＳＯに冷時可溶、
水及びＭｅＯＨに不溶。 ＴＬＣ（シリカ，n-BuOH/W/AcOH=4/2/1)：Ｒｆ0.２１〜
0.３８ ＩＲ(KBr):ν 3418(12.6),3202(11.8),3129(11.6),2363
(32.4),1667( 9.6),1638( 5.0),1620( 6.5),1582( 7.
5),1539( 1.1),1451(15.8),1431(14.4),1397( 6.4),134
1(20.6),1256(26.5),1192(30.3),1152(33.3),1098(26.
6),1021(31.7), 986(26.7), 949(35.4),901(31.0), 866
(34.6), 816(15.4), 702(31.0), 629(29.4),538(30.4),
498(30.8), 457(32.3), 430(35.8) cm-1 ＮＭＲ(d6 -DMSO): δ8.30と8.17,d,2H(フェニレン基);
7.90と7.77,d,2H(フェニレン基);6.70,s,4H(トリアジン
環のNH2 );3.60,s,4H(イミダゾリン環の4,5 位) Ｍａｓｓ：m/e 255( M+ ),226,170,142,129,116,102,7
6,43,28Basic colorless crystals. Melting point: 297 to 307 ° C. Soluble in DMF and AcOH when hot, soluble in DMSO when cold,
Insoluble in water and MeOH. TLC (silica, n-BuOH / W / AcOH = 4/2/1): Rf 0.21-
0.38 IR (KBr): ν 3418 (12.6), 3202 (11.8), 3129 (11.6), 2363
(32.4), 1667 (9.6), 1638 (5.0), 1620 (6.5), 1582 (7.
5), 1539 (1.1), 1451 (15.8), 1431 (14.4), 1397 (6.4), 134
1 (20.6), 1256 (26.5), 1192 (30.3), 1152 (33.3), 1098 (26.
6), 1021 (31.7), 986 (26.7), 949 (35.4), 901 (31.0), 866
(34.6), 816 (15.4), 702 (31.0), 629 (29.4), 538 (30.4),
498 (30.8), 457 (32.3), 430 (35.8) cm -1 NMR (d 6 -DMSO): δ 8.30 and 8.17, d, 2H (phenylene group);
7.90 and 7.77, d, 2H (phenylene group); 6.70, s, 4H (NH 2 of triazine ring); 3.60, s, 4H (4,5th position of imidazoline ring) Mass: m / e 255 (M + ), 226,170,142,129,116,102,7
6,43,28
【００２６】ｐ−（４'-メチルイミダゾリニル-2')−フ
ェニレン−（4",6"-ジアミノ-1",3",5"-s-トリアジン）
−(2")P- (4'-methylimidazolinyl-2 ')-phenylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)
-(2 ")
【００２７】[0027]
【化１０】 [Chemical 10]
【００２８】塩基性無色結晶。融点：３１６〜３２５℃ ＤＭＦ及びＤＭＳＯに熱時可溶、ＡｃＯＨに難溶。水及
びＭｅＯＨに不溶。 ＴＬＣ（シリカ，n-BuOH/W/AcOH=4/2/1)：Ｒｆ0.３２〜
0.４４ ＩＲ(KBr):ν 3476(16.2),3422(14.7),3351(12.4),3303
(12.3),3183(13.3),2963(23.6),2924(24.9),2863(27.
7),1653( 8.4),1615( 4.8),1576( 3.2),1539( 1.6),143
7( 8.5),1397( 6.7),1325(32.4),1302(36.8),1277(27.
0),1260(29.2),1167(39.8),1113(37.4),1055(41.0),101
5(42.8), 982(27.6), 899(40.5), 872(34.1),820(16.
4), 770(44.8), 704(34.2), 673(33.2), 588(32.6),502
(33.9) cm-1 ＮＭＲ(d6 -DMSO): δ8.26と8.16,d,2H(フェニレン基);
7.90と7.77,d,2H(フェニレン基);6.70,br.S,4H（トリア
ジン環のNH2 );3.88〜3.74,m,3H(イミダゾリン環の4,5
位);1.21と1.10,3H(メチル基) Ｍａｓｓ：m/e 269( M+ ),254,240,226,221,170,142,12
9,102,43,28Basic colorless crystals. Melting point: 316 to 325 [deg.] C. Soluble in DMF and DMSO when hot, hardly soluble in AcOH. Insoluble in water and MeOH. TLC (silica, n-BuOH / W / AcOH = 4/2/1): Rf 0.32-
0.44 IR (KBr): ν 3476 (16.2), 3422 (14.7), 3351 (12.4), 3303
(12.3), 3183 (13.3), 2963 (23.6), 2924 (24.9), 2863 (27.
7), 1653 (8.4), 1615 (4.8), 1576 (3.2), 1539 (1.6), 143
7 (8.5), 1397 (6.7), 1325 (32.4), 1302 (36.8), 1277 (27.
0), 1260 (29.2), 1167 (39.8), 1113 (37.4), 1055 (41.0), 101
5 (42.8), 982 (27.6), 899 (40.5), 872 (34.1), 820 (16.
4), 770 (44.8), 704 (34.2), 673 (33.2), 588 (32.6), 502
(33.9) cm -1 NMR (d 6 -DMSO): δ8.26 and 8.16, d, 2H (phenylene group);
7.90 and 7.77, d, 2H (phenylene group); 6.70, br.S, 4H (NH 2 of triazine ring); 3.88-3.74, m, 3H (4,5 of imidazoline ring)
Position); 1.21 and 1.10,3H (methyl group) Mass: m / e 269 (M + ), 254,240,226,221,170,142,12
9,102,43,28
【００２９】[0029]
（実施例１）サクシノニトリル１２．３ｇ(0.154モ
ル）、ジシアンジアミド１５．５ｇ（0.186 モル）、水
酸化カリウム０．８６ｇ及びn-ブタノール１００mlの４
者を30分間加熱還流したのち放冷し、析出してくる結晶
を濾取し、この濾取結晶を充分な量の水と共に煮沸し、
熱時に濾過し、濾液を放冷して析出する２−シアノエチ
ル−（4',6'-ジアミノ-1',3',5'-s-トリアジン）−(2')
の第１晶を濾取した。第１晶の濾取時の濾液を濃縮して
第２晶を濾取した。第１晶と第２晶を合わせて２１．９
ｇの２−シアノエチル−（4',6'-ジアミノ-1',3',5'-s-
トリアジン）−(2')が得られた。Example 1 12.3 g (0.154 mol) of succinonitrile, 15.5 g (0.186 mol) of dicyandiamide, 0.86 g of potassium hydroxide and 100 ml of n-butanol were added.
After heating and refluxing the person for 30 minutes, the mixture is allowed to cool, the precipitated crystals are collected by filtration, and the collected crystals are boiled with a sufficient amount of water,
2-Cyanoethyl- (4 ', 6'-diamino-1', 3 ', 5'-s-triazine)-(2') which precipitates by filtering while hot and cooling the filtrate
The first crystal of was collected by filtration. The filtrate at the time of collecting the first crystal was concentrated to collect the second crystal by filtration. The total of the first crystal and the second crystal is 21.9.
g of 2-cyanoethyl- (4 ', 6'-diamino-1', 3 ', 5'-s-
Triazine)-(2 ') was obtained.
【００３０】得られた２−シアノエチル−（4',6'-ジア
ミノ-1',3',5'-s-トリアジン）−(2')８．０ｇ(0.049モ
ル) 、エチレンジアミン１４．６ｇ（0.24モル）及び単
体硫黄０．０８ｇの３者を１．５時間加熱還流したの
ち、放冷して析出してくる結晶を濾取した。この濾取結
晶に脱硫するために水酸化ナトリウム０．４ｇと適量の
メタノールを加えて２時間加熱還流し、この系を放冷し
て析出する結晶を濾取した。次いでこれに水酸化ナトリ
ウム除去のため水を加えて攪拌し、結晶を濾取し乾燥し
て目的物の２−（イミダゾリニル-2')−エチレン−
（4",6"-ジアミノ-1",3",5"-s-トリアジン）−(2")８．
６６ｇ（収率85.8％）を得た。The obtained 2-cyanoethyl- (4 ', 6'-diamino-1', 3 ', 5'-s-triazine)-(2') 8.0 g (0.049 mol) and ethylenediamine 14.6 g ( 0.24 mol) and 0.08 g of elemental sulfur were heated under reflux for 1.5 hours and then allowed to cool and the precipitated crystals were collected by filtration. 0.4 g of sodium hydroxide and an appropriate amount of methanol were added to the crystals for desulfurization, and the mixture was heated under reflux for 2 hours. The system was allowed to cool and the precipitated crystals were collected by filtration. Then, water is added to this to remove sodium hydroxide and the mixture is stirred, and the crystals are collected by filtration and dried to give 2- (imidazolinyl-2 ')-ethylene
(4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-(2") 8.
66 g (yield 85.8%) was obtained.
【００３１】（実施例２）実施例１で用いた２−シアノ
エチル−（4',6'-ジアミノ-1',3',5'-s-トリアジン）−
(2')８．０ｇ(0.049モル) 、プロピレンジアミン１８．
０ｇ（0.24モル）及び単体硫黄０．０８ｇの３者を２時
間加熱還流したのち、実施例１と同様の方法により後処
理を行ない、目的物の２−（４'-メチルイミダゾリニル
-2')−エチレン−（4",6"-ジアミノ-1",3",5"-s-トリア
ジン）−(2")５．７５ｇ（収率53.3％）を得た。Example 2 2-Cyanoethyl- (4 ', 6'-diamino-1', 3 ', 5'-s-triazine) -used in Example 1
(2 ') 8.0 g (0.049 mol), propylenediamine 18.
After heating and refluxing 3 g of 0 g (0.24 mol) and 0.08 g of elemental sulfur for 2 hours, post-treatment was carried out in the same manner as in Example 1 to obtain the desired product, 2- (4'-methylimidazolinyl).
There were obtained 5.75 g (yield 53.3%) of -2 ')-ethylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-(2").
【００３２】（実施例３）イソフタロニトリル１２．８
ｇ(0.1モル）、ジシアンジアミド９．２４ｇ（0.11モ
ル）、水酸化カリウム０．８６ｇ及びn-ブタノール８０
mlの４者を１時間加熱還流したのち放冷して析出してく
る結晶を濾取水洗してｍ−シアノ−フェニル−（4',6'-
ジアミノ-1',3',5'-s-トリアジン）−(2')２０．８ｇ
（収率98.1％）を得た。Example 3 Isophthalonitrile 12.8
g (0.1 mol), dicyandiamide 9.24 g (0.11 mol), potassium hydroxide 0.86 g and n-butanol 80
After heating and refluxing 4 ml of 1 person for 1 hour and allowing to cool, the precipitated crystals are filtered and washed with water and m-cyano-phenyl- (4 ', 6'-
Diamino-1 ', 3', 5'-s-triazine)-(2 ') 20.8 g
(Yield 98.1%) was obtained.
【００３３】得られたｍ−シアノ−フェニル−（4',6'-
ジアミノ-1',3',5'-s-トリアジン）−(2')５．３ｇ(0.0
25モル) 、エチレンジアミン７．５ｇ(0.125モル）及び
単体硫黄０．０５３ｇの３者を１．５時間加熱還流した
のち、実施例１と同様の方法により後処理を行い、目的
物のｍ−（イミダゾリニル-2')−フェニレン−（4",6"-
ジアミノ-1",3",5"-s-トリアジン）−(2")５．１６ｇ
（収率80.9％）を得た。The resulting m-cyano-phenyl- (4 ', 6'-
Diamino-1 ', 3', 5'-s-triazine)-(2 ') 5.3 g (0.0
25 mol), 7.5 g (0.125 mol) of ethylenediamine and 0.053 g of elemental sulfur were heated under reflux for 1.5 hours, and post-treated in the same manner as in Example 1 to give m- ( Imidazolinyl-2 ')-phenylene- (4 ", 6"-
Diamino-1 ", 3", 5 "-s-triazine)-(2") 5.16 g
(Yield 80.9%) was obtained.
【００３４】（実施例４）実施例３で用いたｍ−シアノ
−フェニル−（4',6'-ジアミノ-1',3',5'-s-トリアジ
ン）−(2')５．３ｇ(0.025モル) 、プロピレンジアミン
９．２５ｇ(0.125モル）及び単体硫黄０．０５３ｇの３
者を１．５時間加熱還流したのち、実施例１と同様の方
法により後処理を行ない、目的物のｍ−（４'-メチルイ
ミダゾリニル-2')−フェニレン−（4",6"-ジアミノ-1",
3",5"-s-トリアジン）−(2")５．８１ｇ（収率86.4％）
を得た。(Example 4) m-Cyano-phenyl- (4 ', 6'-diamino-1', 3 ', 5'-s-triazine)-(2') 5.3 g used in Example 3 (0.025 mol), propylenediamine 9.25 g (0.125 mol) and elemental sulfur 0.053 g 3
After heating under reflux for 1.5 hours, a post-treatment was carried out in the same manner as in Example 1 to give m- (4'-methylimidazolinyl-2 ')-phenylene- (4 ", 6") of the desired product. -Diamino-1 ",
3 ", 5" -s-triazine)-(2 ") 5.81 g (yield 86.4%)
Got
【００３５】（実施例５）テレフタロニトリル１２．８
ｇ(0.1モル）、ジシアンジアミド９．２４ｇ（0.11モ
ル）、水酸化カリウム０．５６ｇ及びn-ブタノール１０
０mlの４者を１時間加熱還流したのち、放冷して析出し
てくる結晶を濾取水洗してｐ−シアノ−フェニル−
（4',6'-ジアミノ-1',3',5'-s-トリアジン）−(2')２
０．１４ｇ（収率95.0％）を得た。Example 5 Terephthalonitrile 12.8
g (0.1 mol), dicyandiamide 9.24 g (0.11 mol), potassium hydroxide 0.56 g and n-butanol 10
After heating and refluxing 4 ml of 0 ml for 1 hour, the mixture was allowed to cool and the precipitated crystals were collected by filtration and washed with water to obtain p-cyano-phenyl-
(4 ', 6'-diamino-1', 3 ', 5'-s-triazine)-(2') 2
0.14 g (yield 95.0%) was obtained.
【００３６】得られたｐ−シアノ−フェニル−（4',6'-
ジアミノ-1',3',5'-s-トリアジン）−(2')５．３ｇ(0.0
25モル) 、エチレンジアミン７．５ｇ(0.125モル）及び
単体硫黄０．０５３ｇの３者を１．５時間加熱還流した
のち、実施例１と同様の方法により後処理を行い、目的
物のｐ−（イミダゾリニル-2')−フェニレン−（4",6"-
ジアミノ-1",3",5"-s-トリアジン）−(2")５．８８ｇ
（収率92.2％）を得た。The resulting p-cyano-phenyl- (4 ', 6'-
Diamino-1 ', 3', 5'-s-triazine)-(2 ') 5.3 g (0.0
25 mol), 7.5 g (0.125 mol) of ethylenediamine, and 0.053 g of elemental sulfur were heated under reflux for 1.5 hours, and then post-treated in the same manner as in Example 1 to give p- ( Imidazolinyl-2 ')-phenylene- (4 ", 6"-
Diamino-1 ", 3", 5 "-s-triazine)-(2") 5.88 g
(Yield 92.2%) was obtained.
【００３７】（実施例６）実施例５で用いたｐ−シアノ
−フェニル−（4',6'-ジアミノ-1',3',5'-s-トリアジ
ン）−(2')５．３ｇ(0.025モル) 、プロピレンジアミン
９．２５ｇ(0.125モル）及び単体硫黄０．０５３ｇの３
者を１．５時間反応させたのち、実施例１と同様の方法
により後処理を行ない、目的物のｐ−（４'-メチルイミ
ダゾリニル-2')−フェニレン−（4",6"-ジアミノ-1",
3",5"-s-トリアジン）−(2")６．２２ｇ（収率92.5％）
を得た。Example 6 5.3 g of p-cyano-phenyl- (4 ', 6'-diamino-1', 3 ', 5'-s-triazine)-(2') used in Example 5 (0.025 mol), propylenediamine 9.25 g (0.125 mol) and elemental sulfur 0.053 g 3
After the reaction was carried out for 1.5 hours, post-treatment was carried out in the same manner as in Example 1 to obtain the desired product p- (4'-methylimidazolinyl-2 ')-phenylene- (4 ", 6". -Diamino-1 ",
3 ", 5" -s-triazine)-(2 ") 6.22 g (yield 92.5%)
Got
【００３８】（実施例７）実施例１で得られた２−（イ
ミダゾリニル-2')−エチレン−（4",6"-ジアミノ-1",
3",5"-s-トリアジン）−(2")（以下、硬化剤Ａとい
う）、実施例２で得られた２−（４'-メチルイミダゾリ
ニル-2')−エチレン−（4",6"-ジアミノ-1",3",5"-s-ト
リアジン）−(2")（以下、硬化剤Ｂという）、実施例３
で得られたｍ−（イミダゾリニル-2')−フェニレン−
（4",6"-ジアミノ-1",3",5"-s-トリアジン）−(2")（以
下、硬化剤Ｃという）、実施例４で得られたｍ−（４'-
メチルイミダゾリニル-2')−フェニレン−（4",6"-ジア
ミノ-1",3",5"-s-トリアジン）−(2")（以下、硬化剤Ｄ
という）、実施例５で得られたｐ−（イミダゾリニル-
2')−フェニレン−（4",6"-ジアミノ-1",3",5"-s-トリ
アジン）−(2")（以下、硬化剤Ｅという）及び実施例６
で得られたｐ−（４'-メチルイミダゾリニル-2')−フェ
ニレン−（4",6"-ジアミノ-1",3",5"-s-トリアジン）−
(2")（以下、硬化剤Ｆという）を用い、ＪＩＳ Ｃ−２
１０５ 16.2の熱板法ゲル化時間試験方法により、本発
明化合物のエポキシ樹脂硬化性を調べた。エポキシ樹脂
〔商品名：ＡＥＲ−３３１、ビスフェノールＡグリシジ
ルエーテル、旭化成工業（株）製〕１００重量部及びコ
ロイダルシリカ〔商品名：アエロジル３００、日本アエ
ロジル（株）製〕２重量部に、本発明化合物を１０重量
部の配合割合で添加し、攪拌混合したのち、３本ロール
機を用いて混練してエポキシ樹脂組成物を調製した。Example 7 2- (imidazolinyl-2 ')-ethylene- (4 ", 6" -diamino-1 ", obtained in Example 1,
3 ", 5" -s-triazine)-(2 ") (hereinafter referred to as curing agent A), 2- (4'-methylimidazolinyl-2 ')-ethylene- (4 obtained in Example 2 ", 6" -Diamino-1 ", 3", 5 "-s-triazine)-(2") (hereinafter referred to as curing agent B), Example 3
M- (imidazolinyl-2 ')-phenylene-obtained in
(4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-(2") (hereinafter referred to as curing agent C), m- (4'- obtained in Example 4
Methylimidazolinyl-2 ')-phenylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-(2") (hereinafter curing agent D
, P- (imidazolinyl-obtained in Example 5)
2 ')-phenylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-(2") (hereinafter referred to as curing agent E) and Example 6
P- (4'-methylimidazolinyl-2 ')-phenylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine) obtained in
(2 ") (hereinafter referred to as curing agent F), using JIS C-2
105 The epoxy resin curability of the compound of the present invention was examined by the hot plate gelation time test method of 16.2. 100 parts by weight of epoxy resin [trade name: AER-331, bisphenol A glycidyl ether, manufactured by Asahi Kasei Kogyo Co., Ltd.] and 2 parts by weight of the compound of the present invention in colloidal silica [trade name: Aerosil 300, manufactured by Nippon Aerosil Co., Ltd.] Was added at a mixing ratio of 10 parts by weight, mixed with stirring, and then kneaded using a three-roll machine to prepare an epoxy resin composition.
【００３９】前記のエポキシ樹脂組成物を用いた１８０
℃の温度におけるゲル化時間及び室温におけるポットラ
イフの測定結果は表１に示すとおりである。なお、ポッ
トライフは２５℃において初期粘度が１０倍値を超える
までに要する日数とした。180 using the above epoxy resin composition
Table 1 shows the measurement results of the gelation time at a temperature of ℃ and the pot life at room temperature. The pot life was the number of days required for the initial viscosity to exceed 10 times the value at 25 ° C.
【００４０】[0040]
【表１】 [Table 1]
【００４１】（実施例８）実施例７においてエポキシ樹
脂１００重量部、コロイダルシリカ２重量部及び硬化剤
Ａ、硬化剤Ｂ、硬化剤Ｃあるいは硬化剤Ｆを各々１０重
量部配合し、混練して調製したエポキシ樹脂組成物を３
mm×１００mm×１５０mmの鋳型に流し込み、１００℃の
温度において４時間、さらに１５０℃の温度で４時間熱
硬化したのち、所定の寸法に切り出し、硬化樹脂性能を
調べた。その結果は表２に示すとおりであり、各評価試
験は次に示す試験規格及び条件により行った。Example 8 In Example 7, 100 parts by weight of epoxy resin, 2 parts by weight of colloidal silica and 10 parts by weight of each of curing agent A, curing agent B, curing agent C or curing agent F were mixed and kneaded. 3 of the prepared epoxy resin composition
It was poured into a mold of mm × 100 mm × 150 mm and heat-cured at a temperature of 100 ° C. for 4 hours and further at a temperature of 150 ° C. for 4 hours, and then cut into a predetermined size to examine the cured resin performance. The results are shown in Table 2, and each evaluation test was performed according to the following test standards and conditions.
【００４２】 熱変形温度 ：JIS K-7207 昇温速度：２℃／分 ガラス転移温度 ：ASTM D696 昇温速度：５℃／分、
但しＴＭＡ法 熱膨張係数 ：ASTM D696 室温からガラス転移温
度まで、但しＴＭＡ法 体積抵抗率 ：JIS K-6911 測定温度：２５℃ 煮沸後体積抵抗率：JIS K-6911 １時間煮沸後、測定温
度：２５℃ 沸騰水吸水率 ：JIS K-7209 １時間煮沸後 誘電率 ：JIS K-6911 １ＫＨｚ、測定温度：
２５℃ 誘電正接 ：JIS K-6911 １ＫＨｚ、測定温度：
２５℃ 曲げ強度 ：JIS K-7203 測定温度：２５℃ 曲げ弾性率 ：JIS K-7203 測定温度：２５℃ 硬度 ：ASTM D2240 測定温度：２５℃ 絶縁破壊電圧 ：JIS K-6911 測定温度：２０℃Heat distortion temperature: JIS K-7207 Temperature rising rate: 2 ° C./minute Glass transition temperature: ASTM D696 Temperature rising rate: 5 ° C./minute
However, TMA method thermal expansion coefficient: ASTM D696 from room temperature to glass transition temperature, but TMA method volume resistivity: JIS K-6911 measurement temperature: 25 ° C volume resistivity after boiling: JIS K-6911 1 hour after boiling, measurement temperature: 25 ° C Boiling water absorption rate: JIS K-7209 After boiling for 1 hour Dielectric constant: JIS K-6911 1KHz, Measurement temperature:
25 ℃ Dielectric loss tangent: JIS K-6911 1KHz, Measurement temperature:
25 ° C Bending strength: JIS K-7203 Measuring temperature: 25 ° C Bending elastic modulus: JIS K-7203 Measuring temperature: 25 ° C Hardness: ASTM D2240 Measuring temperature: 25 ° C Dielectric breakdown voltage: JIS K-6911 Measuring temperature: 20 ° C
【００４３】[0043]
【表２】 [Table 2]
【００４４】[0044]
【発明の効果】本発明化合物を硬化剤として用いる一液
性エポキシ樹脂組成物は、室温における保存安定性に優
れる上に、高温領域において短時間硬化を発現しうるも
のであり、硬化後のエポキシ樹脂は高いガラス転移温度
を示すなど耐熱性に優れた有用な材料として使用でき
る。また本発明化合物は近年実用化されたエポキシ−ア
ダクト型の一液エポキシ用硬化剤と異なり、エポキシ樹
脂に対して相溶が良く均一で透明な硬化樹脂が得られる
ので、塗料、電気絶縁材料及び印刷材料などの用途に好
適である。The one-pack type epoxy resin composition using the compound of the present invention as a curing agent is excellent in storage stability at room temperature and, at the same time, can exhibit curing for a short time in a high temperature region. The resin can be used as a useful material having excellent heat resistance such as showing a high glass transition temperature. Further, the compound of the present invention is different from the epoxy-adduct type one-pack type epoxy curing agent which has been put into practical use in recent years, and it is possible to obtain a cured resin which is well compatible with the epoxy resin and is uniform and transparent. It is suitable for applications such as printing materials.
Claims (2)
を有するジアミノ−ｓ−トリアジン化合物。 【化１】 1. A diamino-s-triazine compound having an imidazoline ring represented by the general formula of Chemical formula 1. [Chemical 1]
を有するジアミノ−ｓ−トリアジン化合物を用いること
を特徴とするエポキシ樹脂の硬化方法。2. A method for curing an epoxy resin, which comprises using a diamino-s-triazine compound having an imidazoline ring represented by the general formula of Chemical formula 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5172215A JP2952135B2 (en) | 1993-06-19 | 1993-06-19 | Diamino-s-triazine compound having imidazoline ring and epoxy resin curing agent containing the compound as active ingredient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5172215A JP2952135B2 (en) | 1993-06-19 | 1993-06-19 | Diamino-s-triazine compound having imidazoline ring and epoxy resin curing agent containing the compound as active ingredient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0710871A true JPH0710871A (en) | 1995-01-13 |
| JP2952135B2 JP2952135B2 (en) | 1999-09-20 |
Family
ID=15937732
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5172215A Expired - Lifetime JP2952135B2 (en) | 1993-06-19 | 1993-06-19 | Diamino-s-triazine compound having imidazoline ring and epoxy resin curing agent containing the compound as active ingredient |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2952135B2 (en) |
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