JPH0710850A - Diamino-s-triazine compound having carbamoyl group and method for curing epoxy resin with the compound - Google Patents
Diamino-s-triazine compound having carbamoyl group and method for curing epoxy resin with the compoundInfo
- Publication number
- JPH0710850A JPH0710850A JP17221693A JP17221693A JPH0710850A JP H0710850 A JPH0710850 A JP H0710850A JP 17221693 A JP17221693 A JP 17221693A JP 17221693 A JP17221693 A JP 17221693A JP H0710850 A JPH0710850 A JP H0710850A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- diamino
- triazine
- epoxy resin
- carbamoyl
- 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
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はカルバモイル基を有する
ジアミノ−ｓ−トリアジン化合物に関するものである。
また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。FIELD OF THE INVENTION The present invention relates to a diamino-s-triazine compound having a carbamoyl group.
The compound of the present invention is also useful as a curing agent or curing accelerator for epoxy resins.
【０００２】[0002]
【従来の技術】従来から多くのカルバモイル化合物がエ
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。しかしながら、これまでカルバモイル基を有す
るジアミノ−ｓ−トリアジン化合物をエポキシ樹脂の硬
化剤あるいは硬化促進剤として使用した例は知られてい
ない。2. Description of the Related Art Conventionally, many carbamoyl compounds have been used as curing agents or curing accelerators for epoxy resins. However, no examples have hitherto been known in which a diamino-s-triazine compound having a carbamoyl group is used as a curing agent or curing accelerator for an epoxy resin.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、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
な分子内にカルバモイル基を有する新規なジアミノ−ｓ
−トリアジン化合物を提供することにある。The object of the present invention is to provide a novel diamino-s having a carbamoyl group in the molecule which is useful as a curing agent or curing accelerator for epoxy resin compositions.
-To provide a triazine compound.
【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、ジニトリルとジシ
アンジアミドから片方にニトリル基を有するジアミノ−
ｓ−トリアジン化合物を合成し、この化合物を出発原料
として単体硫黄の存在下１，２−脂肪族ジアミンを反応
させることにより、イミダゾリン環を有するジアミノ−
ｓ−トリアジン化合物が得られ、さらにこのイミダゾリ
ン環を有するジアミノ−ｓ−トリアジン化合物を水と共
に煮沸することにより、化２の一般式で示される分子内
にカルバモイル基を有するジアミノ−ｓ−トリアジン化
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 As a result of intensive studies conducted by the present inventors in view of such circumstances, as a result of dinitrile and dicyandiamide, a diamino-group having a nitrile group on one side is formed.
A s-triazine compound is synthesized and a 1,2-aliphatic diamine is reacted with this compound as a starting material in the presence of elemental sulfur to give a diamino-containing imidazoline ring.
An s-triazine compound is obtained, and the diamino-s-triazine compound having an imidazoline ring is boiled with water to give a diamino-s-triazine compound having a carbamoyl group in the molecule represented by the general formula (2). It was found that these compounds have an excellent epoxy resin curing action, and completed the present invention.
【０００５】[0005]
【化２】 [Chemical 2]
【０００６】本発明化合物の出発原料となるジアミノ−
ｓ−トリアジン化合物は、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
（Bull. Chem. Soc. Japan），第38巻，1820〜1824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。Diamino-a starting material for the compounds of the present invention
s-triazine compounds are described in British Patent No. 642409,
Synthetic Organic Chemistry, 24, 125-126 (1966) and Bulletin of Chemical Society Japan (Bull. Chem. Soc. Japan), 38, 1820-1824 (1965). Is obtained by the method (1), and its synthetic method is represented by the reaction formula shown in Chemical formula 3.
【０００７】[0007]
【化３】 [Chemical 3]
【０００８】本発明化合物の合成に当たっては、前記の
ジアミノ−ｓ−トリアジン化合物１モルに対して１，２
−ジアミン化合物を３〜１０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カルバモイル基を
有するジアミノ−ｓ−トリアジン化合物が得られ、さら
にこの化合物を水と共に煮沸することにより、目的のジ
アミノ−ｓ−トリアジン環を有する新規なカルバモイル
化合物が得られる。これらの反応を式で表せば化４に示
すとおりである。In synthesizing the compound of the present invention, 1,2 mol of 1 mol of the diamino-s-triazine compound is used.
-A diamino-s-triazine compound having a carbamoyl group is obtained by heating and refluxing a mixture obtained by adding 3 to 10 moles of a diamine compound in the presence of elemental sulfur, and further boiling this compound with water to give the desired compound. A new carbamoyl compound having a diamino-s-triazine ring is obtained. These reactions are represented by formulas as shown in Chemical formula 4.
【０００９】[0009]
【化４】 [Chemical 4]
【００１０】代表的な本発明のカルバモイル基を有する
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 a carbamoyl group of the present invention and their physical properties are as follows.
【００１１】２−アミノエチル−カルバモイル−エチレ
ン−（4',6'-ジアミノ-1',3',5'-s-トリアジン〕−(2')2-Aminoethyl-carbamoyl-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：１８３〜１９３．
６℃ 水、ＤＭＳＯ及びＡｃＯＨに易溶、ＭｅＯＨ及びＤＭＦ
に可溶、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)：Ｒｆ0.１１〜
0.２５ ＩＲ(KBr):ν 3445( 8.6),3391(10.0),3333(18.0),3137
(11.6),3058(14.1),2903(23.1),2361(33.1),1669(12.
7),1636( 4.1),1541( 3.3),1458(12.6),1428(15.2),140
8(21.8),1381(27.1),1329(26.2),1271(27.7),1256(24.
7),1186(26.9),1100(33.4),1059(35.5),1036(38.0), 99
4(30.8), 965(38.9), 911(28.9), 872(32.8),828(32.
2), 814(28.4), 747(34.5), 687(39.9), 592(27.4),542
(34.0), 469(43.7), 405(42.5) cm-1（透過率 ％） ＮＭＲ(d6 -DMSO): δ7.70,s,1H(アミド基);6.49,s,4H
(トリアジン環のNH2 );3.08〜2.88,t,2H(NH2 −CH2 −C
H2 −）; 2.64〜2.43,m,2H(CH2 −CH2 NH-CO-);2.47,b
r.s,4H（NH−CO−CH2 −CH2 −);2.50〜2.00,m,2H(NH2
−CH2 −CH2 −） Ｍａｓｓ：m/e 225( M+ ) は不出現,207,196,195,183,1
66,138,125,111,99,85,68,54,43,30,28Basic colorless crystals. Melting point: 183-193.
6 ℃ Easily soluble in water, DMSO and AcOH, MeOH and DMF
Soluble in, insoluble in acetone and chloroform. TLC (silica, n-BuOH / W / AcOH = 4/2/1): Rf 0.11-
0.25 IR (KBr): ν 3445 (8.6), 3391 (10.0), 3333 (18.0), 3137
(11.6), 3058 (14.1), 2903 (23.1), 2361 (33.1), 1669 (12.
7), 1636 (4.1), 1541 (3.3), 1458 (12.6), 1428 (15.2), 140
8 (21.8), 1381 (27.1), 1329 (26.2), 1271 (27.7), 1256 (24.
7), 1186 (26.9), 1100 (33.4), 1059 (35.5), 1036 (38.0), 99
4 (30.8), 965 (38.9), 911 (28.9), 872 (32.8), 828 (32.
2), 814 (28.4), 747 (34.5), 687 (39.9), 592 (27.4), 542
(34.0), 469 (43.7), 405 (42.5) cm -1 (transmittance%) NMR (d 6 -DMSO): δ7.70, s, 1H (amide group); 6.49, s, 4H
(NH 2 triazine rings); 3.08~2.88, t, 2H ( NH 2 -CH 2 -C
H 2 -); 2.64~2.43, m , 2H (CH 2 -CH 2 NH-CO -); 2.47, b
rs, 4H (NH-CO- CH 2 -CH 2 -); 2.50~2.00, m, 2H (NH 2
-CH 2 -CH 2 -) Mass: m / e 225 (M +) is not appeared, 207,196,195,183,1
66,138,125,111,99,85,68,54,43,30,28
【００１４】２−アミノプロピル−カルバモイル−エチ
レン−（4',6'-ジアミノ-1',3',5'-s-トリアジン）−
(2')2-Aminopropyl-carbamoyl-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：１５９〜１６５℃ 水、ＤＭＳＯ及びＡｃＯＨに易溶、ＭｅＯＨ及びＤＭＦ
に可溶、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)：Ｒｆ0.０８〜
0.２８ ＩＲ(KBr):ν 3428(12.0),3332(11.7),3229(12.8),3069
(18.8),2973(20.2),2872(24.8),2361(35.4),2342(37.
3),1644( 5.6),1624( 7.5),1570( 3.5),1451(12.4),141
2(24.3),1393(31.3),1362(30.1),1333(25.5),1314(36.
0),1283(37.2),1238(40.8),1142(30.4),1115(37.7),108
0(37.9),1028(39.4), 997(38.7), 970(40.2),938(40.
2), 882(48.3), 824(32.4), 789(44.8), 602(30.9),577
(32.8) cm-1 ＮＭＲ(d6 -DMSO)：δ7.77,s,1H(-CONH);6.57,s,4H (ト
リアジン環の -NH2 );2.93と2.87,d,2H(アミノ基隣接の
メチレン基);2.60〜2.40,m,1H(メチル基隣接のメチレン
基);2.50,br,s,4H（エチレン基);2.37,br,s,2H（プロピ
レン基の末端NH2 );0.97と0.87,d,3H(メチル基) Ｍａｓｓ：m/e 239( M+ ) は不出現,210,197,196,183,1
66,139,138,125,111,99,85,68,54,44,43,30Basic colorless crystals. Melting point: 159 to 165 ° C Water, easily soluble in DMSO and AcOH, MeOH and DMF
Soluble in, insoluble in acetone and chloroform. TLC (silica, n-BuOH / W / AcOH = 4/2/1): Rf 0.08-
0.28 IR (KBr): ν 3428 (12.0), 3332 (11.7), 3229 (12.8), 3069
(18.8), 2973 (20.2), 2872 (24.8), 2361 (35.4), 2342 (37.
3), 1644 (5.6), 1624 (7.5), 1570 (3.5), 1451 (12.4), 141
2 (24.3), 1393 (31.3), 1362 (30.1), 1333 (25.5), 1314 (36.
0), 1283 (37.2), 1238 (40.8), 1142 (30.4), 1115 (37.7), 108
0 (37.9), 1028 (39.4), 997 (38.7), 970 (40.2), 938 (40.
2), 882 (48.3), 824 (32.4), 789 (44.8), 602 (30.9), 577
(32.8) cm -1 NMR (d 6 -DMSO): δ7.77, s, 1H (-CONH); 6.57, s, 4H (-NH 2 of triazine ring); 2.93 and 2.87, d, 2H (amino group Adjacent methylene group); 2.60 to 2.40, m, 1H (methyl group adjacent methylene group); 2.50, br, s, 4H (ethylene group); 2.37, br, s, 2H (terminal NH 2 of propylene group); 0.97 and 0.87, d, 3H (methyl group) Mass: m / e 239 (M + ) does not appear, 210,197,196,183,1
66,139,138,125,111,99,85,68,54,44,43,30
【００１７】ｍ−（２−アミノエチル−カルバモイル）
−フェニレン−（4',6'-ジアミノ-1',3',5'-s-トリアジ
ン）−(2')M- (2-aminoethyl-carbamoyl)
-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：２６０〜２６９℃ ＤＭＦ及びＤＭＳＯに可溶、水及びＭｅＯＨに不溶。 ＴＬＣ（シリカ，n-BuOH/W/AcOH=4/2/1)：Ｒｆ0.２８〜
0.３９ ＩＲ(KBr):ν 3362( 8.8),3206( 8.8),2951(18.5),2872
(20.7),2367(31.0),1676(10.7),1626( 4.4),1541( 1.
5),1449( 9.8),1385( 9.5),1298(22.9),1281(20.3),124
6(25.9),1194(29.4),1173(29.1),1103(31.2), 986(34.
7), 941(29.9), 895(34.0), 828(31.3),810(29.7), 766
(33.9), 712(26.0), 623(25.8), 583(29.4),467(40.8),
430(40.4), 411(42.2) cm-1 ＮＭＲ(d6 -DMSO): δ8.66,s,1H(フェニレン基の２位);
8.39〜7.34,m,4H(フェニレン基の4,5,6 位及び-NH-CO
-);6.73,s,4H (トリアジン環の-NH2 );3.33〜3.16,t,2H
( -CH2 −NH2 );2.80〜2.60,t,2H(-CONH-CH2 -);2.19,b
r.s,2H(脂肪族末端アミン) Ｍａｓｓ：m/e 273( M+ ) は不出現,244,243,231,226,2
14,187,169,144,128,119,117,102,76,43,30,28Basic colorless crystals. Melting point: 260-269 ° C Soluble in DMF and DMSO, insoluble in water and MeOH. TLC (silica, n-BuOH / W / AcOH = 4/2/1): Rf 0.28-
0.39 IR (KBr): ν 3362 (8.8), 3206 (8.8), 2951 (18.5), 2872
(20.7), 2367 (31.0), 1676 (10.7), 1626 (4.4), 1541 (1.
5), 1449 (9.8), 1385 (9.5), 1298 (22.9), 1281 (20.3), 124
6 (25.9), 1194 (29.4), 1173 (29.1), 1103 (31.2), 986 (34.
7), 941 (29.9), 895 (34.0), 828 (31.3), 810 (29.7), 766
(33.9), 712 (26.0), 623 (25.8), 583 (29.4), 467 (40.8),
430 (40.4), 411 (42.2) cm -1 NMR (d 6 -DMSO): δ8.66, s, 1H (2nd position of phenylene group);
8.39 ~ 7.34, m, 4H (4,5,6 position of phenylene group and -NH-CO
-); 6.73, s, 4H (-NH 2 of triazine ring); 3.33 to 3.16, t, 2H
(-CH 2 -NH 2); 2.80~2.60 , t, 2H (-CONH-CH 2 -); 2.19, b
rs, 2H (aliphatic terminal amine) Mass: m / e 273 (M + ) does not appear, 244,243,231,226,2
14,187,169,144,128,119,117,102,76,43,30,28
【００２０】ｐ−（２−アミノエチル−カルバモイル）
−フェニレン−（4',6'-ジアミノ-1',3',5'-s-トリアジ
ン）−(2')P- (2-aminoethyl-carbamoyl)
-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：２５２〜２６７℃ 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)：Ｒｆ0.２４〜
0.３８ ＩＲ(KBr):ν 3445( 7.9),3330( 9.3),3264( 9.7),3166
( 7.7),2915(17.2),2865(17.3),2363(26.9),1663( 4.
3),1642( 3.0),1584( 8.8),1536( 1.6),1456(10.6),139
9( 7.8),1364(20.6),1312(17.1),1294(20.7),1262(22.
9),1194(28.8),1165(27.3),1076(26.6),1051(28.3),102
2(23.9), 986( 4.9), 903(30.2), 874(30.4),858(34.
7), 818(18.2), 745(29.2), 629(31.1), 598(32.0),563
(29.8), 513(28.3), 450(36.7) cm-1 ＮＭＲ(d6 -DMSO): δ8.49,s,1H(-CONH-);8.40と8.27,
d,2H(フェニレン基);8.00と7.86,d,2H(フェニレン基);
6.77,br.S,4H( トリアジン環のNH2 );3.37〜3.17,t,2H
( -CH2 −NH2 );2.83〜2.33,m,4H(-CONH-CH2 - と脂肪
族末端アミン基) Ｍａｓｓ：m/e 273( M+ ) は不出現,244,243,231,215,2
14,187,186,144,128,119,117,102,76,43,30Basic colorless crystals. Melting point: 252-267 ° 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 0.24 to
0.38 IR (KBr): ν 3445 (7.9), 3330 (9.3), 3264 (9.7), 3166
(7.7), 2915 (17.2), 2865 (17.3), 2363 (26.9), 1663 (4.
3), 1642 (3.0), 1584 (8.8), 1536 (1.6), 1456 (10.6), 139
9 (7.8), 1364 (20.6), 1312 (17.1), 1294 (20.7), 1262 (22.
9), 1194 (28.8), 1165 (27.3), 1076 (26.6), 1051 (28.3), 102
2 (23.9), 986 (4.9), 903 (30.2), 874 (30.4), 858 (34.
7), 818 (18.2), 745 (29.2), 629 (31.1), 598 (32.0), 563
(29.8), 513 (28.3), 450 (36.7) cm -1 NMR (d 6 -DMSO): δ8.49, s, 1H (-CONH-); 8.40 and 8.27,
d, 2H (phenylene group); 8.00 and 7.86, d, 2H (phenylene group);
6.77, br.S, 4H (NH 2 of triazine ring); 3.37 to 3.17, t, 2H
(-CH 2 -NH 2); 2.83~2.33 , m, 4H (-CONH-CH 2 - and aliphatic terminal amine groups) Mass: m / e 273 ( M +) is not appeared, 244,243,231,215,2
14,187,186,144,128,119,117,102,76,43,30
【００２３】[0023]
（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、この濾取した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２
１．９ｇ（収率86.6%)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 heated under reflux for 30 minutes and then allowed to cool, The precipitated crystals are collected by filtration, the collected crystals are boiled with a sufficient amount of water, filtered while hot, and the filtrate is allowed to cool to precipitate 2-cyanoethyl- (4 ', 6'-diamino -1 ', 3', 5'-s-triazine)-
The first crystal of (2 ') was collected by filtration. The filtrate at the time of collecting the first crystal was concentrated to collect the second crystal by filtration. The first crystal and the second crystal are 2 in total
1.9 g (yield 86.6%) of 2-cyanoethyl- (4 ', 6'-diamino-1', 3 ', 5'-s-triazine)-(2') was obtained.
【００２４】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、この系を放冷した
のち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. To desulfurize the filtered crystals, 0.4 g of sodium hydroxide and an appropriate amount of methanol were added 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 was added to the mixture to remove sodium hydroxide and the mixture was stirred, and the crystals were 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%).
【００２５】次いで、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")
５．０ｇ(0.024モル) に適当量の水を加えて２時間加熱
還流した。反応が終了したのち、系を冷却して不溶物を
濾別し、濾液を乾固して得られた乾固物をエタノールを
用いて再結し、目的物の２−アミノエチル−カルバモイ
ル−エチレン−（4',6'-ジアミノ-1',3',5'-s-トリアジ
ン〕−(2')４．３６ｇ（収率80.7％）を得た。Then, 2- (imidazolinyl-2 ')-ethylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]-(2")
An appropriate amount of water was added to 5.0 g (0.024 mol) and the mixture was heated under reflux for 2 hours. After the reaction was completed, the system was cooled, the insoluble matter was filtered off, the filtrate was evaporated to dryness, and the dried solid matter was reconstituted with ethanol to obtain the desired product, 2-aminoethyl-carbamoyl-ethylene. There was obtained 4.36 g (yield 80.7%) of-(4 ', 6'-diamino-1', 3 ', 5'-s-triazine]-(2').
【００２６】（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
理を行い、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 give 2- (4'-methylimidazolinyl-2 ')-. Ethylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-
5.75 g (yield 53.3%) of (2 ") was obtained.
【００２７】次いで、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")５．０ｇ(0.023モル) に適当量の水を加えて
２時間加熱還流した。反応が終了したのち、系を冷却し
て不溶物を濾別し、濾液を乾固して得られた乾固物をエ
タノールを用いて再結し、得られた結晶をさらにイソプ
ロピルアルコールと共に加熱し、熱時に濾過を行って不
溶物を濾別し、濾液を冷却して析出する結晶を濾取し
た。この結晶をｎ−ブタノールを用いてさらに再結した
ところ、目的物の２−アミノプロピル−カルバモイル−
エチレン−（4',6'-ジアミノ-1',3',5'-s-トリアジン）
−(2')３．４７ｇ（収率63.1％）が得られた。Then, 2- (4'-methylimidazolinyl
-2 ')-Ethylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]-(2") 5.0 g (0.023 mol) was added with an appropriate amount of water to give 2 After the reaction was completed, the system was cooled and the insoluble matter was filtered off, the filtrate was evaporated to dryness, and the dried solid matter was reconstituted with ethanol to obtain further crystals. When heated with isopropyl alcohol and filtered while hot, the insoluble matter was filtered off, the filtrate was cooled, and the precipitated crystals were collected by filtration.The crystals were recrystallized with n-butanol to obtain the desired product. 2-aminopropyl-carbamoyl-
Ethylene- (4 ', 6'-diamino-1', 3 ', 5'-s-triazine)
3.47 g (yield 63.1%) of-(2 ') was obtained.
【００２８】（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.
【００２９】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、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 then 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.
【００３０】次いで、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")
５．０ｇ(0.02 モル) に適当量の水を加えて２時間加熱
還流した。反応が終了したのち、系を冷却して析出して
くる結晶を濾取して目的物のｍ−（２−アミノエチル−
カルバモイル）−フェニレン−（4',6'-ジアミノ-1',
3',5'-s-トリアジン）−(2')５．０２ｇ（収率93.7％）
を得た。Then, m- (imidazolinyl-2 ')-phenylene- [4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]-(2")
An appropriate amount of water was added to 5.0 g (0.02 mol) and the mixture was heated under reflux for 2 hours. After the reaction is completed, the system is cooled and the precipitated crystals are collected by filtration to give the desired product, m- (2-aminoethyl-).
Carbamoyl) -phenylene- (4 ', 6'-diamino-1',
5.02 g of 3 ', 5'-s-triazine)-(2') (yield 93.7%)
Got
【００３１】（実施例４）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 4 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.
【００３２】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、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.
【００３３】次いで、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")４．０ｇ(0.016モル) にエチレングリコール７ml及
び水１mlを加えて２時間加熱還流した。反応が終了した
のち、系を冷却して析出してくる結晶を濾取し、アセト
ンを用いて洗浄したところ、目的物のｐ−（２−アミノ
エチル−カルバモイル）−フェニレン−（4',6'-ジアミ
ノ-1',3',5'-s-トリアジン）−(2')２．３２ｇ（収率5
4.1％）が得られた。Then, p- (imidazolinyl-2 ')-phenylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-
Ethylene glycol (7 ml) and water (1 ml) were added to 4.0 g (0.016 mol) of (2 ") and the mixture was heated under reflux for 2 hours. After the reaction was completed, the system was cooled and precipitated crystals were collected by filtration to remove acetone. When the product was washed with, p- (2-aminoethyl-carbamoyl) -phenylene- (4 ', 6'-diamino-1', 3 ', 5'-s-triazine)-(2') 2 was obtained. .32 g (yield 5
4.1%) was obtained.
【００３４】（実施例５）実施例１で得られた２−アミ
ノエチル−カルバモイル−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−アミノプロピル−カルバ
モイル−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−（２−アミノエチル−カルバモイル）−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）及び実施例４で得られ
たｐ−（２−アミノエチル−カルバモイル）−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）を用い、ＪＩＳ Ｃ−２１０
５ 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 5 2-Aminoethyl-carbamoyl-ethylene- (4 ', 6'-diamino obtained in Example 1
-1 ', 3', 5'-s-triazine]-(2 ') (hereinafter referred to as curing agent A), 2-aminopropyl-carbamoyl-ethylene- (4', 6 'obtained in Example 2. -Diamino-1 ', 3', 5'-s-triazine)-(2 ') (hereinafter referred to as curing agent B), m- (2-aminoethyl-carbamoyl) -phenylene-obtained in Example 3 (4 ', 6'-diamino-1', 3 ', 5'-s-triazine)
-(2 ') (hereinafter referred to as curing agent C) and p- (2-aminoethyl-carbamoyl) -phenylene- (4', 6'-diamino-1 ', 3', 5 obtained in Example 4 '-s-triazine)-(2')
(Hereinafter referred to as curing agent D), using JIS C-210
5. The epoxy resin curability of the compound of the present invention was investigated 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.
【００３５】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.
【００３６】[0036]
【表１】 [Table 1]
【００３７】（実施例６）実施例５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あるいは硬化剤Ｃ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３mm×１０
０mm×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 6 An epoxy resin prepared by mixing 100 parts by weight of an epoxy resin, 2 parts by weight of colloidal silica and 10 parts by weight of each of a curing agent A, a curing agent B or a curing agent C and kneading them in Example 5. Composition 3mm x 10
It was poured into a mold of 0 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.
【００３８】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
【００３９】[0039]
【表２】 [Table 2]
【００４０】[0040]
【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
れている。また本発明化合物をエポキシ樹脂の硬化剤あ
るいは硬化促進剤として用いた場合、硬化収縮が小さ
く、優れた靱性を有する硬化物が得られるので、塗料及
び電気絶縁材料等に好適なエポキシ樹脂組成物を提供し
うる。The one-pack type epoxy resin composition using the compound of the present invention as a curing agent has excellent storage stability at room temperature. Further, when the compound of the present invention is used as a curing agent or curing accelerator for an epoxy resin, a cured product having a small curing shrinkage and excellent toughness can be obtained. Can be provided.
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 a carbamoyl group 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 a carbamoyl group represented by the general formula of Chemical formula 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5172216A JP2978033B2 (en) | 1993-06-19 | 1993-06-19 | Diamino-s-triazine compound having a carbamoyl group and epoxy resin curing agent containing the compound as an active ingredient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5172216A JP2978033B2 (en) | 1993-06-19 | 1993-06-19 | Diamino-s-triazine compound having a carbamoyl group and epoxy resin curing agent containing the compound as an active ingredient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0710850A true JPH0710850A (en) | 1995-01-13 |
| JP2978033B2 JP2978033B2 (en) | 1999-11-15 |
Family
ID=15937752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5172216A Expired - Lifetime JP2978033B2 (en) | 1993-06-19 | 1993-06-19 | Diamino-s-triazine compound having a carbamoyl group and epoxy resin curing agent containing the compound as an active ingredient |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2978033B2 (en) |
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| JP2016034906A (en) * | 2014-08-01 | 2016-03-17 | 四国化成工業株式会社 | Triazine compound, synthesis method of the compound, and epoxy resin composition |
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1993
- 1993-06-19 JP JP5172216A patent/JP2978033B2/en not_active Expired - Lifetime
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| WO2015019777A1 (en) | 2013-08-05 | 2015-02-12 | 三菱瓦斯化学株式会社 | Benzoguanamine compound having aminomethyl group or salt thereof, and method for producing same |
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| JP2016034906A (en) * | 2014-08-01 | 2016-03-17 | 四国化成工業株式会社 | Triazine compound, synthesis method of the compound, and epoxy resin composition |
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| US9974169B2 (en) | 2015-02-03 | 2018-05-15 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg, metal-foil-clad laminate, resin composite sheet, and printed wiring board |
| EP3168263A4 (en) * | 2015-02-03 | 2018-06-20 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg, metal-foil-clad laminate, resin composite sheet, and printed wiring board |
| TWI683856B (en) * | 2015-02-03 | 2020-02-01 | 日商三菱瓦斯化學股份有限公司 | Resin composition, prepreg, metal foil-clad laminate, resin composite sheet, and printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2978033B2 (en) | 1999-11-15 |
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