JPS5984884A - Novel imidazole compound, synthesis of said compound and curing of epoxy resin using said compound - Google Patents

Abstract

NEW MATERIAL:1-{ beta'-[2',6'-Diaminotriazinyl-(4')]}-ethyl-2-methylimidazolium-beta- carboxyethyl-betaine of formula. USE:A curing agent and a cure accelerating agent, especially useful for the curing of epoxy resin. It is weakly acidic colorless crystal soluble easily in water, ammonia water, acetic acid and dilute hydrochloric acid, hardly soluble in methanol and ethanol, insoluble in pyridine and dimethylformamide, and having a melting point of 188-190 deg.C. PROCESS:The compound of formula can be prepared by the addition reaction of 1-{beta'-[2',6'-diaminotriazinyl-(4')]}-ethyl-2-imidazole with acrylic acid in a solvent such as ethanol at 80-90 deg.C for 2-4hr. If necessary, a polymerization inhibitor of acrylic acid is added to the reaction system.

Description

Detailed Description of the Invention 1-[β/(2/·6′-diaminotriazinyl-(4/))-ethel-2-methylimidazolium-β-carboxyethyl represented by the linear structural formula of the present invention This invention relates to a gold wire method for betaine and imidazole compounds, and a method for curing epoxy resins using the compounds.

The above-mentioned imidazole compound is a new substance, which is obtained by adding 1-[β/-(2/, bl-diaminotriazinyl-(41J)-ethyA.-2-methylimidazole and acrylic acid) as shown in the following formula. You can see the reaction.

The triazinylimidazole compound serving as the starting material in the above reaction formula is a compound selected by the method described in Japanese Patent Publication No. 47-36591.

When reacting the triazinylimidazole compound and acrylic acid, the molar ratio of the imidazole compound and acrylic acid is set to be 1.0 or more, and a 60 to 98% ethanol solution, preferably around 90% ethanol solution is used as the solvent. It is best to heat the solution for 2 to 4 hours at a temperature of 80 to 90° C., which corresponds to a reflux device, with the addition of an acrylic acid polymerization inhibitor if necessary.

As the reaction progresses, the betaine compound precipitates, making it difficult to stir the reaction system, so it is desirable to employ a reaction apparatus equipped with a kneader.

The reaction product can be purified by filtering and washing with a 60-98% ethanol solution.

The properties of the novel 1-[β-(2',6'-diaminotriazinyl-(4/))-ethyl-2-methylimidazolium-β-carboxyquethyl-betaine according to the present invention are as follows. It is.

Properties: Weakly acidic, colorless crystals, easily soluble in water, aqueous aqueous solution, acetic acid, aqueous acetic acid and dilute hydrochloric acid, sparingly soluble in methanol and ethanol, insoluble in pyridine dimethylformamide and methane.

Melting point 188-190℃ 'i'Lc (Silica G%1tOHs Is color development) 2R70,00-0,10 Silon r: 340 [1,5340,5210,51
40,1630 (m5 absorption, triazine), 155 (1
(M+ absorption, triazine and carboxylate), 14
45 (second absorption 1. triazine), 1405 (#!4m
4 absorption ruboxylate), 1340.1285.12t
SO,1265,1165,11o5.1050,10
30.995.960.870,840,810 (5th
Absorption, triazine) NMR (pso) δ7.37, S, 2I ((4,51ffnOton>
; 4゜51, t% 4B (α-methylene at position 1 and α-methylene at position 6); 2.97, t, 4H β-methylene at position 11 and β-methylene at position 5 1; 2.58, day ,3H(
2nd methyl) Mass! m/e 247 (M”-Coo)
, 219 (24701ar-OHs, 13B (dimethylene-diaminotriazine) A method for curing an epoxy resin using 7 ethyl betaine as a saponifying agent and curing accelerator will be described.

The term "epoxy resin" as used herein is an abbreviation for a polyepoxy compound having more than one epoxy group on average in its molecule.

When a system consisting of an epoxy resin and a curing agent or a curing agent and an oxidation promoter has good shelf life and storage stability, this system is called a one-component epoxy resin compound or a one-component epoxy resin compound, and is The curing agent contained is called a latent curing agent, and the curing accelerator is also called a youthful accelerator, and the betaine compound can be used as both a latent curing agent and a latent accelerator.

The one-component epoxy resin formulation obtained by the method of the present invention exhibits little increase in system viscosity, which causes a decrease in workability, during long-term storage at room temperature, is less likely to cause phase separation, and is highly stable in yarn. It has good stability, and when cured, it cures quickly and efficiently by heating, and is an excellent cured product that is well-balanced in terms of electrical insulation, mechanical strength properties, chemical resistance, etc. give.

These cured products are useful for sealing and insulating coating of various semiconductor parts such as diodes and transistors, and 2V chromtronics parts such as ceramic capacitors and resistors.

In addition, the Betaine Compound Co., Ltd., various curing agent components, such as aliphatic polyamines, aromatic polyamines, amine salts, quaternary ammonium salts, dicyandiamide original slips, melaban,
It can be used as a curing accelerator or co-curing agent for polycarboxylic acids, polycarboxylic acid anhydrides, polyhydric phenols, condensates of phenols and formaldehyde, polycarboxylic acid hydrazine, and the like.

The blending ratio of the betaine compound used as a curing agent in the method of the present invention is 0.5 phr to 50 phr (100 parts by weight of epoxy resin), and the addition of other curing agents or co-curing agents The appropriate blending ratio when used as a hydroxide is 0.01 to 50 phr, preferably 0.05 phr (10 phr).

One molecule of the polyepoxy compound in the present invention is
It contains more epoxy groups than flint, and this group is located at the terminal position of OH* 0-\0
' or may be interposed in the middle of the molecular formula, and the polyepoxy compound may be linear aliphatic, cycloaliphatic, aromatic, or heterocyclic, and may contain hydroxyl groups, alkyl groups, alkoxy groups, ester groups, acetal groups. It may be substituted with a non-interfering substituent such as a group or an ether group.

The most desirable polyepoxy compounds are bispheno-kA,
Bisphenol F Lusorcin, Hydroquinone, 4.4
'-diphenol, dihydroxydiphenyl sulfone,
It is a polyglycidyl ether of polyhydric phenol such as phenol, formaldehyde resin, cresol, and formaldehyde resin.

Examples of other suitable polyepoxy compounds include glycidyl ethers of polyhydric alcohols such as ethylene glycol, glopylene glycol, glycerin, trimethylolpropane, and 1,4-butanediol, heptallic acid, tetrahydroheptalic acid, and hexathalic acid. Glycidyl amines derived from polyglycidyl esters of polyhydric carboxylic acids such as hydrophthalic acid, methylendomethylenetetrahydroheptalate adipic acid, dimer acid, polyamines such as aniline, 4.l-diaminodiphenylmethane,
Vinylcyclohexene dioxide, 5,4-epoxycyclohexylmethyl-3,4-edoxycyclohexanecarboxylate, bis-(6,4-epoxy-6-
These include epoxidized polyolefins such as methyl (7-chlorohexylmethyl)-adipate, or epoxidized vegetable oils.

The method of the present invention can also carry out similar curing treatment for systems containing pigments, plasticizers, fillers, and reactive diluents or solvents for monoepoxy compounds such as butyl glycidyl ether and phenyl glycidyl ether, as necessary. It can be done.

The curing temperature Fi in the present invention is 60 to 240°C,
Preferably it is in the range of 100 to 180°C.

The method of the present invention will be specifically explained below using Examples. Units are not specified unless otherwise specified! Displayed by NK.

Example 1 1 mol of diaminotriazinylimidazole (219F)
and 90% ethanol 703/'l in a stainless steel kneader with a capacity of 2e, and while cooling by running cooling water through the jacket of the kneader, add 1.1 mol (7 ml) of acrylic acid.
9, 21), A mixed solution consisting of #/10.8f and 78 g of 90% ethanol was charged in portions over 10 minutes while stirring at a rate of 5 seconds to give fcg and 5 molecules of MJ. @MfN was carried out for a total of 4 hours (internal temperature around 88°C).Then, the thread was cooled and the precipitated crystals were separated in a centrifuge at 27°C.
11 (95% yield) was collected by filtration. The melting points of the crystals seen here are 184-1), 0.20-0.50 (extremely thin, unreacted diaminotriazinylimidazole phase a), o, s
o~0.35 (extremely thin, unreacted acrylic acid phase).

In addition, a part of the crystals collected by filtration was extracted using a Soxhlet extractor to 95%
Extract and wash briefly with ethanol, and extract the residue with 1-[β/[2
/,6/-diaminotriazinyl-(4y)]-]ethyl-2-methylimidazolicum-βcarboxyethyl-
For identification of betaine, thorns (m, p, 1a 8-190°C) were used.

Example 2 1 mol (219 g) of diaminotriazinylimidazole charged in a thimble of a Soxhlet extractor was mixed with 1.1 mol (79.2 f) of acrylic acid and 0.7 mol of hydroquinone.
3 with a mixed solvent consisting of 800 g and 90% ethanol.
The extract was further heated under reflux for 1 hour, then cooled, and the precipitated crystals were collected by filtration using a centrifuge to obtain crude 1-[
β′-(2′・6′-diaminotriadiene-(4/)
)-ethyl-2-methylimidazolium-β-carboxyethyl-betaine (209.517296 units) was obtained. The melting point of this crystal was 185-188°C, and the TLO was the same as in Example 1.

Example 3 1-[β'-(2',6'-diaminotriazinyl-(
A case where 4/))-ethyl-2-methylimidazolium-β-carboxyethyl-betaine is used alone as a curing agent will be described.

By passing 100 parts of epoxy resin (trade name: Epicote 828, manufactured by Yuka Fel 1), 10 parts of betaine compound, and 2 parts of colloidal silica (trade name: Erosil 300, manufactured by Nippon Aerosil LL) through a three-roll FIk. The storage stability of the mixture was determined by storing it at a temperature of 20°C, measuring the change in viscosity, and determining the end point when the viscosity reached 10 times the initial value. Approximately 0.7 g of the sample was measured in terms of number of days, and the gelation time was 150*Q. Place about 0.7 g of the sample on a hot iron plate preset at 5℃, spread the sample to a size of about 2 oxsomvl with a stainless steel spatula, and Knead the sample while pressing it evenly at a reciprocating speed.
As a result of occasionally lifting the chamber 2 and determining the time until a thread is not drawn between the sample and the chamber, the gelation time Ifi of the above formulation is 78 seconds, and the storage stability is 120 days or more. It showed that.

Example 4 100 parts of epoxy resin (trade name: Ebicor) 828) and 1-[βI-(2/, 6/-diaminotriazinyl-(4)'))-ethyl-2-methylimidazolium-
8 parts of β-carboxyethyl-heta:1.

One part of Idarushiri Chikara (product name: Erosil 50Q) was mixed in the same manner as in Example 1 to prepare a homogeneous formulation. This composition is a pink-white liquid with a specific gravity of 1.181/axs and a viscosity of 22,000 cpsf at 25°C, and its gelation time is 119 seconds at 150°C.The storage stability at 5°C and 20°C is both 120°C or higher. It showed that.

The formulation was then heated at a temperature of 100°C for 2 hours and for a further 15 hours.
They were heated at a temperature of 0° C. for 4 hours to thermally cure them, and the properties of the cured products were investigated, as shown in the table below.

Example 5 A formulation example for adhesives in which the betaine compound of the present invention is used to accelerate the curing of dicyandiamide will be described.

70 parts of Epicote 828, 30 parts of Epicote 854, 30 parts of Epicote 854, J5 Chi with thixotropic properties
, manufactured by National Red), 30 parts of extender pigment (trade name: Mantaru P1 Tsuchiya Kaolin R), 6 parts of dicyandiamide
1 part, and 2 parts of 1-[β/-(2/·6'-diaminotriazinyl-(4)')-ethyl-2-methylimidazolium-β-carboxylic ether-betaine were uniformly mixed using a three-roll machine. After kneading, an adhesive formulation was obtained. This product exhibits storage stability of more than 1 month at 40°C and 120°C.
It cured rapidly at temperatures above '011 and exhibited strong adhesive strength. The specifications of the cured product heat-cured in the same manner as in Example 4 are shown.

Example 6 A formulation example for electrical casting using the betaine compound of the present invention as an accelerator for 1&anhydride will be described.

100 parts of Epicort 828, acid anhydride curing agent (trade name Epiclon B-570, manufactured by Dainippon Ink and Chemicals)
80 parts of
A mixture was obtained by stirring the mixture with a stirrer (Hydo, manufactured by Koitama Tekko). This formulation has a film capacitor in addition to the μ for casting.
It is recognized that it can also be used as an impregnating varnish for ignition coils, etc.

The properties of the graded product heat-cured at 80°C for 2 hours, 120'C for 1 hour, and 150°C for 1 hour are as shown in the table below. December 13th, Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office1, Indication of the Case, Patent Application No. 47900 of 1982, Title of Invention: New Imidazole Compound, Method of Synthesizing the Compound, and Epoxy Resin Curing Method Using the Compound, 3, Amendment. Relationship with the case of the person who made the amendment: Patent applicant 4, claim 5 of the specification to be amended, content of the amendment as shown in the attached sheet (attached sheet) Claims after amendment Lamb-β-carboxyethyl- Betaine, a new imidazole metal product shown by the structural formula.

(2) Legalization of own imidazole-him to Toyokita Nuisui's request (1), which is characterized by the addition of triazinyl-imidazole and acrylic acid represented by the structural formula.

(3) As a hardening agent or hardening accelerator, Toyo i'fm ball (
7) Use the imidazo-J Lech combination described in Q(1).
X-Ru Evo Tsuchi no Kyo version hard decoy friend removal

Claims (1)

[Scope of Claims] (1) 1-(β'+ (2/·6'-diaminotriazinyl-(4/))-ethyl-2-methylimidazolium-β-carboxyceter- represented by the structural formula Betaine. (2) 1-[β′-(2′・6′) characterized by adding triazinyl-imidazole and acrylic acid represented by the structural formula
-Cyabanotriazinyl-(47)-ethel-2-methylimidazolium-β-carboxyethyl-betaine synthesis method. (8) As a curing agent or curing accelerator, 1-(〆-(2/, 6/-diaminotriazinyl-(4)'))-ether-2-methylimidazoly, Tam-β shown by the structural formula - using carboxyethyl-betaine%
Characteristic epoxy resin curing method.