WO1996028490A1

WO1996028490A1 - Heat-resistant epoxy resin composition

Info

Publication number: WO1996028490A1
Application number: PCT/JP1996/000621
Authority: WO
Inventors: Satoru Miyake; Kenichi Osawa; Toshinari Koda; Motohiko Hidaka; Norio Tanaka; Kiyohisa Takahashi
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 1995-03-14
Filing date: 1996-03-13
Publication date: 1996-09-19
Also published as: AU4953496A

Abstract

A thermosetting epoxy composition comprising one or more trifunctional epoxy compounds having a molecular structure wherein the three epoxy groups are disposed symmetrically, and one or more N-substituted melamines of general formula (I), (wherein X is (a) and R1 to R6 are each independently H, C¿1?-C18 alkyl, C1-C18 hydroxyalkyl, C4-C8 cycloalkyl, C5-C9 cycloalkylmethyl or C5-C9 methylcycloalkyl, with the proviso that three to five members of R?1 to R6¿ must be hydrogen, or alternatively R?5 and R6¿ may be united to form -(CH¿2?)4-7- or -CH2CH2-O-CH2-CH2-), characterized in that the amount of the active hydrogen atom present in the primary and/or secondary amino groups of the N-substituted melamine(s) is 0.1 to 0.7 equivalent per equivalent of the epoxy group of the trifunctional epoxy compound(s); and a heat-resistant epoxy resin composition obtained by thermosetting the above epoxy composition. The above epoxy composition is easy to handle and the above epoxy resin composition exhibits extremely high heat and chemical resistances.

Description

Description ifii i-based epoxy resin Technical field

The thermosetting epoxy composition of the present invention is useful for improving the ifi properties of epoxy adhesives, paints, casting materials, laminate materials, and the like. Background art

Conventional epoxy resins have been widely used in adhesives, paints, casting materials, laminated materials, etc. due to their excellent adhesion to materials such as glass, high mechanical strength, and excellent workability in curing.

In recent years, demands for further performance improvement in these fields have become more sophisticated, and fields that cannot be handled by bisphenol-based epoxy resins, which have been the mainstream in the past, have also increased. Tetraglycidylxylylenediamine, tetraglycidyldiaminodiph-xylmethane, tetrax (4- New epoxy compounds such as (hydroxyphenyl) ethanetetraglycidyl ether have been developed. In addition, the development of curing agents used in addition to epoxy compounds has been advanced. Particularly in the field of amine-based curing agents, Mannich-modified amines, thiourea-modified amines, Schiff's salty amines (ketiminized), and the addition of Michael New curing agents such as modified amines have been proposed.

Further, there is an attempt to add N-substituted melamine as a near-amine curing agent to an epoxy compound to improve workability such as pot life after the compounding.

As such an epoxy resin compound, an epoxy resin compound containing a substituted melamine described in Japanese Patent Application Laid-Open No. 56-72019 is disclosed in Japanese Patent Application Laid-Open No. 60-20211. Epoxy resin containing the substituted melamine and the novolak-type phenol resin described in the above Fatty fflfig products are disclosed. Recent development trends include improvement of ilii i properties, improvement of flexibility, and improvement of workability such as pot life after compounding, and various combinations of epoxy compounds and curing agents can be used according to the purpose. is there. However, in terms of strength, the combination of aliphatic amines, which originally have poor f f properties, with epoxy compounds designed to increase WH¾ properties has practicality on the S surface and extremely high properties. The power to do the purpose, the power to be very difficult. And it is extremely difficult to select an appropriate curing agent that is easy to handle.

For example, the epoxy compounds such as tetraglycidylxylylenediamine, tetraglycidyldiaminodiphenylmethane, and tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether mentioned above can be used in an acid anhydride curing system or a diaminediphenylsulfone curing system such as diaminodiphenylsulfone. , But each combination with such hardeners has the following specific problems:

In the acid anhydride curing system, the acid anhydride itself is vulnerable to moisture absorption and is hydrolyzed to a dicarboxylic acid, so that curing failure occurs in an atmosphere having ΔS during curing. For this reason special consideration is given to the preservation method after blending with the eboxy compound, and the field of use is also limited;

In the diaminodifluorosulfone hard-dyeing system, diaminodifluorosulfone itself has a high viscosity and its solubility in epoxy compounds is not so high, so it is dissolved by adding organic ^ HJ and distilled off. This is an ingenuity to cure while curing, and there is a problem in workability when it is not desired to mix an organic solvent.

It has been proposed that N-substituted melamine having a near-triazine skeleton is used as a curing agent for epoxy resins to improve storage stability and workability. Epoxy resin blended with N-substituted melamine described in JP-A-56-72019 ^; The epoxy resin composition containing the N-substituted melamine and the novolac phenolic resin described in No. 0-202117 ^ IS has the purpose of improving the workability such as improving the bot life after the compounding, but the proper epoxy resin The ugliness of the cured product is not sufficient, because no spleen is used and the spleen is incorrect.

SUMMARY OF THE INVENTION An object of the present invention is to provide an i®-epoxy compound which can be easily handled and become an extremely heat-resistant epoxy resin by thermosetting, and an iti-epoxy resin obtained by thermosetting the epoxy resin. They try to do things.

Disclosure of the invention

That is, the present invention relates to one or more trifunctional epoxy compounds having a molecular structure in which the positions of the three epoxy groups are symmetrical, and the formula (I)

[I]

(Where X is

FT

N

\

Are shown, R ¹ to R ^e are each independently H, alkyl groups of d-, hydroxycarboxylic alkyl C ₄ -8 cycloalkyl group, cycloalkyl methylate the C ₆ -0 C represents a methylcycloalkyl group of the following formula, provided that 3 to 5 of R ^{1 to} R ⁶ are H, or R ⁶ and R ^e together form one (CH ₂ ) 4-7 ― Or one CH ₂ CH ₂ -0-CH ₂ CH ₂ may be formed. )

A thermosetting epoxy resin containing one or more of N-substituted melamines represented by the following: active hydrogen of 1-amino group and Z or secondary amino group in N-substituted melamine; The amount is 0.1 to 0.7 equivalent per equivalent of epoxy group of the trifunctional epoxy compound, and the heat resistance obtained by converting the curable epoxy compound and the thermosetting epoxy compound. It relates to the epoxy resin material.

Hereinafter, the present invention will be described in detail. Examples of the trifunctional epoxy compound used in the present invention, which has a molecular structure in which the positions of the three epoxy groups are symmetric, include 1,3,5-tri (glycidyloxy) benzene and 1,3,5-trimesic acid triglyceride. Glycidyl ester, triglycidyl succinate, tris (hydroxyphenyl) methane triglycidyl ether, Formula [III]

(III)

(However, Xt, X _2, which may be the same or different, indicates to the H or methyl.) Substituted triglycidyl isocyanurate shown in Fig. 3 is a trifunctional epoxidation with three woven groups having a weaving structure ^! Any of these may be used, and these may be used alone or as a mixture. Among them, the formula [Π]

(II)

Tris (hydroxyphenyl) methane triglycidyl ether represented by, ftrf triglycidyl isocyanurate represented by formula (π ι) (X i, x ₂ fluorinated), tris-(-methyl) glycidyl isocyanurate (X, but methyl, chi ₂ is hydrogen) and tris - - methyl) glycidyl iso Xia isocyanurate (chi ₁ force 7j element, chi ₂ is methyl) is especially preferred.

As the Ν-substituted melamine, the primary amino group and the Ζ or secondary amino group represented by the formula [I] have an active hydrogen number of 3 to 5, and have the following various functional groups. Are preferred. That is, the number of alkyl groups is 1 to 18 and may be linear or branched. More preferably, the number of alkyl groups is 1 to 12. ^ Is a hydroxyalkyl group having 1 to 18 hydroxyl groups, which may be linear or branched. The position of the hydroxy group is not particularly limited, but a more preferred number of the hydroxy α-alkyl group is 1 to 12. The number of cycloalkyl groups is preferably from 4 to 8, more preferably a cyclopentyl group or a cyclohexyl group. ^ A cycloalkylmethyl group with a number of 5 to 9, specifically cyclobutylmethyl cyclopentylmethyl, cyclohexylmethyl cycloheptylmethyl and cyclooctylmethyl And more preferably a cyclopentylmethyl group and a cyclohexylmethyl group. ^ A methylcycloalkyl group having a number of 5 to 9, specifically, methylcyclobutyl methylcyclo π-pentyl group, methylcyclohexyl group, methylcycloheptyl group, and methylcyclooctyl group, more preferably cyclopentylmethylcyclo. It is a xylmethyl group.

In addition, in the formula (I), R ⁵ and R ^{6 of} X

― (CH ₂ ) 4-7 ― or one CH ₂ CH ₂ — 0— CH ₂ CH ₂ may be formed. More preferably, they are a mono (CH ₂ ) ₄ —pyrrolidino group and a — (CH ₂ ) ₅ —piperidino group. These N-substituted melamines may be used alone or as a mixture. The N-substituted melamine used in the present invention can be easily obtained by a method similar to a conventionally known synthesis method. For example:

Journal of the 'OB' American 'Chemical' Society (J. Am. Chem. Soc.), Vol. 73, pp. 2984, 1951, describes 2-cyclo-1,3-, 5-triazine derivatives and alkylamines. How to get it. A method obtained by reacting a 2,4,6-trimethylthio-1,3,5-triazine derivative and an alkylamine described in Chem. Ber. (Vol. 18, page 2755, 1885);

U.S. Pat. No. 2,228,161, Method of obtaining by reacting 2,4,6-triamino-1,3,5-triazine with alkylamine hydrochloride described in 1941: German Patent 889,593 1953 A method for obtaining 2-piperidino-1,4,6-diamino-1,3,5-triazine by reacting the cyanopiperidine with cyanoguanidine described in 1). A method of reacting cyanuric chloride and the corresponding alkylamines described in JP-A-3-215564;

In the presence of a 1,3,5-triazine derivative described in Japanese Patent Application No. 6-166618 filed by the present applicant and an alcohol in the presence of a period V [I or VII catalyst, How to respond;

1,3,5-Triazine derivative and periodic table No. VII described in Japanese Patent Application No. 6-280370 are reacted with alcohol in the presence of catalyst VI11 and hydrogen-containing gas; and ,

1,3,5-Triazine derivative and period described in JP-A-6-292791 No. VII, a method for converting to a olefin in the presence of a mixed gas of catalyst VI11 and ^ Z hydrogen monoxide o

It may be manufactured by any of the above or other known methods.However, when used in the electronic field, there is little hydrolyzable chlorine remaining in N-substituted melamine. A method of reacting melamine with aldehydes in the presence of a specific catalyst in a hydrogen atmosphere, a method of obtaining melamine in the presence of a specific catalyst in a hydrogen Z-oxidation atmosphere. It is preferable to use a method obtained by reacting the compounds.

Specific examples of N-substituted melamine are 2,4-bis (amino) — 6— (2-hydroxyshethyl) amino-1,3,5-triazine, 2,4-bis (amino) -1,6-butylamino — 1, 3, 5—triazine, 2,4-bis (amino) -1-6-cyclohexylamino-1,3,5-triazine, 2,4-bis (amino) — 6—dodecylamino-1,3 , 5—triazine, 2,4-bis (amino) — 6-stearylamino-1,3,5-triazine, 2,4-bis (amino) -16_methylamino1,3,5-triazine, 2, 4-bis (amino) -1-6-dibutylamino-1,3,5-triazine, 2,4-bis (amino) -1-6-dinonylamino-1,3,5-triazine, 2,4-bis (amino) — 6-didodecylamine 1,3,5-triazine, 2,4-bis (amino) 1-6-distearylia No 1, 3, 5-triazine, 2-Amino - 4, 6- bis (2-hydroxy-E chill § Mino) 1,3,5-triazine, 2-amino-4,6-bis (isopropylamino) -1,3,5-triazine, 2-amino-4,6-bis (hexylamino) — 1,3 5-triazine, 2-amino-4,6-bis (stearylamino) -1,3,5-triazine, 2,4,6-tris (ethylamino) -1,3,5-triazine, 2,4,6 —Tris (2-hydroxyethylamino) -1,3,5-triazine, 2,4,6-tris (isopropylamino) -1,3,5-triazine, 2,4,6-tris (butylamino) 1) 1,3,5-triazine, 2,4,6-tris (cyclohexylamino) — 1,3,5-triazine, 2,4,6-tris (2-ethylhexylamino) 1,3, 5-Triazine, 2,4,6-tris (dodecylamino) 1 1,3,5-Triazine, 2,4,6-tris (stearylamino) _ 1 , 3,5-triazine, 2,4-bis (amino) -1-6-piperidino-1,3,5-triazine, 2,4-bis (amino) -6-pyrrolidinol 1,3,5-triazine and 2, 4 Bis (amino) 1 6-morpholino — 1,3,5-triazine, etc., but as mentioned above, the active fe number of primary amino group and / or secondary amino group Is 3 to 5, the alkyl group of the substituent has 1 to 18 carbon atoms, and the hydroxyalkyl group has 1 to 18 carbon atoms, and any of 1 to 12 is more preferable.

Further, the number of substituents of the cycloalkylmethyl group or the methylcycloalkyl group is preferably from 5 to 9, and more preferably from 6 to 7. The number of cycloalkyl groups is preferably from 4 to 8, more preferably from 5 to 6. When the secondary amino group forms a ring structure with an alkylene group, the number of alkylene groups is preferably 4 to 7, and more preferably 4 to 5. Instead of this alkylene group, an ethyleneoxyethylene group may be used. The ratio of the above specific epoxy compound and N-substituted melamine is 1 equivalent of epoxy group On the other hand, it is preferable to cure the primary amino group and the amino or secondary amino group of the N-substituted melamine represented by the formula 1 at a ratio of 0.1 to 0.7 equivalent. Further, it is more preferable to cure with it which becomes 0.2 to 0.6 equivalent.

Such SJS ^ may be carried out without a solvent as in a casting material, or an appropriate organic solvent such as a coating varnish or a varnish for a laminated layer M may be used. When organic solvents are used, ketone solvents such as methyl isobutyl ketone, ester solvents such as butyl acetate, ether solvents such as dioxane, alcohol solvents such as butanol, and cellosolves such as butyl sorb Solvents, carbitol solvents such as butyl carbitol, aromatic carbon solvents such as toluene and xylene, K-based solvents, amide solvents such as dimethylformamide and dimethylacetamide, and sulfoxides such as dimethylsulfoxide Examples of the solvent include pyrrolidone solvents such as N-methylpyrrolidone and the like, and any organic solvent may be used as long as it does not significantly inhibit the hardness. As the value, 80 to 250 ° is ίίϋ, but 100 to 220 ° C is more preferable. In the case of using a low-boiling solvent, using autoclave etc., at a pressure 2~1 0 O k gZ cm ² about under pressure, the reaction temperature Te 8 0-2 5 0, better good Or from 100 to 220. In addition, the heating may be performed at a constant rate until the end of the curing reaction, but may be performed while changing the temperature from a low temperature to a high temperature at once, for example, 10 CTCX for 1 hour → 15 O 'C x 3 hours → 20 O' C 5 hours → '·', B-stage or oligomerization at relatively low temperature, then post-curing at high temperature, etc. Good. Curing may be carried out without a catalyst. Examples of the reaction catalyst include tertiary amines such as N, N-dimethylpentylamine, quaternary ammonium such as tetraethylammonium bromide, and triphenylphosphine. 3rd class phosphine, Trifune Ordinary epoxy hard kSJ cores such as quaternary phosphonium such as rumonobendylphosphonium bromide, imidazole type such as 2-ethyl-4-methylimidazole, and Lewis acid type such as boron trifluoride-monoethylamine complex Any catalyst may be used as long as it is used, but a Lewis acid catalyst is particularly preferred. The amount used is preferably 1 part by weight or less with respect to 100 parts by weight of the epoxy compound. In addition, as long as the object of the present invention is ^, an arbitrary component can be further contained. For example, silicone oil-based, amide-based, ester-based antifoaming agents, hindered phenol-based, hindered amine-based, etc. By adding a small amount of various additives such as stabilizers, ^ stones such as stearic acid ^, silicone resin-based and fluorine resin-based release agents according to the purpose, more preferable fi-epoxy resin M ^ can get.

(Action)

Epoxy resin materials composed of an epoxy compound and N-substituted melamine have been conventionally known.However, a specific epoxy compound is used, and furthermore, excellent flHft properties can be obtained depending on the mixing ratio with the N-substituted melamine. Was found.

Examples of the trifunctional epoxy compound having a molecular structure in which the positions of the three epoxy groups are symmetrical include 1,3,5—tri (glycidyloxy) benzene, 1,3,5—trimesic acid used in the present invention. Tris (hydroxyphenyl) methane triglycidyl, such as triglycidyl ester, in which three epoxy groups are rotationally symmetric with respect to an axis perpendicular to the ring plane at the center of the benzene ring The three epoxy groups are rotationally symmetrical with respect to the axis of the carbon-7j element bond of the central methine group, such as ether.Thick acid triglycidyl ester, trig Lysidyl isocyanurate and its alkyl group-substituted tris-((dimethyl) glycidyl isocyanurate, tris- (j3-methyl) glycidyl isocyanurate and the like triazine trione like triglycidyl isocyanurate The three epoxy groups are in a rotationally symmetrical position with respect to the axis perpendicular to the ring plane at the center of the ring, including tris (hydroxyphenyl) methane triglycidyl ether and triglycidyl. Isocyanurate, tris (α-methyl

) Glycidyl isocyanurate and tris- (S-methyl) glycidyl isocyanurate are particularly preferred. When these are used in combination with N-alkylated melamines, the reason why the heat resistance is higher than that of other polyfunctional epoxy compounds is not necessarily clear, but tris (hydroxyphenyl) methane triglycidyl. The structure is very similar to that of the ether, and the phenol novolac polyglycidyl ether having a slightly larger number of epoxy groups is less likely to exhibit ff ^ property. It is easy to progress without stress defects, and it is easy to take a relatively regular and dense structure during curing. As the N-substituted melamine used in the present invention, the primary amino group and the Z or secondary amino group represented by the formula (I) have an active primary number of 3 to 5, and R ^{1 to} R ⁶ The number of the alkyl group and the pendant oxyalkyl group is preferably from 1 to 18, and more preferably from 1 to 12. The number of cycloalkyl groups is preferably from 4 to 8, more preferably from 5 to 6. Further, the number of substituents of the cycloalkylmethyl group or the methylcycloalkyl group is preferably from 5 to 9, and more preferably from 6 to 7. Furthermore, in the formula [I], X of R ⁵ and are together a _{_{connexion, - (CH 2) 4 -}} 7 -, or one CH ₂ CH ₂ one 0- CH ₂ CH ₂ may be one formed . More preferably, they are one (CH ₂ ) ₄ —pyrrolidino group and one (CH ₂ ) ₅ —piperidino group. R ¹ to R ^e are all hydrogen in the formula [I], namely, the melamine emissions themselves active fe element is six prone to curing failure due to poor compatibility. Conversely, even when the number of alkyl groups or hydroquinalkyl groups is 19 or more, the activity as a curing agent is poor, and there is a problem that poor curing is likely to occur. When the active element number is 0 to 2, there is a problem that the activity as a curing agent is poor, and poor curing is likely to occur. ^ Cycloalkyl groups other than numbers 4-8, ^ cycloalkyl methyl groups other than numbers 5-9 or methylcycloalkyl groups are problematic for the economics of N-substituted melamine.

The above-mentioned curing reaction between the symmetric epoxy compound and the N-substituted melamine is based on a mechanism in which a primary or secondary amino group of the N-substituted melamine is added to the epoxy group of the epoxy compound, and a catalyst of the N-substituted melamine. The mechanism by which the epoxy group is further added to the 0 H group generated by the polymer chain by the addition reaction, and the mechanism by which the epoxy group undergoes ring-opening polymerization by the catalytic action of N-substituted melamine. Progress simultaneously. Therefore, for 1 equivalent of the epoxy group, 1 equivalent of the active 14τ element of the N-substituted melamine represented by the formula [I] is too large, and the active is cured at a ratio of 0.1 to 0.7 equivalent. It is preferable to cure at a ratio of 0.2 to 0.6 equivalent. When the activity and element content are less than 0.1, the curing speed becomes extremely slow.On the other hand, when the activity exceeds 0.7 equivalent, the unreacted れない -substituted melamine, which is not incorporated into the polymer by chemical bonding, remains moist. However, the resin produced has problems such as foaming at high temperatures and abnormal plasticization.

Such a catalyst may be a non-catalyst, but a catalyst such as a tertiary amine, a quaternary ammonium, or a Lewis acid may be used as the catalyst. However, catalysts such as 4-monum and Lewis acid may become a source of chlorine and fluorine ions in the electronic materials field, and may be less than 1% by weight of the resin M ^. It is preferred to use. When performing the above-mentioned hardening with a solution, there is no particular limitation as long as the hardening is not inhibited, but in casting polymerization, distillation before casting, and drying or vacuum distillation in varnishes for coating purposes, etc. Those that are no longer used are preferred. Solvents that can easily inhibit curing include bonbonic acid-based solvents, 1S¾X is a secondary amine-based solvent, and a solvent having a phenol-tfoK acid group. It is preferable that the amount is 1 part by weight or less based on 100 parts by weight of the compound.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to Examples. The epoxy compounds (A1) to (A4), N-substituted melamines (B1) to (B6), and melamine (Ml ), Boron trifluoride monoethylamine (C1) was prepared. Epoxy compound

(A 1); Tris (hydroxyphenyl) methane triglycidyl ether (Tactyx 742, trade name, manufactured by Dada Chemical Co., Ltd., epoxy content 6.3 equivalent k) was used as it was.

(A2); Triglycidyl isocyanurate (trade name: TEPIC-S, manufactured by Nissan Chemical Industries, Ltd., a high-quality product of triglycidyl isocyanurate, epoxy group content: 10.0 kg / kg) was used as it was.

(A3): Bisphenol A-type epoxy compound having a molecular weight of about 380 (Epicoat 828, trade name, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy group content: 5.3 equivalent / kg) was used as it was. (A4): A phenol novolak type epoxy resin (oil-based seal epoxy ttS, trade name: Epicoat 152, epoxy group content: 5.7 equivalents M / kg) was used as it was.

N-substituted melamine

(B 1); 2,4-bisamino-6-butylamino-1,3,5-triazine In a four-necked flask equipped with a stirrer, a meter and a condenser, cannyl chloride 184.

After dissolving 4 g (1.0 mol) and 80 OmL of acetonitrile at room temperature, the system was cooled, and 307.7 g (5.0 mol) of 28% aqueous ammonia was reacted with vigorous stirring. Was added dropwise over 2 hours while keeping the temperature at 10 or less. Then, 1 hour Hisage拌to warm to room temperature and then aged for an additional 4 h warming to gradually 4 5 O ^e C. After cooling to room temperature, the contents were separated by α and washed with ion exchange of ^ 4. Then, it is dried in vacuum and 2,4-bisamino-6-chloro-1,3,5-triazine 11

5 g (79% yield) was obtained.

Next, in a four-necked flask equipped with a stirrer, a meter and a condenser, was placed 14.5 g (0.1 mol) of the obtained 2,4-bisamino-16-chloro-1,3,5-triazine. ), 100 g of ion-exchanged water and 29.2 g (0.4 mol) of n-butylamine were added, the mixture was refluxed with stirring, and reacted for 6 hours. After cooling to room temperature, the contents were separated and washed with ion exchange, and then washed with toluene. Then, it was vacuum dried to obtain 17.5 g of powdery 2,4-bisamino-6-butylamino-1,3,5-triazine. Melting point: 1 67.

(B 2); 2,4-bis (amino) -1-6- (2-hydroxyethylamino) -1,3,5-triazine

In the same manner as for N-substituted melamine (B1) using monoethanolamine instead of n-butylamine, powdered 2,4-bis (amino) 16- (2-hydro Kishetylamino) — 1, 3, 5-triazine (13, 9 g) was obtained. Melting point: 223

(B 3); 2,4,6-tris (butylamino)-1,3,5-triazine In an autoclave equipped with a stirrer and S-meter, add 12.6 g (0.1 mol) of melamine, 1, 4 one Jiokisan 200 g, n-butyl aldehyde 72. 0 g (1. 0 mol), were charged 5% Pd on activated carbon 2. 0 g, after nitrogen gas substitution, a 7-containing gas as the first Ki圧4 Ok cm ² , Reaction ί¾180. SIS at C for 6 hours. After completion, the mixture was slowly cooled to room temperature, and the catalyst and solids were removed by fractionation. Then, the solvent was distilled off to obtain a sticky liquid crude product. This was developed by silica gel column chromatography using an acetone-hexane mixed solvent as an eluent while changing the mixing ratio successively from 100 to 1/100, and the product was isolated. The agent was distilled off to obtain 19.6 g of liquid 2,4,6-tris (butylamino) -1,3,5-trizine.

(B 4); 2-amino-4,6-bis (cyclohexylamino) -1,3,5-triazine

After dissolving 18.4 g (0.1 mol) of cyanuric chloride and 5 OmL of acetonitrile at room temperature with stirring in a four-necked flask equipped with a stirrer, a meter, and a condenser, the system was cooled and cooled. , Ion exchange ϋτ 35 g, cyclohexylamine 9.9 g (0.

1 mol) and triethylamine 10.ig (o. 1 mol),

Was added dropwise over 2 hours while keeping the temperature at 5 ^eC or less. After stirring for 2 hours at 5 more hands, it was added dropwise 2 8% aqueous ammonia 7 OML, 1 hour at 5 ^e C, 1 hour at 20 ° C, and stirred for 2 hours at 50. Thereafter, until in 60 ^ and, Kishiruamin 54. 5 g of (0.55 mol) was added cyclohexane, was further stirred ^ teeth 3 hours 70 ^e C.

To this is added dropwise 18 g of ion-exchanged water, and the mixture is cooled down to 1 (cooled to TC, and the precipitated crystals are discriminated. 16.5 g of 2-amino-3,6-bis (cyclohexylamino) _1,3,5-triazine in the form of a solid was obtained. At 1 53;

(B 5); 2,4,6-tris (2-ethylhexylamino) 1, 1,3,5-triazine

Using 2-ethylhexylaldehyde instead of n-butyraldehyde, in the same manner as for N-substituted melamine (B3), liquid 2,4,6-tris (2-ethylhexylamino) — 25.5 g of 1,3,5-triazine were obtained.

(B 6); 2,4-bis (amino) -1 6- (stearylamino) -1,3,5-triazine

2,4-Bisamino-6-chloro-1,3,5-triazine was obtained in the same manner as in N-substituted melamine (B1). In a four-necked flask equipped with a stirrer, a meter and a condenser tube, 14.5 g (0.1 mol) of the obtained 2,4-bisamino-6-chloro-1,3,5-triazine was added. 60 g of the mixture, 60 mL of 1,4-dioxane, and 26.9 g (0.1 mol) of n-stearylamine were added, and the mixture was allowed to reflux with stirring, followed by stirring at 3:00. Further, 20 g (0.1 mol) of a 20% aqueous solution of 7jc sodium oxide was added dropwise over 1 hour, and stirring was continued for 2 hours. After cooling to room temperature, the solvent was distilled off, and 100 mL of ion exchange ^ 10O and 10 OmL of toluene were added to extract the product invertible, and the product was thoroughly washed with water. Thereafter, the leaked solvent was distilled off to obtain 34.4 g of powdery 2,4-bis (amino) -6- (stearylamino) -1,3,5-triazine. : 9 C.

(B 7); 2,4-bis (amino) 1-6-piberidino 1,3,5-triazine

In the same manner as for N-substituted melamine (B1), powdered 2,4-bis (amino) -6-piberidino 1,3,5-triazine is obtained using piperidine instead of n-butylamine. Was. SL, 210 ° C

Melamine (Ml); Melamine (Nissan Chemical Co., mtl¾, powder) Was.

Boron trifluoride Z Monoechiruamin (C 1): _c Example was used a commercially available reagent Bok 7 and Comparative Example Bok 5

A silicone rubber spacer made by cutting two glass plates 14 mm in length, 240 mm in width and 240 mm in width x 3 mm in thickness with a mold release agent cut into a U-shape with a thickness of 1 mm and a width of 1 mm A fixation clip was used to secure a casting polymerization cell with an inner volume of 13 Ommx width 22 Ommx thickness lmm. Table 1 shows the epoxy compounds (A1) to (A4), N-substituted melamines (B1) to (B7), melamine (Ml), and boron trifluoride / monoethylamine (C1). After melt-mixing at a weight ratio, pour into it, cure as shown in Table 2, cool to room temperature, remove the casting polymerization cell, and obtain a cured product of epoxy resin iM; Table 3 shows the results of the viscoelastic spectrum of the cured product, its tensile properties at high temperatures, and its elongation at high temperatures.

In addition, EZH shown in Table 1 represents an equivalent ratio of an epoxy group to an amino group activity of N-substituted melamine.

-8 ΐ-

ΖΌ / l ο ητ, 0 0 0 0 0 0 0 0 0 0 ΟΟΐ

90 0 / ΐ 0 0 0 0 0 0 Τ6 0 0 0 0 ΟΟΐ 0

8Ό / ΐ 0 0 0 0 0 0 0 0 0 0 0 ΟΟΐ ε

ΓΟ / ΐ ΐ 0 0 0 0 0 0 0 28 800800 ΐ 0 0 0 ζ

9 * 0/1 0 0 0 0 0 0 0 0 S'H 0 ΟΟΐ 0 0 ΐ

S'0 / ΐ 0 0 δ'9ΐ 0 0 0 0 0 0 0 0 0 00 ΐ ί m

ΖΌ / \ 0 0 0 Ζ7> \ 0 0 0 0 0 0 0 09 OS 9

ZW 0 0 0 0 8 20 0 0 0 0 0 OS 01 9

Ζ'0 / l ΐ 0 0 0 0 9 ΐ 0 0 0 0 0 001 0 f m

8'0 / ΐ 0 0 0 0 0 0 '^ Z 0 0 0 0 ΟΟΪ 0 8

ΓΟ / Ι ΐ 0 0 0 0 0 0 9S '80 0 0 0 ΟΟΐ ζ

9Ό / ΐ 0 0 0 0 0 0 0 0 8 * δΐ 0 0 0 ΟΟΐ ΐ%

H a ΐθ m 丄 a 98 sa 89 za εν zv IV

¾9 0 / 96dT / XDd 06ΜΖ / 96 No.

² ^

Hardening conditions

First stage Second stage Third stage Fourth stage Example 1 150 ° C 3hr 180'C 4hr Example 2 150 ^e Cx3hr 180 ^e Cx4hr Example 3 100 ^e CX2hr 130. Cx2hr 150 ^e Cx2hr 200 ° C 4hr

Example 4 100 ^e C 2hr 130 ^e Cx2hr 150 ° C x2hr 200 ^e C 4hr

Example 5 150 ^{^e} Cx3hr 180 ^e Cx4hr one embodiment ^{^{6 150 e C 3 r 180 e}} Cx4 r - an embodiment 7 150 ° Cx3hr 180 ^e Cx4hr - one Comparative Example ^{1 150 ° Cx3hr 180 e C 4} r 200 e Cx3hr — Comparative Example 2 150 ^e Cx3hr 180 ° Cx4hr 200 ^e Cx3hr — Comparative Example 3 150 ^e Cx3hr 180 ^e Cx4hr 200 ^e C 3 r

Comparative Example 4 100 ° Cx2hr 130 ^e C 2hr 150 ^e C 2hr 200 ° Cx4 r

Comparative Example 5 150 ^e Cx3 r 180 ° Cx4 r

(m)

The obtained cured epoxy resin material is cut into length 5 0111111> <width 5111111 and thickness 1111111 by a motorized diamond and power meter to obtain a viscoelastic spectrum! Did ^. Similarly, it was cut to dimensions of 15 Omm long x 10 mm wide x 1 mm thick, and subjected to bending strength! ^. Table 3 shows the test results. The method is shown below.

Viscoelastic spectrum ^ (T1)

Using Seiko Denshi viscoelastic scan Bae Kutorometa SDM 5600, to measure the viscoelasticity scan Bae spectrum up to room temperature or et 35 O ^e C, the cured product of the epoxy resin舰物 As the glass transition, induction ¾E contact (hereinafter, called for beak of t an, (referred to). Peak S of an, 5 is, in .smallcircle when more than 22 O ^e C, when 1 80-21 9-hand厶When the value is 1 179 or less, it is indicated by X.

High temperature tensile release (T2) and high temperature elongation (T3)

A Using 'A' and 'D' S Tensilon UTM-4-100, measure the tensile strength and elongation at a temperature of 150 at a distance of 5 mm between the chucks and a crosshead of i $ 5 mmZ. did. When the tension exceeds 3 OMpa, it is indicated by a triangle, when it is 20 to 3 OMpa, it is indicated by a triangle, and when it is less than 20 Mpa, it is indicated by an x mark. When the elongation exceeds 6%, it is indicated by a triangle, when it is 3-6%, it is indicated by a triangle, and when it is less than 3%, it is indicated by an X.

Table 3

Test report

T1 T2 T3

Example 1 〇〇〇

Example 2 〇〇〇

Example 3

Example 4 〇〇〇

Example 5 〇〇〇

Example 6

Example 7

Comparative Example 1 X X 〇

Comparative Example 2 X 〇 △

Comparative Example 3 X X 〇

Comparative Example 4 Δ Δ X Comparative Example 5 Δ 〇 X The results in Table 3 show that the epoxy resin compositions of Comparative Examples 1 to 5 have sufficient performance among the viscoelastic spectrum of the cured product, high-temperature bow I, and high-temperature elongation. On the other hand, the epoxy resin product of the example shows that the performance is excellent in all of these properties.

Industrial applicability

The thermosetting epoxy product of the present invention can be diluted with an organic solvent according to the formula below to prepare a relatively low viscosity of 2 to 1000 cps. Also, without using a solvent, after mixing the evoxy compound and the N-substituted melamine, they are pre-heated to form a B-stage or oligomer and adjusted to a relatively low viscosity of 1000 to 1000 cps. It has the feature of being able to. The storage stability after mixing is extremely high, at least 6 months at room temperature, and the blending stability with various liquid materials. In addition, the fiber before curing can be easily cured. This curing is usually a gas furnace, a hot air furnace, an infrared ray Italy, microwave oven, can be cured in degrees about 1 0 0~ 2 0 0 ^e C in 1-5 hours using an induction heating furnace or the like. When diluted and used with an organic solvent, the solvent can be volatilized and the above-mentioned step S can be performed. Furthermore, it is possible to mix and trap inorganic fillers such as silica particles, alumina particles, and glass, and it has good ^ f properties with wood materials, materials, and various objects. Thus, the thermosetting epoxy composition of the present invention is easy to handle.

In addition, the ii resin obtained by thermosetting the curable epoxy compound of the present invention has extremely high resistance and high chemical resistance. Therefore, ^ vehicles, ceramic paints '^^, concrete paints' glue, sealinks for construction / adhesion, paper and processing i ^ agents, glass cloth epoxy composites, carbon composites, boron fiber reinforced Composite materials, female transmutation, pharmaceuticals' binder for pesticides, plastic It is also useful for applications such as surface coating agents for coatings, glass breakage prevention coating agents, female-type maskin U, and resin sealants for electronic components.

Claims

The scope of the claims

1. 1X or two or more trifunctional epoxy compounds having a molecular structure in which the positions of the three epoxy groups are opposite to each other and the formula [I]

]

(Where X is

R,

N

\

Are shown, R ¹ to R ⁶ are each independently H, an alkyl group of C doctor _18, hydroxycarboxylic alkyl d-, cycloalkyl methylation group C ₄ -8 cycloalkyl ^ C ₅ -8 , C ₆ - represents a methyl cycloalkyl group _9, however, a 3-5 of R ¹ to R ⁶ is H, or R ⁵ and R ⁶ together such connexion, one (CH ₂₎ 4- 7 One or one CH ₂ CH ₂ 0—CH ₂ CH ₂ may be formed. )

A functionalizable epoxy compound containing one or more N-substituted melamines represented by the formula: wherein the amount of active hydrogen of 1-amino group and Z or secondary amino group in N-substituted melamine is 3 A curable epoxy compound whose content is 0.1 to 0.7 equivalent per equivalent of epoxy group of the functional epoxy compound.

2. A trifunctional eboki with a symmetrical molecular structure where the three ethoxy groups are located The formula is cm

(Π)

3. The epoxidizable epoxy compound according to claim 1, which is a tris (hydroxyphenyl) methane triglycidyl ether represented by the formula:

3. A trifunctional epoxy compound having a symmetrical molecular structure with three epoxy groups is represented by the formula [I II]

X] λ · 2 0 ^ 2 Size 1

CH— CH- CH _2N JJ CH ₂ -CH— CH

, 'N N,'

o o

O N people. (I II)

CH Cool CH— CH

o

(However, X 1 and X ₂ may be the same or different and represent H or a methyl group.)

The curable epoxy composition according to claim 1, which is a substituted triglycidyl isocyanurate represented by the following formula:

4. A modified epoxy resin obtained by subjecting the ii! L modified epoxy compound described in any one of claims 1 to 3 to a fig.