JPH0959352A - Epoxy compound-acid anhydride composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition containing an epoxy compound, an acid anhydride curing agent and a specific cure accelerator, having excellent storage stability, compounding stability, quick curability, adhesivity, chemical resistance, etc., formulable to obtain a low viscosity composition and useful for the coating, adhesion, etc., of ceramics. SOLUTION: This composition is composed of (A) an epoxy compound (e.g. a compound having >=2 epoxy groups such as a bisphenol A epoxy resin), (B) an acid anhydride (e.g. tetrahydrophthalic anhydride or hexahydrophthalic anhydride) as a curing agent and (C) a compound of the formula [X is amino, a 1-18C mono or dialkylamino, morpholino, piperidino, etc.; R<1> and R<2> are each a 1-12C (hydroxy)alkyl, a 4-8C cycloalkyl, etc.] as a cure accelerator. Preferably, the amount of the component C is 0.1-5 pts.wt. based on 100 pts.wt. of the component A and that of the component B is 0.7-1.2 equivalent based on 1 equivalent of the epoxy group of the component A.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an epoxy resin, particularly an epoxy / anhydride composition which is fast-curing and at the same time has long-term storage stability, and an epoxy / anhydride obtained by curing the same. The present invention relates to a resin composition. INDUSTRIAL APPLICABILITY The epoxy acid anhydride composition of the present invention is useful for curing workability and physical properties of casting materials, laminating materials, sealing materials, embedded resin materials, adhesives, paints and the like.

[0002]

2. Description of the Related Art Epoxy resin is an adhesive, a paint, a casting material, a sealing material, an embedding resin material because of its good adhesion to metal materials, glass, etc., high mechanical strength, and good workability in curing. It has been widely used as a laminated material. Epoxy resin is an epoxy compound, depending on the application, an amine curing agent, a mercaptan curing agent, a phenol resin curing agent,
It is designed to mix various curing agents such as acid anhydride curing agents to cure them, but to impart low-temperature curability, short-time curability, etc. In some cases, a curing accelerator such as an ammonium-based, tertiary phosphine-based, quaternary phosphonium-based, imidazole-based, or azabicyclo compound-based curing accelerator is used in combination.

In recent years, demands for further performance improvement in various application fields of cured epoxy resin products have become more severe, and in the amine curing agent compounding system, there is a large change in viscosity after compounding and there is a problem in long-term storage stability. The number of fields that cannot be handled by products is increasing. Further, in acid anhydride curing systems and phenol resin curing systems, it has been the mainstream as a curing accelerator in the past.
Primary amine-based, quaternary ammonium-based, tertiary phosphine-based,
A compound containing a quaternary phosphonium-based compound, an imidazole-based compound, an azabicyclo compound-based compound, etc. has the same problem. To improve these, modified epoxy adduct, modified aliphatic amine, modified polyamide amine, Mannich modified amine, thiourea modified amine , Schiff base-modified amines (obtained by ketimination), Michael addition-modified amines, imidazole quaternary salts and the like have been proposed.

There have been attempts to use N-substituted melamine as an amine-based curing agent to improve storage stability and workability after compounding. As such an epoxy resin composition,
JP-A-56-72019 discloses an epoxy resin composition containing N-substituted melamine. In British Patent No. 1192790, as an amine-based curing agent,
An epoxy resin composition containing N-substituted melamine or guanamine having two or more primary amino groups is disclosed.

There has been an attempt to improve stability such as pot life after compounding and workability by using N-substituted melamine as a curing accelerator for epoxy compound / phenol resin curing system. As such an epoxy resin composition, an epoxy resin composition containing an N-substituted melamine and a novolac type phenol resin described in JP-A-60-202117 is disclosed.

[0006]

[Problems to be Solved by the Invention] In the case of producing an epoxy compound / acid anhydride type cured resin, a tertiary amine type, a quaternary ammonium type, a tertiary phosphine type, a quaternary phosphonium type, an imidazole type, an azabicyclo compound type, etc. Unless the curing accelerator is added, the reactivity between the epoxy and the acid anhydride is poor, the productivity of the cured resin is extremely reduced, and it is practically difficult to make it a resin. However, when such a curing accelerator is also used as a catalyst, the reaction generally proceeds even at a relatively low temperature, the viscosity increases with time, and further gelation occurs, making the formulation unusable.

Further, as a method for extending the pot life, there is a means of using a small amount of the above-mentioned curing accelerator or using a low-activity curing accelerator. However, these methods cause foaming and cracking especially during the curing reaction at high temperature. And other defects are likely to occur.
The above-mentioned British Patent No. 1192790 discloses an epoxy compound / acid anhydride curing resin and an epoxy compound / amine curing resin, and two or more primary amino groups are used as an amine curing agent. There is disclosed an epoxy resin composition in which a benzoylurea-based or sulfonylurea-based curing accelerator is used in combination with an N-substituted melamine, guanamine, or the like, which is N-substituted having two or more primary amino groups. Although melamine, guanamine, and the like are shown to exhibit good properties, examples of acid anhydride curing systems disclose combinations with benzoylurea and sulfonylurea accelerators.

According to the present invention, an acid anhydride type curing agent is used for an epoxy compound, and a substituted triazine having a specific structure is used as the curing accelerator in a limited amount.
It has good pot life, storage stability and workability after compounding.
It is intended to provide an epoxy / acid anhydride composition which does not cause defects such as foaming and cracks in a resin after curing, and an epoxy / acid anhydride resin composition obtained by curing the same.

[0009]

That is, the present invention relates to an epoxy / acid anhydride composition prepared by mixing an epoxy compound and an acid anhydride as an epoxy curing agent, and the formula [I] is used as a curing accelerator.

[0010]

Embedded image

(Wherein X is an amino group, a C _1-18 monoalkylamino group, a C _1-18 dialkylamino group, a morpholino group, a piperidino group, a methyl group or a phenyl group,
R ¹ and R ² are each independently a C _1-12 alkyl group, a C _1-12 hydroxyalkyl group, a C _4-8 cycloalkyl group, a C _5-9 cycloalkylmethyl group or a C _{5 -9}
Is a methylcycloalkyl group. And an epoxy / acid anhydride resin composition characterized by containing a substituted triazine represented by the formula (4) and an epoxy / acid anhydride resin composition obtained by curing the same.

Hereinafter, the present invention will be described in detail.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy compound used in the present invention preferably has at least two epoxy groups in the molecule from the viewpoint of heat resistance and mechanical strength of a cured resin. Examples of the epoxy compound having two epoxy groups include a bisphenol A-based epoxy resin obtained by the reaction of bisphenol A and epichlorohydrin, a bisphenol F-based epoxy resin obtained by the reaction of bisphenol F and epichlorohydrin, and bisphenol S and epichlorohydrin. Bisphenol S-based epoxy resin and the like obtained by reaction with
These preferably have a molecular weight of about 300 to 5,000. In the epoxy compound having three or more epoxy groups, a novolac-based epoxy resin obtained by a reaction of a phenol novolac resin or a cresol novolac resin with epichlorohydrin, triglycidyl isocyanurate, tris (α-methylglycidyl) isocyanurate, tris (β) -Methylglycidyl) isocyanurate, tris (hydroxyphenyl) methane triglycidyl ether, 1,3,5-tri (glycidyloxy) benzene, 1,3,5-trimesic acid triglycidyl ester, tetraglycidyl xylylenediamine, tetraglycidyl Diaminodiphenylmethane, tetrakis (4-
Examples thereof include hydroxyphenyl) ethane tetraglycidyl ether. Further, in order to reduce the viscosity of the compound or to impart flexibility to the cured resin, as an aliphatic epoxy compound having two epoxy groups, neopentyl glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, etc. Glycol diglycidyl ethers, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and other polyol diglycidyl ethers, and aliphatic epoxy compounds having three or more epoxy groups, such as glycerin polyglycidyl ether and pentaerythritol polyglycidyl You may use together polyol polyglycidyl ethers, such as ether and trimethylol propane polyglycidyl ether. Incidentally, since epoxy compounds such as phenyl glycidyl ether and butyl glycidyl ether having one epoxy group lower the crosslink density,
The amount used should be limited so that the average number of epoxy groups in the epoxy compound is at least 2.

The acid anhydride used in the present invention includes phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic acid anhydride, methylnadic acid anhydride, and anhydride. 1 in the molecule of maleic acid, succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, etc.
Those having one acid anhydride group are desirable. Further, those having two acid anhydride groups in the molecule such as pyromellitic anhydride, cyclobutane tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid anhydride, and tetralin-diacid anhydride, and carboxylic acid such as trimellitic acid anhydride. Those in which a group and an acid anhydride group coexist generally have a high melting point and poor solubility in an epoxy compound, a solvent, etc., so that the resin tends to be inhomogeneous during the curing reaction, and the compounding amount is uniform in the system. Although it is limited to a copolymerizable amount, it is preferably 10% by weight or less of the total acid anhydride.

The ratio of the epoxy compound to the acid anhydride is such that the acid anhydride group is 0.7 to 1 equivalent to 1 equivalent of the epoxy group.
It is 1.2 equivalents, preferably 0.8 to 1.1 equivalents, and more preferably 0.9 to 1.0 equivalents. The substituted triazine used as a curing accelerator for the epoxy resin used in the present invention has at least two secondary amino groups as shown in the formula [I], and also has one of the following various functional groups. Those having are preferred.

That is, X is an amino group and has 1 to 18 carbon atoms.
Monoalkylamino group of alkyl group, carbon number is 1 to 1
A dialkylamino group having an alkyl group of 8, a morpholino group, a piperidino group, a methyl group or a phenyl group,
Among these, an amino group, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having an alkyl group having 1 to 12 carbon atoms, or a piperidino group is more preferable.

The secondary amino groups R ¹ and R ² have 1 carbon atoms.
In the case of an alkyl group having 12 to 12, it may be linear or branched, and a more preferable alkyl group has 1 to 9 carbon atoms, and in the case of a hydroxyalkyl group having 1 to 12 carbon atoms, a linear or branched alkyl group. The position of the hydroxy group is not particularly limited, but a more preferable alkyl group has 1 to 9 carbon atoms, and a cycloalkyl group having 4 to 8 carbon atoms is more preferable, and a cyclopentyl group or cyclohexyl group is more preferable. In the case of a cycloalkylmethyl group having 5 to 9 carbon atoms, for example, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group or a cyclooctylmethyl group,
More preferably, it is a cyclopentylmethyl group or a cyclohexylmethyl group, and in the case of a methylcycloalkyl group having 5 to 9 carbon atoms, for example, a methylcyclobutyl group, a methylcyclopentyl group, a methylcyclohexyl group, a methylcycloheptyl group or a methylcyclooctyl group. The base,
More preferably, it is a cyclopentylmethyl group or a cyclohexylmethyl group. These substituted triazines may be used alone or in combination.

The formula [I] -substituted triazine used in the present invention can be easily obtained by a method similar to the conventionally known synthetic method. For example, the Journal of American Chemical Society (J. Am. Chem. Soc.)
73, 2984, 1951, 2-chloro-
A method obtained by reacting a 1,3,5-triazine derivative with an alkylamine. Hemische Berichte (Chem Be
r. ) Vol. 18, p. 2755, 1885, 2,
A method obtained by reacting a 4,6-trimethylthio-1,3,5-triazine derivative with an alkylamine. US Pat. No. 2,228,161, 2,4,6 described in 1941
-A method obtained by reacting triamino-1,3,5-triazine with an alkylamine hydrochloride. German Patent 889,5
No. 93, a method for reacting cyanopiperidine and cyanoguanidine described in 1953 to obtain 2-piperidino-4,6-diamino-1,3,5-triazine. JP-A-3-2
Examples thereof include a method of reacting cyanuric chloride described in No. 15564 with a corresponding alkylamine.

Japanese Patent Application No. 6-16 filed by the present applicant
No. 6,618, 1,3,5-triazine derivative and a method of reacting with alcohol in the presence of Group VII or VIII catalyst of the periodic table, 1,3,5-described in Japanese Patent Application No. 6-280370. Method for reacting triazine derivative with alcohol in the presence of Group VII or VIII catalyst and hydrogen-containing gas, and 1,3,5-triazine derivative and periodic table described in Japanese Patent Application No. 6-292791 Examples include a method of reacting with an olefin in the presence of a Group VII or VIII catalyst and a carbon monoxide / hydrogen mixed gas. Any method may be used, but when used in the field of electronic materials, a substituted triazine is used. A method in which melamine is reacted with alcohols in the presence of a specific catalyst, which has a small amount of hydrolyzable chlorine remaining therein, and melamine is reacted in the presence of a specific catalyst in a hydrogen atmosphere. How obtained by reacting dehydrogenase acids, preferably by methods such as obtained by reacting an olefin under the presence specific catalyst with melamine to hydrogen / carbon monoxide atmosphere.

Illustrative of such a substituted triazine is 2-amino-4- (mono-2-hydroxyethyl).
Amino-6-monoethylamino-1,3,5-triazine, 2-amino-4,6-bis (monoethylamino)-
1,3,5-triazine, 2-amino-4,6-bis (monobutylamino) -1,3,5-triazine, 2-
Amino-4,6-bis (monocyclohexylamino)-
1,3,5-triazine, 2-amino-4,6-bis (monocyclohexylmethylamino) -1,3,5-triazine, 2-amino-4,6-bis (methylcyclohexylamino) -1,3 , 5-Triazine, 2-amino-4,6-bis (mono-2-ethylhexylamino)-
1,3,5-triazine, 2-amino-4,6-bis (monododecylamino) -1,3,5-triazine,
2,4-bis (mono-2-hydroxyethylamino)-
6-methyl-1,3,5-triazine, 2,4-bis (monoethylamino) -6-methyl-1,3,5-triazine, 2,4-bis (monobutylamino) -6-methyl- 1,3,5-Triazine, 2,4-bis (monocyclohexylamino) -6-methyl-1,3,5-triazine, 2,4-bis (mono-2-ethylhexylamino) -6-methyl-1 , 3,5-triazine, 2,4-
Bis (monododecylamino) -6-methyl-1,3,5
-Triazine, 2,4-bis (mono-2-hydroxyethylamino) -6-phenyl-1,3,5-triazine, 2,4-bis (monoethylamino) -6-phenyl-1,3,5 -Triazine, 2,4-bis (monobutylamino) -6-phenyl-1,3,5-triazine,
2,4-bis (monocyclohexylamino) -6-phenyl-1,3,5-triazine,

2,4-bis (mono-2-ethylhexylamino) -6-phenyl-1,3,5-triazine,
2,4-bis (monododecylamino) -6-phenyl-
1,3,5-triazine, 2,4,6-tris (monoethylamino) -1,3,5-triazine, 2,4,6-
Tris (mono-2-hydroxyethylamino) -1,
3,5-triazine, 2,4,6-tris (monoisopropylamino) -1,3,5-triazine, 2,4,6
-Tris (butylamino) -1,3,5-triazine,
2,4,6-Tris (monocyclohexylamino)-
1,3,5-triazine, 2,4,6-tris (mono-
2-ethylhexylamino) -1,3,5-triazine, 2,4,6-tris (monododecylamino) -1,
3,5-triazine, 2,4-bis (monoethylamino) -6-diethylamino-1,3,5-triazine,
2,4-bis (mono-2-hydroxyethylamino)-
6-di (mono-2-hydroxyethyl) amino-1,
3,5-triazine, 2,4-bis (butylamino)-
6-dibutylamino-1,3,5-triazine, 2,4
-Bis (monocyclohexylamino) -6-dibutylamino-1,3,5-triazine,

2,4-bis (mono-2-ethylhexylamino) -6-dibutylamino-1,3,5-triazine, 2,4-bis (monododecylamino) -6-di (mono-2-ethylhexyl) ) Amino-1,3,5-triazine, 2,4-bis (2-hydroxyethylamino)-
6-piperidino-1,3,5-triazine, 2,4-bis (monoethylamino) -6-piperidino-1,3,5
-Triazine, 2,4-bis (monobutylamino) -6
-Piperidino-1,3,5-triazine, 2,4-bis (monocyclohexylamino) -6-piperidino-1,
3,5-Triazine, 2,4-bis (mono-2-ethylhexylamino) -6-piperidino-1,3,5-triazine, 2,4-bis (monododecylamino) -6-piperidino-1,3 , 5-Triazine, 2,4-bis (mono-2-hydroxyethylamino) -6-morpholino-
1,3,5-triazine, 2,4-bis (monoethylamino) -6-morpholino-1,3,5-triazine,
2,4-bis (monobutylamino) -6-morpholino-
1,3,5-Triazine, 2,4-bis (monocyclohexylamino) -6-morpholino-1,3,5-triazine, 2,4-bis (mono-2-ethylhexylamino) -6-morpholino-1 , 3,5-triazine, 2,
4-bis (monododecylamino) -6-morpholino-
Various substances such as 1,3,5-triazine can be used.

The amount of the substituted triazine represented by the formula [I] is 0.1 to 5 relative to 100 parts by weight of the epoxy compound.
Weight part is preferable, and the ratio which becomes 0.2-3 weight part is more preferable. In this way, as the curing reaction conditions of the epoxy acid anhydride composition of the present invention blended, it may be solvent-free like a casting material, or a paint varnish or a laminate impregnating varnish. Alternatively, a suitable organic solvent may be used. When an organic solvent is used, a ketone solvent such as methyl isobutyl ketone, an ester solvent such as butyl acetate, an ether solvent such as dioxane, an alcohol solvent such as butanol, a cellosolve solvent such as butyl cellosolve, and butyl carbitol. Carbitol solvent,
Aromatic hydrocarbon solvents such as toluene and xylene, amide solvents such as dimethylformamide and dimethylacetamide, sulfoxide solvents such as dimethyl sulfoxide, N
Examples thereof include pyrrolidone-based solvents such as methylpyrrolidone, but any organic solvent may be used as long as it does not significantly inhibit the curing reaction.

The curing reaction temperature is preferably 80 to 250 ° C, more preferably 100 to 220 ° C.
When a low boiling point solvent is used, an autoclave or the like is used and the reaction temperature is 80 to 250 ° C., preferably 100 to 100 ° C. under a pressure of about ² to 100 kg / cm ^2.
The reaction can be carried out at 220 ° C. The temperature may be constant until the end of the curing reaction, or may be increased from a low temperature to a high temperature at a constant rate, for example, 100 ° C. × 1 hour → 150 ° C. × 3 hours → 200. ℃
× 5 hours → ..., such as a method of B-stage or oligomerization at a relatively low temperature and then post-curing at a high temperature.

Further, as long as the object of the present invention is achieved, it may further contain any component, for example, a defoaming agent such as silicone oil type, amide type, ester type, hindered phenol type, hindered amine type. A more preferable heat-resistant epoxy resin composition by adding a small amount of various additives such as a stabilizer such as a metal soap such as stearate, a silicone resin-based release agent and a fluorine resin-based release agent according to the purpose. Is obtained.

As an epoxy resin composition composed of an epoxy compound and a substituted triazine, an epoxy resin composition containing an N-substituted melamine having a triazine skeleton is disclosed in JP-A-56-72019. This is an example in which a substituted melamine is applied as an amine-based curing agent. In general amine curing agents, depending on the mixing ratio, not only addition reaction of epoxy with amino hydrogen of primary amino group or secondary amino group, but also addition reaction of OH group with epoxy group and epoxy group It is known that a reaction such as anionic polymerization of 1) also occurs, and the reaction between the epoxy compound and the N-substituted melamine is similar to this, and therefore the bonding mode of the polymer is an amine bond and / or an ether bond.

Further, as an example of using N-substituted melamine as a curing accelerator for an epoxy compound / phenolic resin curing system, a novolac type phenol resin described in JP-A-60-202117 and a small amount of N-substituted melamine are disclosed. An epoxy resin composition containing the above is disclosed. The main reaction is the addition reaction between the epoxy and the phenolic OH group, and the bonding mode of the polymer is an ether bond.

On the other hand, in the curing reaction of the epoxy acid anhydride, the addition reaction between the epoxy and the acid anhydride group is the main reaction, and the bonding mode of the polymer is the ester bond. Which of these epoxy curing systems is used is selected in consideration of the application and the required performance. When curing an epoxy / acid anhydride composition, unless a curing accelerator is added as a catalyst, the reactivity between the epoxy and the acid anhydride is poor, and the productivity of the cured resin is extremely reduced, resulting in substantial resinification. It is difficult. Examples of such curing accelerators include tertiary amine-based, quaternary ammonium-based, tertiary phosphine-based, quaternary phosphonium-based, imidazole-based, and azabicyclo compound-based compounds. However, when such a curing accelerator is also used as a catalyst, the reaction generally proceeds even at a relatively low temperature, the viscosity increases with time during storage, and further gelation occurs, making the formulation unusable. . There are many types of these curing accelerators, but the more active the higher the curing rate of the resin, the less stable the compounded formulation becomes.
With low activity, stability after compounding is good,
There is a general tendency that the curing reaction of the resin becomes slow and the workability of the cured product is deteriorated.

As a fact that cannot be predicted by the above studies, the reason why such a reason is not always clear in the epoxy acid anhydride composition using the specific substituted triazine of the present invention as a curing accelerator, but the stability after compounding is not clear. Of the present invention have been found to be extremely good, and the curing reaction is sufficiently fast, and the workability of producing a cured product is also good, and as a result of intensive studies, the present invention has been completed. .

The substituted triazine used in the present invention is as shown in formula [I]. In formula [I], X is an amino group, and melamine in which R ¹ and R ² are all hydrogen, X is Methyl group, acetoguanamine in which R ¹ and R ² are all hydrogen, X is a phenyl group, and R ¹ and R ²
Benzoguanamine There are all hydrogens, X N, N-dialkylamino group and R ¹ and R ² are all hydrogen N, N-dialkylated melamine, X is a piperidino group and R ¹ and R ² are all hydrogen, 2,4-diamino-6
-Piperidino-1,3,5-triazine, X is a morpholino group, and 2,4-diamino-6-morpholino-1,3,5-triazine in which R ¹ and R ² are all hydrogen; When there are 2 to 3 amino groups and 0 secondary amino groups, the activity is insufficient and curing failure occurs, or when curing at high temperature, a reaction occurs at once and the reaction becomes inhomogeneous. The rapid evaporation of volatile components causes foaming and cracks. The same results are obtained in the case of tetraalkylated acetoguanamine, tetraalkylated benzoguanamine, hexaalkylated melamine, etc., which has two or more tertiary amino groups but has zero secondary amino groups. Similarly, the same result is obtained when X is a monoalkylamino group and R ¹ and R ² are all hydrogen, that is, a monoalkylated melamine and a pentaalkylated melamine each having one secondary amino group.

From the above, it is easy for the site that is the center of activity expression as a promoter of the substituted triazine in the present invention to be a monoalkylamino group, a mono (hydroxyalkyl) amino group or the like, that is, a secondary amino group. Can understand. The reason for this is not clear, but for example,
In the case of hexaalkylated melamine, tetraalkylated benzoguanamine, etc., it is considered to be one of the tertiary amines, but due to the structure directly linked to the triazine ring, the steric hindrance around the N atom is larger than that of ordinary tertiary amines. Is mentioned. Further, those having two or more primary amino groups have the original properties of triazine, but have almost no properties as amines, and the reactivity to epoxy and acid anhydride is too weak. To be Further, the one having two or more secondary amino groups of the present invention is not only good as an amine, but also good in that it has less steric hindrance than hexaalkylated melamine, tetraalkylated benzoguanamine and the like. It is presumed that it shows excellent performance.

In British Patent No. 1192790, as an amine-based curing agent, N-containing two or more primary amino groups is used.
An epoxy resin composition is disclosed in which a substituted melamine or guanamine is blended and a benzoylurea-based or sulfonylurea-based curing accelerator is used in combination. In this system, an N-substituted melamine or guanamine having two or more primary amino groups is disclosed. It is exemplified that the above shows good properties, but in the examples of acid anhydride curing system, benzoylurea system,
The present invention relates to a combination with a sulfonylurea-based accelerator and is not disclosed in the present invention.

In the epoxy compound and the acid anhydride, the mixing ratio of each component is 0.7 to 1.2 equivalents of the acid anhydride group to 1 equivalent of the epoxy group, preferably 0.8 to 1.
It is 1 equivalent, and more preferably 0.9 to 1.0 equivalent. If it is less than 0.7 equivalent, there is a problem that the cured product is easily colored and the crosslink density is lowered. The reason for this is not necessarily clear, but it is presumed that some side reaction such as polymerization reaction between epoxies easily occurs. On the other hand, when it exceeds 1.2 equivalents, unreacted acid anhydride and carboxylic acid groups derived from it increase inside the cured product, resulting in increased water absorption of the cured product and deterioration of chemical resistance such as alkali. When applied to electronic materials, it may cause deterioration of insulation.

The amount of the substituted triazine represented by the formula [I] is 0.1 to 5 relative to 100 parts by weight of the epoxy compound.
Part by weight is preferable, and it is more preferable to cure at a ratio of 0.2 to 3 parts by weight. If it is less than 0.1 part by weight, sufficient curing reactivity cannot be obtained, and conversely, if it exceeds 5 parts by weight, the storage stability after compounding is lowered. When the above curing reaction is carried out in a solution, the solvent is not particularly limited as long as it does not inhibit the curing reaction, but in casting polymerization, it is distilled off before casting, and in varnishes for coating purposes, etc., it is dried or distilled under reduced pressure. Those that are easy to remove are preferred. Examples of the solvent that easily inhibits the curing reaction include a carboxylic acid solvent and a solvent having a phenolic hydroxyl group. Even when it is unavoidably used, it is 1 part by weight or less relative to 100 parts by weight of the epoxy compound. It is preferable that In addition, primary or secondary amine solvents should not be contained at all, because they have extremely high reactivity with epoxy and acid anhydride and catalytic action and extremely accelerate the change over time.

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following examples and comparative examples. The epoxy compounds (A1) to (A6) and the acid anhydrides (B1) to be used in the examples and comparative examples will be described below.
(B4), substituted triazines (C1) to (C10), commercially available triazines (D1) to (D5), commercially available curing accelerator (E
1) to (E3) and solvents (F1) to (F2) were prepared.

Epoxy compounds (A1) to (A5) (A1); Bisphenol A having a molecular weight of about 380
Type epoxy compound (trade name of Yuka Shell Epoxy Co., Ltd.
Epicoat 828, epoxy group content 5.3 equivalents / k
g) was used as is. (A2): tris (hydroxyphenyl) methane triglycidyl diether (trade name: Tactics 742, manufactured by Dow Chemical Co., epoxy group content: 6.3 equivalent / kg)
Was used as is.

(A3); Phenolic novolac type epoxy resin (trade name Epicoat 1 manufactured by Yuka Shell Epoxy Co., Ltd.)
52, epoxy group content 5.7 equivalent / kg) was used as it was. (A4); Triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., trade name TEPIC-L, isolated and purified low melting point isomer of triglycidyl isocyanurate, epoxy group content 10.0 equivalents / kg) was used as it was. .

(A5): A bisphenol A type epoxy compound having a molecular weight of about 900 (Epicote 1001, trade name, manufactured by Yuka Shell Epoxy Co., epoxy group content 2.0 equivalent / kg) was used as it was. Acid anhydrides (B1) to (B4) (B1); methylhexahydrophthalic anhydride A commercially available reagent was used as it was.

(B2): Hexahydrophthalic anhydride A commercially available reagent was used as it was. (B3); Methyl nadic acid anhydride A commercially available reagent was used as it was. (B4); pyromellitic dianhydride A commercially available reagent was used as it was.

Substituted triazines (C1) to (C10) (C1); 2-amino-4,6-bis (monobutylamino) -1,3,5-triazine Four equipped with stirrer, thermometer and cooling tube In the mouth flask,
After dissolving 18.5 g (0.1 mol) of cyanuric chloride and 150 mL of acetonitrile at room temperature, a mixed solution of 7.3 g (0.1 mol) of n-butylamine and 20 g of ion-exchanged water was added thereto at a reaction temperature of 5 ° C. The solution was added dropwise over 2 hours while maintaining the following. Then, while maintaining the temperature at 5 ° C. or lower, a solution of 10 g (0.1 mol) of potassium hydrogen carbonate and 40 g of ion-exchanged water was added dropwise over 1 hour, and then 28% ammonia water 1
5.2 g (0.25 mol) was added dropwise at the same temperature, gradually heated and stirred at 50 ° C. for 4 hours. Then, the contents were separated by filtration and washed with a large amount of ion-exchanged water. After that, it is vacuum dried to give 2-amino-4-butylamino-
6-Chlor-1,3,5-triazine was obtained. The total amount of the crystals was dispersed in 100 g of ion-exchanged water, 8.1 g (0.11 mol) of n-butylamine was added, and the mixture was heated to the reflux temperature with stirring and reacted for 2 hours. Further, sodium hydroxide 4.0 g (0.1 mol) and ion-exchanged water 2
0 g of the solution was added dropwise over 1 hour and reacted at the reflux temperature for 2 hours. After cooling to room temperature, the product was extracted with 100 ml of toluene, the organic layer was washed 5 times with 80 ml of ion-exchanged water, and the solvent was distilled off under reduced pressure to give 2-amino-4,6-bis (monobutylamino). -1,3,5-triazine 27g
I got

(C2); 2-amino-4,6-bis (monocyclohexylamino) -1,3,5-triazine In a four-necked flask equipped with a stirrer, thermometer and cooling tube,
After dissolving 18.4 g (0.1 mol) of cyanuric chloride and 50 mL of acetonitrile with stirring at room temperature, the system was cooled, and 35 g of ion-exchanged water, 9.9 g (0.1 mol) of cyclohexylamine and triethylamine were added thereto. 10.
1 g (0.1 mol) of the mixture was added dropwise over 2 hours while maintaining the reaction temperature at 5 ° C or lower. After further stirring at 5 ° C for 2 hours, 70 mL of 28% ammonia water was added dropwise, and the mixture was stirred at 5 ° C for 1 hour, 20 ° C for 1 hour, and 50 ° C for 2 hours. Then, the temperature was raised to 60 ° C., 54.5 g (0.55 mol) of cyclohexylamine was added, and the temperature was further raised to 70 ° C. and stirred for 3 hours. 180g of deionized water
Was added dropwise, the mixture was cooled to 10 ° C. with stirring, the precipitated crystals were separated by filtration, washed with a large amount of ion-exchanged water, and vacuum dried to give powdery 2-amino-4,6-bis ( Monocyclohexylamino) -1,3,5-triazine 1
6.5 g was obtained.

(C3); 2,4,6-Tris (monobutylamino) -1,3,5-triazine In an autoclave equipped with a stirrer and a thermometer, melamine was added.
12.6 g (0.1 mol), 1,4-dioxane 200
g, n-butyraldehyde 72.0 g (1.0 mol),
After 2.0 g of 5% Pd-supporting activated carbon was charged and the atmosphere was replaced with nitrogen gas, hydrogen gas was reacted at an initial pressure of 40 kg / cm ² at a reaction temperature of 180 ° C. for 6 hours. After completion of the reaction, the mixture was slowly cooled to room temperature, filtered to remove the catalyst and solids, and the solvent was distilled off to obtain a viscous liquid reaction product crude product. This was developed by silica gel column chromatography using an acetone / hexane mixed solvent as an eluent while sequentially changing the mixing ratio to 100/1 to 1/100, isolating the product, and then distilling off the solvent. And liquid 2,
19.6 g of 4,6-tris (monobutylamino) -1,3,5-triazine was obtained.

(C4); 2,4,6-tris (mono-2
-Ethylhexylamino) -1,3,5-triazine In the place of n-butyraldehyde, 2-ethylhexylaldehyde was used in the same manner as the N-substituted melamine (B3) to obtain liquid 2,4,6- Tris (mono-2-ethylhexylamino) -1,3,5-triazine 25.5
g was obtained.

(C5); 2,4-bis (monobutylamino) -6- (monododecylamino) -1,3,5-triazine N-substituted melamine (C1) In the same manner as in the case of using ammonia water. Then, n-dodecylamine was used to obtain solid 2,4-bis (monobutylamino) -6- (monododecylamino) -1,3,5-triazine.

(C6); 2,4-bis (monobutylamino) -6-piperidino-1,3,5-triazine N-substituted melamine (C1) In the same manner as in (1), piperidine was used instead of aqueous ammonia. Powdered 2,4-bis (monobutylamino) -6-piperidino-1,3,5
-Triazine was obtained.

(C7); 2,4-bis (mono-2-ethylhexylamino) -6-monobutylamino-1,3,3
5-triazine In the same manner as N-substituted melamine (C1), mono-2-ethylhexylamine was used instead of n-butylamine,
Furthermore, waxy 2,4-bis (mono-2-ethylhexylamino) -6-monobutylamino-1,3,5-triazine was obtained by using n-butylamine instead of aqueous ammonia.

(C8); 2-amino-4,6-bis (2
-Hydroxyethylamino) -1,3,5-triazine In place of n-butylamine, monoethanolamine was used in the same manner as in the substituted triazine (C1), and powdered 2,4-bis (amino) -6- (2-Hydroxyethylamino) -1,3,5-triazine was obtained.

(C9); 2,4-bisamino-6-monobutylamino-1,3,5-triazine In a four-necked flask equipped with a stirrer, a thermometer and a cooling tube,
After dissolving 184.4 g (1.0 mol) of cyanuric chloride and 800 mL of acetonitrile at room temperature, the system was cooled, and 28% ammonia water 303.
7 g (5.0 mol) was added dropwise over 2 hours while maintaining the reaction temperature at 10 ° C or lower. Then, the mixture was heated to room temperature and stirred for 1 hour, then gradually heated to 50 ° C. and aged for 4 hours. After cooling to room temperature, the contents were separated by filtration and washed with a large amount of ion-exchanged water. Then, vacuum dry,
115 g (yield 79%) of 4-bis (amino) -6-chloro-1,3,5-triazine was obtained.

Then, the obtained 2,4-bis (amino)-was placed in a four-necked flask equipped with a stirrer, a thermometer and a condenser.
1-4.5 g of 6-chloro-1,3,5-triazine (0.
1 mol), deionized water 100 g, n-butylamine 2
9.2 g (0.4 mol) was added, the temperature was raised to the reflux temperature while stirring, and the reaction was carried out for 6 hours. After cooling to room temperature, the contents were separated by filtration, washed with a large amount of deionized water, and then
Washed with toluene. Then, it is vacuum dried to obtain powdery 2,4-bis (amino) -6-monobutylamino-1,
17.5 g of 3,5-triazine was obtained.

(C10); 2,4-bis (amino) -6
-Dibutylamino-1,3,5-triazine Powdered 2,4-bis (amino) -6-in the same manner as the substituted triazine (C1) using dibutylamine instead of n-butylamine. Dibutylamino-1,
3,5-triazine was obtained.

Commercially available triazines (D1) to (D5) (D1); Melamine Melamine (manufactured by Nissan Chemical Industries, Ltd., powder) was used as it was. (D2): Benzoguanamine A commercially available reagent was used as it was.

(D3): Acetoguanamine A commercially available reagent was used as it was. (D4); 2,4-bis (amino) -6-vinyl-1,
3,5-Triazine A commercially available reagent was used as it was. (D5); N, N-diallylmelamine A commercially available reagent was used as it was.

Commercially available curing accelerators (E1) to (E3) (E1); 2,4,6-tris (dimethylaminomethyl) -phenol Commercially available reagents were used as they were. (E2); 2-Ethyl-4-methylimidazole A commercially available reagent was used as it was.

(E3); 2-Methylimidazole A commercially available reagent was used as it was. Solvents (F1) to (F2) (F1); methyl ethyl ketone A commercially available special grade reagent was used as it was.

(F2): Methyl isobutyl ketone A commercially available special grade reagent was used as it was. Examples 1 to 8 and Comparative Examples 1 to 10 Epoxy compounds (A1) to (A5), acid anhydrides (B1) to (B4), substituted triazine (C1) to
(C10), commercial triazines (D1) to (D5), commercial curing accelerators (E1) to (E3), solvents (F1) to (F).
After mixing 2) at the weight ratios shown in Tables 1 and 2, the evaluation of the curing activity, the appearance of the cured resin, and the storage stability test were performed. Table 1 shows examples of the present invention, and Table 2 shows comparative examples.

The E / An shown in the table represents the equivalent ratio of the epoxy group and the acid anhydride group.

[0057]

[Table 1]

[0058]

[Table 2]

(Evaluation) The storage stability, curing activity, and polymer (cured product) of the epoxy / acid anhydride composition were evaluated by the methods (T1) to (T3) shown below. The results of these tests are shown in Table 3. Curing activity test (T1) A hot plate with a temperature controller was heated to 200 ° C., and 0.2 g of each composition shown in Table 1 and Table 2 was added thereto.
Let's take it and stir it with a bamboo stick with a diameter of 3 mm,
The time until the occurrence of thread breakage and gelation (hereinafter referred to as gel time) was measured to examine the curing activity. 20
The gel time at 0 ° C. is 120 seconds or less, marked with ○, and 121 to 300 seconds with Δ, marked with 300 to 1800.
Each second is indicated by an X mark, and when more than 1800 seconds is indicated by XX.

Storage stability test (T2) Each composition shown in Table 1 and Table 2 was stored at 23 ° C.
Using the H-type viscosity, changes in the number of storage days and the viscosity were measured at 25 ° C. If the number of days required to double the viscosity immediately after compounding is 10 days or more, it is marked with a circle, when 5 to 9 days is marked with a triangle, and when 2 to 4 days is marked with a cross. When it is less than time, each is represented by XX.

Cast Polymerization Test (T3) Silicone rubber made by cutting two 140 mm long × 240 mm wide × 3 mm thick glass plates coated with a release agent into a “U” shape having a thickness of 3 mm and a width of 10 mm. Hold the spacer and fix with the fixing clip, length 130mm ×
A casting polymerization cell having an inner volume of 220 mm width × 1 mm thickness was prepared. Each composition shown in Table 1 and Table 2 was poured into this, and it was further heated in an oven at 100 ° C. for 2 hours.
After heat curing at 0 ° C. for 3 hours, the mixture was cooled to room temperature, the casting polymerization cell was removed, and the appearance of the cured product of the epoxy resin composition was observed. Since Examples 6, 7 and 8 in Table 1 contain a volatile organic solvent, the solvent was distilled off in advance by an evaporator and then poured into a cell. ○: No cracks
Each symbol is represented by the same symbol. Similarly, when there are no air bubbles, the symbol ○ indicates 1 to
When the number is 5, the number is indicated by Δ, and when there are 6 or more or large volatile content boiling marks, the symbol is indicated by X.

[0062]

[Table 3]

The results in Table 3 show that the epoxy / acid anhydride resin compositions of Comparative Examples 1 to 10 do not have sufficient performance in any one of curing activity, storage stability and properties of the cured product.
All of the epoxy / acid anhydride resin compositions of Examples 1 to 8 are shown to be excellent in all of these performances.

[0064]

The epoxy / acid anhydride composition of the present invention may be diluted with an organic solvent, if necessary, and then added in an amount of 2 to 1000 c.
It can be prepared to have a relatively low viscosity of ps, and after mixing the epoxy compound, the acid anhydride and the substituted triazine according to the claims without using a solvent, it is preheated to be B-staged or oligomerized to compare 1000 to 100000 cps. It has a characteristic that it can be prepared to have a relatively low viscosity. The storage stability after mixing is 7 days or more at room temperature, which is extremely high for an epoxy / acid anhydride system, and the compounding stability with various liquid materials is also good. Further, the epoxy / acid anhydride composition of the present invention can be easily cured. This curing is carried out at 1 to 5 at 100 to 200 ° C. using an ordinary electric furnace, hot air furnace, infrared furnace, microwave furnace, induction heating furnace, or the like.
It can be cured in about an hour. Even when it is diluted with an organic solvent and used, the solvent can be volatilized under the above conditions. Furthermore, fillers such as silica particles, alumina particles, and glass fibers can be mixed and impregnated into the reinforcing material. Good adhesion to wood, metal materials, various inorganic materials, etc., and chemical resistance Is also high,
Paint vehicle, ceramic coating / adhesion, concrete coating / adhesion, sealing agent for construction / construction materials, adhesive for paper and wood processing, glass cloth / epoxy composite material, carbon fiber reinforced composite material, boron fiber reinforced composite material, fiber treatment agent It is also useful as a binder for pharmaceuticals and agricultural chemicals, a plastic surface coating agent, a glass breakage preventing coating agent, a film-forming masking agent, and a resin-based sealing agent for electronic parts.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Motohiko Hidaka 1 722, Tsuboi-cho, Funabashi, Chiba Prefecture Nissan Chemical Industry Co., Ltd. Central Research Laboratory

Claims (4)

[Claims] 1. An epoxy / acid anhydride composition comprising an epoxy compound and an acid anhydride as an epoxy curing agent, the formula [I]: being a curing accelerator. ( _Wherein X represents an amino group, a C _1-18 monoalkylamino group, a C _1-18 dialkylamino group, a morpholino group, a piperidino group, a methyl group or a phenyl group, and R ¹ and R ²
_Are each independently a C _1-12 alkyl group, a C _1-12 hydroxyalkyl group, a C _4-8 cycloalkyl group, C
_{5-9 is} a cycloalkylmethyl group or a C _5-9 methylcycloalkyl group. ) An epoxy / acid anhydride composition comprising a substituted triazine represented by 2. With respect to 100 parts by weight of the epoxy compound,
The substituted triazine represented by the formula [I] is contained in an amount of 0.1 to 5 parts by weight, and the acid anhydride group of the acid anhydride is 0.7 to 1.2 with respect to 1 equivalent of the epoxy group of the epoxy compound. The epoxy acid anhydride composition according to claim 1, characterized in that it is contained in an equivalent ratio. 3. The epoxy acid anhydride composition according to claim 1, wherein the epoxy compound is an epoxy compound having at least two epoxy groups. 4. An epoxy / anhydride resin composition produced by heat-curing the epoxy / anhydride according to any one of claims 1 to 3.