JPS588701B2 - Epoxy resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin composition that has low toxicity, is easy to handle, and exhibits excellent electrical properties when cured.

BF3 complex as a polymerization or curing catalyst for epoxy compounds,
Amines or organometallic compounds are known, and amine compounds and acid anhydrides are known as curing agents.

By the way, when a BF3 complex or amines are used as a polymerization or curing catalyst, the polymerization rate is good, but the disadvantages are that the degree of polymerization is low and the mechanical or electrical properties in the cured state are poor. Moreover, when an organometallic compound is used, there is a disadvantage that it tends to lose its activity during storage.

On the other hand, when an amine compound is used as a curing agent, it has the advantage of being able to be cured at a low temperature, but on the other hand, there are problems in that it has a poor pot life, is toxic, and is difficult to handle.

Furthermore, when an acid anhydride is used, it not only requires high humidity for the curing reaction, but also has the disadvantage that it is difficult to handle because it easily sublimes, and it can cause damage to the equipment.

Therefore, it is an object of the present invention to provide an epoxy resin composition that is easy to handle, easy to polymerize and cure, and exhibits excellent electrical insulation properties in the cured state.

To explain the present invention in detail below, the present invention provides a catalyst for polymerizing a) an epoxy compound having at least one epoxy group in the molecule, and b an epoxy compound, and an o. ooi~5% by weight and 0.
Alkoxy compounds, phenoxy compounds, acyloxy compounds of aluminum mixed in a proportion of 01 to 5% by weight,
Or a chelate compound of aluminum and β-diketone or O-ketophenol, or an alkoxy group,
Phenoxy group, acyloxy group, or β-diketone 0
- A resin composition comprising as essential components an aluminum compound bonded to two or more selected from the group of ketophenol ligands, a catalyst comprising an organosilicon compound having a hydroxyl group, and a C adsorbing inorganic compound.

That is, the present invention is an epoxy resin composition characterized by using an organosilicon compound-aluminum compound system containing a hydroxyl group as a polymerization or curing catalyst for the epoxy compound, and also using an inorganic compound having adsorption properties.

Examples of the organosilicon compound having a hydroxyl group bonded to Si, ie, an organosilane or polysiloxane compound, which constitute a component of the catalyst in the present invention include the following.

That is, the general formula (wherein R and R' may be the same or different for an alkyl group, phenyl group, aralkyl group, vinyl group, or allyl group, and qr is a positive group of 0 to 3) q0r is an integer within 3) Organosilane or general formula (where R1,
R2, R3, R4, R5, R6, R7, R8, R9, R
IO is an alkyl group, a phenyl group, a vinyl group, an aralkyl group, an allyl group, or a hydroxyl group, and at least one is a hydroxyl group, and s, t, x, and y are positive integers 2 from O to 2, and s+t and x+y are each within 2, uw is a positive integer of θ to 2, and a and b each represent O or a positive integer of 1 or more).

However, the above organosilane and organopolysiloxane compounds may be used alone or in a mixed system of two or more, and the amount added is 0.01 to 0.01 to
A range of 5% by weight is preferred.

In the present invention, other components constituting the latent curing catalyst for the epoxy resin together with the organosilicon compound include an aluminum alkoxy compound, phenoxy compound, or acyloxy compound, and a β-diketone type compound or an aluminum-based central atom. - It is a chelate compound having a ketophenol type compound as a ligand.

In the present invention, alkoxy groups include methoxy, theethoxy, ingropoquine, etc., phenoxy groups include phenoxy, P-methylphenoxy, etc., and acyloxy groups include acetoxy, propionyloxy, impropionyloxy, 7'lyloxy, steryloxy, etc. These include, but are not limited to.

Compounds useful in the present invention include, for example, aluminum triisogropoxide, aluminum t-butoxide, aluminum triacetate, aluminum tristearate, aluminum tribenzoate, and the like.

In the present invention, the β-diketone type compound used as a ligand for chelate formation is a compound having the following chemical formulas (1), (2) and (3).

(In the formula, R represents an alkyl group or a halogen-substituted alkyl group.

) Specifically, compound (1) is acetylacetone,
Examples of the compound (2) include ethyl acetoacetate, and examples of the compound (3) include diethyl malonate.

Further, the O-ketophetol type compound used in the present invention is a compound represented by the following chemical formula (4).

(In the formula, R' represents a hydrogen atom alkyl group, a rogen-substituted alkyl group, or an alkoxy group.

) Specific examples include salicylaldehyde and ethyl 10-hydroxyphenyl ketone.

In these compounds, the ketone in the skeleton forms a chelate bond with the aluminum element and exhibits catalytic ability.
Although changes in parts of the above compound other than the chelate bond forming part affect the degree of catalytic activity to some extent, it is not enough to cause loss of catalytic ability.

Generally speaking, in the above compound group, the O-
The ketophenol type compound has the highest catalytic activity <A, followed by the β-keto ester type compound of formula (2), and the β-keto ester type compound of formula (4).
Although the activity tends to decrease in the order of the diester type compound and the β-diketone type compound of formula (1), both are usable in the present invention.

Examples of the chelate compounds used in the present invention include tris(acetylacetonato)aluminum, tris(
trifluoroacetylacetonato)aluminum, tris(pentafluoroacetylacetato)aluminum,
Examples include tris(nitylacetoacetate)aluminum, tris(sactylaldehydato)aluminum, and tris(diethylmalonato)aluminum, as well as chelate compounds in which aluminum in these compounds is replaced with iron or vanadium.

Furthermore, in the present invention, it is not necessary that all the bonding hands of the metal atom be bonded to a ligand.

When such a group is substituted, the chelate compound becomes even more active.

These chelate compounds may be used alone or in a mixed system of two or more, and the amount added is o. It may be about ooi to 1%.

Among the epoxy compounds that are the main components in the present invention, monofunctional epoxy compounds include ethylene oxide, propylene oxide, butene oxide, styrene oxide, phenyl glycidyl ether, butyl glycidyl ether, and the like.

The polyfunctional epoxy compound is not particularly limited, but includes, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, alicyclic epoxy resin, triglycidyl isocyanate, and hydantoin epoxy. Heterocyclic-containing epoxy resin, hydrogenated bisphenol A epoxy resin,
Aliphatic epoxy resins such as propylene glycol-diglycidyl ether and pentaerythritol-polyglycidyl ether, epoxy resins obtained by the reaction of aromatic, aliphatic or alicyclic carboxylic acids with shrimp chlorohydrin, spiro ring-containing epoxy Resin, glycidyl ether type epoxy resin which is a reactive composition of ortho allyl phenol novolak compound and epichlorohydrin, diallyl bisphenol compound having an allyl group at the orn position of each hydroxyl group of bisphenol A and epichlorohydrin. Any of the reaction products, such as glycidyl ether type epoxy resin, may be used.

Furthermore, the adsorptive inorganic compound which is an essential component of the composition of the present invention and which is added for the purpose of increasing the activity of the catalyst is an organic compound such as amorphous silica, crystalline silica, zeolite, silica alumina, or alumina. Examples include compounds that have an adsorption effect.

The reasons why these adsorbing compounds activate the catalyst system are the stabilization of silanol groups, the increase in apparent acidity due to hydrogen bonding between silanol groups and inorganic materials, and the collision caused by the concentration effect on the adsorbate surface. This seems to be due to an increase in frequency.

Since the epoxy resin composition according to the present invention contains an inorganic compound having an adsorption function as a component, the activity of the organosilicon compound catalyst containing an organoaluminum compound monohydroxyl group is enhanced.

Therefore, if the epoxy compound is monofunctional, the polymerization yield will be increased, and if it is polyfunctional, the cured product will have good electrical and mechanical properties, making it suitable for casting and molding materials. demonstrate.

Next, examples of the present invention will be described.

Example 1 After adding and dissolving 0.4 g of aluminum acetylacetonate and 1.0 g of diphenylsilanediol into distilled and purified cyclohexane oxide 2001, 300 mesh zeolite}5A2Of was dispersed and heated at 60°C for 15 minutes.
After a period of reaction, a white solid polymer was obtained with a yield of 68%.

For comparison, the reaction was carried out under the same conditions as above except that diphenylsilanediol was not used, and the yield was 53%.
Met.

Example 2 After adding and dissolving 0.7 g of aluminum acetylacetonate and 1.0 g of diphenylsilanediol to 200 g of distilled and purified cyclohexene oxide, 20 g of crystalline silica powder was dispersed and reacted at 50° C. for 15 hours. A white solid polymer was obtained with a yield of 65%.

For comparison, a polymerization reaction was carried out under the same conditions as above except that only one of aluminum acetylacetonate or diphenylsilanediol was used, and almost no polymerization was observed.

Example 3 100 parts by weight of alicyclic epoxy resin Chinnox 221 (trade name, Chisso Corporation), 0.45 parts by weight of aluminum acetylacetonate, HO group-containing organosilicon compound S
Mix 0.45 parts by weight of H6018 (trade name, Toray Silicone Co., Ltd.) and 30 parts by weight of amorphous silicon powder,
The mixture was poured into a mold and cured by heating at 130° C. for 15 hours to obtain a plate with a thickness of 1 mm.

The curing reaction of this cured resin board has progressed sufficiently, and 15
Dielectric voltage junction at 0℃ is 1.

It was 6%.

Example 4 Bisphenol F type epoxy resin Epiclon 830 (trade name, Dainippon Ink Co., Ltd.) 100 parts by weight, aluminum acetylacetonate 1.0 parts by weight, HO group-containing organosilicon compound SH6018 (trade name, Toray Silicone Co., Ltd.) 4
．． 0 parts by weight and 30 parts by weight of crystalline silica powder were mixed, poured into a mold, and heated and cured at 180° C. for 15 hours to obtain a cured resin plate with a thickness of 1 mm.

Also, when the dielectric voltage contact of this board was measured, it was 150℃.
It was 2.1%.

Example 5 0.14 g of aluminum acetylacetonate and 0.06 g of diphenylsilanediol were added and dissolved in 100 g of distilled and purified cyclohexene oxide.
0 mesh zeolite}9F5g was dispersed at 40℃.
After 0 hours of reaction, a white solid polymer was obtained with a yield of 27%.

For comparison, the reaction was carried out under the same conditions as above except that zeolite}9F was not used, and the yield was 22%.

Example 6 A polymer was synthesized in the same manner as in Example 1, except that the aluminum compounds shown in the table below were used as the aluminum compounds.

Similarly, the yield of the polymer is also shown.

As is clear from the above results, all catalyst systems of the present invention had excellent catalytic ability.

Claims (1)

[Scope of Claims] 1 a. An epoxy compound having at least one epoxy group in the molecule, and b. 0.001 to 5% by weight and 0.00% by weight of the epoxy compound, respectively, as a catalyst for polymerizing the epoxy compound.
Alkoxy compounds, phenoxy compounds, acyloxy compounds of aluminum mixed in a proportion of 01 to 5% by weight,
Or, if aluminum and β-diketone, << is a chelate compound with O-ketophenol, or an alkoxy group,
Phenoxy group, acyloxy group or β-diketone, O-
An epoxy resin characterized by comprising as essential components an aluminum compound bonded to two or more types selected from the group of ketophenol ligands, a catalyst consisting of an organosilicon compound having a hydroxyl group, and an adsorbent inorganic compound. Composition. 2. An epoxy resin composition according to claim 1, wherein the epoxy compound is an alicyclic epoxy compound.