JPS6041082B2 - Eboxy resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin composition, which exhibits good storage stability particularly at room temperature, and has various properties such as rapid curing reaction at temperatures of about 13,000 ℃ or more. The present invention relates to an epoxy resin composition that becomes a cured product.

When curing epoxy resin, for example, wind polyamiso,
Hardening agents such as acid anhydrides or phenols, or 'B
) It is common practice to add and blend a curing catalyst, typified by a BF3 collar body or a tertiary amine compound, into an epoxy resin.

However, in the worst case, when polyamine is used, there is the disadvantage that the composition cannot be stored for a long time due to its strong reactivity with epoxy resin, and when acid anhydride is used, it is difficult to cure at high temperatures. It has the disadvantage of requiring long heating times. On the other hand, in the case of [BI], although it is possible to cure at a relatively low temperature when a BF3 flange is used, there is a drawback that the electrical and mechanical properties of the cured resin at high temperatures are poor. Furthermore, when a tertiary amine is used, a high temperature is required for the curing reaction, and there are also operational problems such as skin irritation. Furthermore, when curing epoxy resins, attempts have been made to add and blend metal late compounds as latent curing catalysts. However, in this case, not only does the curing reaction require a high temperature of 20,000 °C or more, but the amount of the metal chelate compound added is relatively large at about 2%, and the compound has poor properties due to its poor dissolution and dispersibility. There is a disadvantage that it is difficult to form a hardened resin layer. The inventors of the present invention proceeded with studies to address these points, and as a result, discovered that organosilanes or organopolysiloxanes having a hydrolyzable group bonded to Si in the molecule and an aluminum compound having an organic group are latent. When added to epoxy resin as a curing catalyst, it exhibits excellent storage stability at room temperature, but when heated above about 130°C, it easily undergoes a curing reaction, resulting in good curing of electrical and mechanical properties. It has been found that a resin layer can be obtained.

Based on the above findings, the present invention aims to provide an epoxy resin composition that is easy to handle and suitable for insulation treatment of electrical equipment.

The present invention will be described in detail below. } This is an epoxy resin composition characterized by containing an aluminum compound having an organic group as a latent curing catalyst in an epoxy resin.

In the present invention, the organosilane or polysiloxane compound having a hydrolyzable group bonded to Si and forming a component of the latent curing catalyst for the epoxy resin includes the following.

That is, the general formula (wherein R, R', and R'' may be an alkyl group, a phenyl group, an aralkyl group, a vinyl group, or an allyl group, and may be the same or different, and q and r are positive groups of 0 to 3). is an integer of q+r within 3) or the general formula (wherein R,, R2, R3, R4, R5,
R6, R7, R8, R9, R, o are alkyl groups, phenyl groups, pinyl groups, aralkyl groups, allyl groups or hydrolyzable groups, and at least one is a hydrolyzable group, s
, t, x, y are positive integers from 0 to 2, and s + t and x + y
are each within 2, U and W are positive integers from 0 to 2, a, b
each represents a positive integer of 0 or 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 from 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01.
A range of 5% by weight is preferred.

In the present invention, the other component constituting the latent curing catalyst for the epoxy resin together with the organosilicon compound is an alkoxy compound of aluminum, a phenoxy compound, or an acyloxy compound. In the present invention, alkoxy groups include methoxy, ethoxy, isopropoxy, etc., phenoxy groups include phenoxy, p-methylphenoxy, etc., and acyloxy groups include acetoxy, propionyloxy, isopropionyloxy,
Examples include butylreoxy, stearyloxy, etc.
It is not limited to these. Compounds useful in the present invention include, for example, aluminum, triisopropoxide, aluminum, t-butoxide, aluminum, triacetate, aluminum, tristearate, aluminum, tribenzote, and the like. Furthermore, in such a compound, one or two of an alkoxy group, a phenoxy group, or an acyloxy group may be substituted with an organic ligand. In the present invention, B-diketone type compounds and O-hydroxyketone type compounds can be used as the organic ligand. A B-diketone type compound is a compound represented by the following chemical formulas (1', ■, and [31. (In the formula, R represents an alkyl group or a halogen-substituted alkyl group.) Also, a 0-hydroxyketone type compound is a compound represented by the following chemical formula.

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

) These compounds may be used alone or in a mixed system of two or more, and the amount added may be about 0.001 to 1% by weight based on the epoxy resin.

The epoxy resin which is the main component in the present invention is commonly known and is not particularly limited.

For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin such as triglycidyl isocyanate and hydantoin epoxy, hydrogenated bisphenol A type epoxy resin, propylene Aliphatic epoxy resins such as glycol diglycidyl ether and pentaerythritol holiglycidyl ether, epoxy resins obtained by the reaction of aromatic, aliphatic or cycloaliphatic carboxylic acids with epichlorohydrin, spiro Ring-containing epoxy resin, glycidyl ether type epoxy resin which is a reaction product of ortho-allyl-phenol borac compound and ethyl chlorhydrin, diallyl bisphenol having an allyl group at the ortho position of each hydroxyl group of bisphenol A Any glycidyl ether type epoxy resin, which is a reaction product of a compound and epichlorohydrin, may be used. The epoxy resin composition according to the present invention has the advantage that it has good storage stability and is easy to handle in work since it undergoes a rapid curing reaction at a temperature of, for example, about 130 qo. Furthermore, by selecting the type and composition ratio of the epoxy resin, it is not only suitable for casting, impregnation, molding, etc. as a so-called solvent-free type, but also easily dissolves in low-boiling point solvents such as dioxane and tetrahydrofuran. Therefore, it can be easily applied to glass cloth, paper, etc., so it can also be used for forming laminates. Moreover, the cured resin maintains and exhibits excellent heat resistance, mechanical properties, and electrical insulation properties. The epoxy resin composition according to the present invention may be composed solely of the above epoxy resin-organosilane or organopolysiloxane-aluminum compound having an organic group, or may be appropriately blended with an inorganic filler etc. to obtain the same effect. There is.

Next, examples of the present invention will be described.

Example 1 As an epoxy resin, Epicoat 828 (trade name, manufactured by Shell Chemical Co., Ltd.; bisphenol A type, epoxy resin 190) was used as an epoxy resin.
~210, molecular weight 380) 70 parts by weight, Epiquat 10
0/(Product name, manufactured by Shell Chemical Co., Ltd.; Bisphenol type A,
An epoxy resin composition was prepared by using 3 parts by weight of epoxy equivalent (450 to 480, molecular weight 900), 2 parts by weight of aluminum triisopropoxide as an aluminum compound, and 2 parts by weight of triphenylmethoxysilane as a silicone compound. It was adjusted.

When this material was poured into a mold consisting of two glass plates sandwiching one bar of substrate and heated at 180 qo for 1 hour, it was cured. Using this cured resin board, we measured the dielectric positive tan (tan6) value and found that it was 2 at 200 qo.
．． It was 3%. Example 2 As an epoxy resin, Epicoat 8285 lid military, Epicoat 152 (trade name,
Made by Shell Chemical Co., Ltd.: Phenol novolak type, epoxy equivalent weight 172-179) Using 5 parts by weight, aluminum tritium butoxide 1 as the aluminum compound
An epoxy resin composition was prepared using 2 parts by weight of triphenylmethoxysilane as the silicone compound.

This product was heated at 180 qo for one morning in the same manner as in the above example to obtain a resin plate on the first side. This one's tan6
The value was 3.5% at 200o○. Example 3 As an epoxy resin, ERL4221 (trade name, UCC
manufactured by Seikoho-type epoxy compound, epoxy equivalent weight 145, molecular weight 290) 5 parts by weight, using parts by weight of Epikot 10015, 1 part by weight of aluminum triacetate as an aluminum compound, 1 part by weight of diphenyljethoxysilane as a silicon compound. The resin plate on the first side was obtained by heating at 180° C. for 1 hour in the same manner as in Example 1.

The tan6 value of this product was 200qo and 2.4%. Example 4 As an epoxy resin, Epicoat 807 (trade name, manufactured by Shell Chemical Co., Ltd.; bisphenol F type, epoxy equivalent: 170
, molecular weight 340) 7, parts by weight of Epiquat 10013, 2 parts by weight of aluminum triberezoate as the aluminum compound, and 1 part by weight of triphenylmethoxysilane as the silicone compound. In the same manner, it was heated at 180 qo for one period to obtain one rib of resin plate.

The n6 value of this product was 3.5% at 20 p0.
Examples 5 and 6: Comparative Examples 1 and 2 Epoxy compounds: Epicote 828, Epicote 1〇〇10 Acid anhydride curing agent: Epiclone B-570 (trade name, Dainippon Ink ■: Compound of the following formula 〇)・Organosilicon compound: dimethoxydiphenylsilane.

・Organic aluminum compound: ■Aluminiumisoprop.

Poxide, ■Aluminum stearate, ●BF3/monoethylamine The above materials were blended into the compositions (parts by weight) shown in Table 1 to prepare resin compositions for Examples 5 and 6 and Comparative Examples 1 and 2.

18 of the cured resin plate obtained by curing at 160°C for 1 hour
Nene n6 value and heat distortion temperature at 0qo (DIN53
458) was measured.

The results are shown in the same table. Table I Example 7 Parts by weight of alicyclic epoxy resin Chissonox 221 (trade name, Chisso Corporation) 6, parts by weight of glycidyl epoxy resin Shodine 540 (trade name, Showa Denko K.K.) 4, 21 (3. 0.5 parts by weight of 4-cyclohexeneoxy)ethyltrimethoxysilane, 0.5 parts by weight of aluminum triisopropoxide. A casting resin composition was prepared by mixing parts by weight of a box and 18 parts by weight of silica powder with a particle size of 200 mesh.

On the other hand, a coil element is made by winding a flat rectangular copper wire into a disk shape with aromatic polyamide non-woven fabric Nomex (trade name, DuPont) tape wound twice in a 1' overlap, and aromatic polyamide non-woven fabric is placed between each stage. The coils were stacked in five tiers, and the outer periphery was wrapped twice with a 1'a layer of coarse glass tape to form a coil. The above-mentioned coil was housed in a technique mold, placed in a vacuum impregnation tank, and the pressure was reduced to 1 skin Hg.
~110 ○ heating temperature) is poured into the casting mold and the gauge pressure is 5.
The coil was cast under pressure at k9/ground for 5 hours.

Take out this Azusa type rear coil from the tank 150qC x 5
Heat treatment was performed sequentially for 170 oo x 1 feeding time to harden the resin and obtain a Western-style coil. The thus obtained stand-up coil was subjected to a heat cycle test with electrical heating and cooling in the range of 155 to 40 qO, and no cracks were observed in the cast resin layer, showing good results.

It also showed good performance in heat shock tests conducted between 80 qo and 10 pm, and had highly reliable functionality even when installed roughly in a dry type transformer. As is clear from the above examples, the resin composition of the present invention is suitable for impregnation and casting, and is also soluble in low boiling point and non-polar organic solvents, so it can be used in laminates, molding materials, prepregs, pinned materials, etc. It can be said to be suitable as an insulating material for electrical equipment such as tapes, replacements, and bearing materials.

Claims (1)

[Claims] 1 (a) At least one organosilane or organosiloxane compound having at least one Si-bonded hydrolyzable group per molecule in an amount of 0.01 to 5% by weight based on the epoxy resin, and (b ) An epoxy resin composition characterized in that an epoxy resin contains an alkoxy compound, a phenoxy compound, or an acyloxy medium of aluminum in an amount of 0.001 to 5% by weight based on the epoxy resin.