JPS58187426A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:A composition, prepared by incorporating a polyfunctional carboxylic acid (anhydride) as a curing agent and an alcoholic compound in an epoxy resin having plural oxirane rings, curable rapidly to give cured articles without air bubbles, and having improved light transmittance. CONSTITUTION:A composition prepared by incorporating (A) 100pts.wt. epoxy resin having two or more epoxy groups in the molecule, e.g. bisphenol A type epoxy resin, with (B) preferably 80-100pts.wt. polyfunctional carboxylic acid or an acid anhydride thereof, e.g. phthalic acid (anhydride) or trimellitic acid (anhydride), as a curing agent and (C) preferably 1-30pts.wt. alcoholic compound, e.g. hexyl alcohol or ethylene glycol, and if necessary a curing accelerator, inorganic filler, pigment, etc. EFFECT:The cured article has improved electrical characteristics, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an epoxy resin composition, and more specifically,
This invention relates to an epoxy resin composition whose cured product does not contain bubbles and has excellent optical transparency.

[Technical background of the invention and its problems]

Conventionally, cured resin products made of epoxy resin compositions have been used in various technical fields because they have excellent electrical properties.
? It has come to be widely used in

For example, an acid anhydride-based hardener or an amine-based hardened steel ring is used to harden such an epoxy resin composition. In general, when using these hardeners, the cured wood made using an acid anhydride hardener has better mechanical properties and electrical properties than those made using an amine hardener. It is known that the properties of the cured product are excellent, and that the properties of the cured product are particularly good at high temperatures.

However, when an acid anhydride curing agent is used, there is a problem in that a high temperature is required for the curing reaction because the reaction rate is slow.

For the purpose of improving industrial productivity, rounding is
Using a basic compound of J3 grade as a reaction accelerator,
An addition to Ik# is being made. However, in this case, there is a problem in that the acid anhydride and the basic compound cause a decarbonation reaction during heat curing, and bubbles remain in the imh cured product. Therefore, for example, when used as an insulating material for high-voltage equipment, its corona resistance is significantly impaired, and when used as a sealing resin for a light-emitting element's electrical-to-optical conversion polymer, it This results in a significant decrease in permeability.

In order to prevent such problems, conventionally, resin compositions have been prepared with low I! It is cured using a step-cure method in which the temperature is raised stepwise from the side. In this step curing method, since the curing reaction takes a long time, it is not preferable from the viewpoint of improving productivity to be used as a material for electrically produced products such as 11fi sealed semiconductors.

[Purpose of the invention]

The purpose of the present invention is to solve the above-mentioned difficulties, to produce an epoxy resin whose resin composition cures quickly at a certain knitting degree or above, and whose cured resin does not contain bubbles and has excellent light transmittance. It is also possible to provide a composition.

[Summary of the invention]

As a result of extensive research, the present inventors have discovered that the above object can be achieved by adding to the epoxy resin composition an alcohol compound whose boiling point is higher than the curing temperature of the epoxy resin composition, and have completed the present invention. reached.

That is, the epoxy resin composition of the present invention comprises (a) an epoxy resin having two or more oxirane rings in the molecule, (b) polyvalent carbo/# or its acid anhydride, and (C)
It is characterized by consisting of an alcohol compound.

In the following, the invention will be explained in more detail.

As the epoxy TK4 used in the present invention, any epoxy TK4 having two or more oxirane rings in the molecule can be used. Such epoxy resins include, for example, bispheno-/LA type epoxy resin; bisphenol F type epoxy resin; phenol-Norac type epoxy Ili alicyclic epoxy resin 1
Triglycidyl isocyanurate, dantoin epoxy complex-containing epoxy resin, hydrogenated bisphenol A type epoxy 411 fat; aliphatic epoxy resin such as propylene dalycol-diglycidyl ether, pentaerythritol-polyglycidyl ether; aromatic A glycidyl ester type epoxy resin obtained by the reaction of a group, aliphatic or Vi cyclic carboxylic acid with epichlorohydrin; Certain glycidyl ether type epoxy resins include glycidyl ether type epoxy resins which are reaction products of diallyl and suphenol compounds having an allyl group at the 0-position of each hydroxyl group of bisphenol A and epichlorohydrin. .

In the present invention, 1111 or two or more strains selected from the group consisting of the above-mentioned nine epoxy resins are used.

The polyhydric carboxylic acid or acid anhydride used in Kien F14 is used as a curing agent for epoxy resin. Such polyhydric carboxylic acid/acid or its acid anhydride may be any of those commonly used as curing agents, such as phthalic acid, trimellitic acid, tetrahydrophthalic acid, hequinahydro-7 Polycarboxylic acids such as taric acid, methyltetrahydrophthalic acid, methylhexhydrophthalic acid, chlorendittaic acid, and phthalic anhydride, detrahyde9phthalic anhydride, hequinahydrophthalic anhydride, trimellitic anhydride, anhydride Examples include acid anhydrides such as chlorendic acid, nadic anhydride, methylnadic anhydride, methyleneendomethylene phthalic anhydride, totyrynyl succinic anhydride, methylnatodihydrophthalic anhydride, and methylhexylhydrophthalic anhydride. A selected coffin or more than 281 books from these groups are used.

The blending amount of the above-mentioned polycarboxylic acid or its acid anhydride is
It is preferably 40 to 120 parts by weight, more preferably 80-'' to 100 parts by weight of epoxy tree.
It is 109 parts by weight. If the amount is less than 403,111 parts or more than 120 parts by weight, the curability of the resin composition will decrease.

The alcohol compound used in the present invention is h+!
It is added to suppress foaming during hardening of Xis. Any alcohol compound may be used as long as it has a boiling point higher than the curing temperature of the epoxy resin composition, such as hexyl alcohol,
Octyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, stearyl alcohol and other ossalunyls; glycols such as ethylene glycol, propylene gelylcol, butanediol, hexa/diol, neopentyl glycol; glycerin, penta Erythritol type polyhydric alcohols, polyols such as ethylene glycol and polypropylene glycol, polycyclohexanol group type III concentrated alcohols, nibenzyl alcohol, cinnamyl alcohol◆, aromatic alcohols;
and complex alcohol 11 of furfuryl alcohol
1%, and the lumberjacks who were more widespread than the group consisting of these.
Alternatively, 28 or more - is used.

The amount of the alcohol compound mentioned above is epoxy 411
The amount is preferably 1 to 30 parts by weight based on fjltoo parts by weight. If the amount is less than 1 part by weight, a sufficient foaming inhibiting effect will not be obtained, while if it exceeds 30 parts by weight,
The resulting tree jIIIiI! The side heat property of the compound decreases.

In the present invention, a curing accelerator, an inorganic filler, a pigment, a mold release agent, a coupling agent, a rubber plasticizer, a thermoplastic resin, a glass fiber, an anti-aging agent, etc. are added as appropriate. , there is no problem even if it is added and blended.

[Embodiments of the invention]

Examples 1 to 4 As epoxy resins, Epikote 828 (manufactured by Shell Chemical Co., Ltd., bisphenol A [epoxy resin To) and IRL-4221 (manufactured by UCC Co., Ltd., Type III Epoxy 7) were used.
Hexahydrophthalic anhydride and methylhexahydrophthalic anhydride were used as curing agents, and the alcohol compounds were ethylene glycol, stearyl alcohol, GP-600 (Sanyo Kasei Co., Ltd. li!),
Using polyether polyol, average molecular weight Ji 600 ), and decyl alcohol, four starch epoxy superfat compositions were prepared in the predominant amounts (weight S) shown in the table. still,
Benzyldimethylamine or DBU as a curing accelerator
(manufactured by Sanyo Chemical Co., Ltd., 1,8-diaza-bicyclo(5,
4,0) Undecene-7) was added and blended.

For each of the above resin compositions, 30111 was subjected to an 18 φ IK test, and the presence or absence of foaming was visually observed in an oil bath at 125C.

For these Is4 fat compositions, 125 tl? After heating for 2 hours, heat at 155C for 4 hours to harden, 41! A cured fat product was obtained.

Thermal expansion needle (
Shinku Riko Co., Ltd. #l, ULVAC, DL-1500
)Using#! The expansion coefficient was measured, and the glass transition point was determined from one point of inflexion. In addition, using a spectrophotometer (manufactured by Takasu Seisakusho Co., Ltd.), we determined the light intensity at 600 nmV (9).

Their binding is shown in the table along with the blending amount.

Comparative Examples 1 to 3 Epoxy resin compositions for three glazes were prepared in the same manner as in Examples except that the pulcohol compound was not used or the compounding lid was changed.

Regarding these epoxy resin compositions, the presence or absence of foaming, glass transition point, and light transmittance were measured in the same manner as in Examples.

The formulations and results are shown in the table along with Examples.

As is clear from the table, it was confirmed that the epoxy resin composition of the present invention exhibited no foaming at all during its curing.

Furthermore, it was confirmed that the cured resin has a high glass transition point, excellent thermal properties, and has no air bubbles in the cured resin, so it has excellent light transmittance.

〔Effect of the invention〕

The epoxy resin composition of the present invention does not generate any bubbles during its curing reaction due to the addition of an alcohol compound. Therefore, a cured resin having excellent optical transparency can be obtained, and is suitable as an insulating material for high-voltage equipment or a resin for sealing electrical-optical conversion elements.

Furthermore, since foaming does not occur during curing, it is possible to obtain a hardened Ni product in a short time.

Therefore, it can be used for sealing semiconductors etc. and as a fat.
It is clear that this will greatly contribute to improving productivity.

Claims (1)

[Claims] (JL) An epoxy tree containing two or more oxiranes in the molecule, 1Φ) a polycarboxylic acid or its acid anhydride, and (C)
An epoxy resin composition comprising an alcohol compound.