JPS6147724A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent transparency, heat-resistance and storage properties, by compounding an acid anhydride hardener, a cure accelerator and a specific fatty acid to a resin mixture of a bisphenol A epoxy resin and triglycidyl isocyanurate. CONSTITUTION:The objective resin composition can be produced by compounding (A) 100pts.(wt.) of a mixed epoxy resin composed of (i) 50-80pts. of a bisphenol A epoxy resin having a melting point of 60-170 deg.C and (ii) 20-50pts. of triglycidyl isocyanurate or its derivative with (B) 30-150pts. of an acid anhydride hardener, (C) 0.1-10pts. of a cure accelerator selected from imidazole compounds, 1,8-diaza-bicyclo(5.4.0)undecene-7 or its salt, and organic phosphine compound, and (D) 0.5-5pts. of a compound selected from >=16C saturated monobasic fatty acid and >=16C hydroxyfatty acid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an epoxy resin composition, and more specifically,
The present invention relates to an epoxy resin composition for pressure molding that has good transparency and heat resistance, and excellent storage properties.

[Technical Background of the Invention and Problems 1] As a resin for sealing elements and parts that require transparency, such as light-emitting elements and light-receiving elements such as light-electric conversion elements, resins with high light transmittance and It must also have good properties such as heat resistance, electrical properties, and moisture resistance. Conventionally, alicyclic epoxy resins and low-viscosity bisphenol A-type epoxy resins have been used as materials that have high transmittance over all wavelengths of visible light. When these resins are used for pressure molding, such as transfer molding, a curing catalyst is added,
It is necessary to solidify by aging (generally heating). However, it has the disadvantage that aging significantly reduces its shelf life to several days at room temperature.

On the other hand, solid bisphenol A type epoxy resins are advantageous in this respect, do not require aging, and do not have to worry about reducing shelf life, but have the disadvantage of having lower heat resistance than the above-mentioned epoxy resins. In contrast, novolak-type epoxy resins do not have problems with shelf life or heat resistance, but they have the disadvantage of being colored, yellowish brown or reddish brown, and having extremely poor transparency. Like resins, they have drawbacks in at least one of transparency, shelf life, and heat resistance.

[Object of the Invention] The object of the present invention is to eliminate the above-mentioned drawbacks, namely:
An object of the present invention is to provide an epoxy resin composition for pressure molding that has good transparency and heat resistance and excellent storage properties.

[Summary of the Invention] The epoxy resin composition of the present invention comprises: (a) a mixture consisting of 50 to 80 parts by weight of a bisphenol A epoxy resin having a melting point of eo to 170°C and 20 to 50 parts by weight of triglycidyl isocyanurate or a derivative thereof; Epoxy resin 100 parts by weight (b) Acid anhydride curing agent 30 to 150 parts by weight (c) Group consisting of imidazole compounds, 1,8-diazalbicyclo(5,4,0) undecene or its salts, and organic phosphine compounds 0.1 to 10 parts by weight of at least one curing accelerator selected from
It is characterized by comprising 0.5 to 5 parts by weight of at least one compound selected from the group consisting of the above oxyfatty acids.

The mixed epoxy resin used in the present invention has a melting point of 60 to 17
50 to 80 parts by weight of bisphenol A type epoxy resin at 0°C and triglycidyl in cyanurate or its derivative 2
0 to 50 parts by weight.

Examples of bisphenol A epoxy resins include Epicoat 1001 (trade name, epoxy equivalent: 470,
Melting point: 265°C, manufactured by Shell), Epikote 1004 (
Product name, epoxy equivalent: 850, melting point: 100°C, manufactured by Shell), Ebicor) 1007 (product name, epoxy equivalent: 2000, melting point: 130°C, manufactured by Shell), Evicron 1050 (product name, epoxy equivalent: 450) ,
Melting point = 65°C, manufactured by Dainippon Ink Co., Ltd.), Epicron 405
0 (trade name, epoxy equivalent: 850, melting point: 100°C,
Dainippon Ink Co., Ltd.), DER [1 (trade name, epoxy equivalent: 450, melting point = 70°C, Dow Chemical Co., Ltd.),
IIER664 (trade name, epoxy equivalent = 825, melting point: 100°C, manufactured by Dow Chemical Company), DH, R887
(Product name, epoxy equivalent: 1800, melting point: 120°C
(manufactured by Dow Chemical Company), and at least one selected from the group consisting of these is used. These resins are solid at room temperature (25°C) and have a melting point of usually 60 to 170°C, preferably 65 to 170°C.
It is ℃.

If the melting point is less than 80°C, it will be unsuitable for pressure molding unless preliminary reaction (ripening) is carried out for a long time, and aging treatment will result in a decrease in shelf life. On the other hand, if the temperature exceeds 170°C, it is difficult to mix uniformly unless heated and mixed at a high temperature, and furthermore, high temperature treatment causes coloring, resulting in a decrease in transparency.

Examples of triglycidyl isocyanurate derivatives include those obtained by reacting a part of the epoxy group of triglycidyl isocyanurate with another reactive compound.

Examples of this reactive compound include bisphenol A
Compounds with phenolic hydroxyl groups such as carboxylic acid anhydrides.

Examples include dicarboxylic acids, compounds having alcoholic hydroxyl groups such as polyethylene glycol, and fatty acid polyamides having amino groups.

The triglycidyl isocyanurate M conductor is blended in an amount of 20 to 5 parts by weight based on 50 to 80 parts by weight of the bisphenol A type epoxy resin.
The reason why it is limited to 0 parts by weight is that if it exceeds 50 parts by weight, it will not be possible to obtain an excellent shelf life.
On the other hand, if it is less than 20 parts by weight, the heat resistance of the cured product will not be sufficient, and if it is left at high temperatures, it will turn brown and transparency will decrease, and the heat cycle characteristics of the molded product will decrease, such as emitting light. This is because, when used in devices, defects such as wire breakage are likely to occur.

The acid anhydride curing agent used in the present invention may be any commonly known one, such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride. acid, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and the like. These may be used alone or in a mixture of two or more.

These acid anhydride curing agents have a carboxylic acid anhydride group of 0.5 to 1.
It is blended at a ratio of 5 parts, and the blending ratio is:
Usually, 30 to 1 part by weight per 100 parts by weight of total epoxy resin.
The amount is 50 parts by weight, preferably 40 to 130 parts by weight.

If this blending ratio is outside the above range, the heat resistance and electrical properties will drop significantly, which is not preferable.

The curing accelerator used in the present invention is an imidazole compound, 1
,8-diaza-bicyclo(5,4,0)undecene-7
or at least one compound selected from the group consisting of salts thereof and organic phosphine compounds.

Examples of the imidazole compound include 2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-7enylimidazole, 2-undecylimidazole, and 2-heptadecylimidazole.

1.8-Diaza-bicyclo(5,4゜0) undecene-
Examples of the salts of 7 include -phenol salt, 2-ethylhexanoate, oleate, and acidic carbonate.

Examples of the organic phosphine compound include triphenylphosphine, tricyclohexylphosphine, tributylphosphine, methyldiphenylphosphine, and the like.

These may be used alone or in a mixture of two or more.

The blending ratio of component (c) is usually all epoxy resin.
The amount is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight. If this blending ratio is less than 0.1 part by weight, there is no effect of accelerating curing, while -
If it exceeds 110 parts by weight, heat generation during curing will be large;
As a result, cracks appear in the cured product and significant coloring occurs, and the light transmittance decreases.

Component (d) used in the present invention is at least one compound from the group consisting of saturated monovalent fatty acids having 18 or more carbon atoms and oxyfatty acids having 18 or more carbon atoms.

Examples of saturated fatty acids include palmitic acid, stearic acid, isostearic acid, behenic acid, liglyceric acid, cerotic acid, and montanic acid. Examples of oxyfatty acids include oxystearic acid, Rapalmitic acid.

Examples include ricinoleic acid, and at least one selected from the group consisting of these is used. carbon number 1
The reason why it is limited to 8 or more is because if it is less than 16, not only the effect as a mold release agent cannot be obtained sufficiently, but also a decrease in the heat distortion temperature and mechanical properties of the cured epoxy resin is observed. .

Furthermore, if necessary, saturated fatty acids having 10 or more carbon atoms such as lauric acid and myristic acid, and m-fatty acids having 18 or more carbon atoms such as cetyl alcohol, isocetyl alcohol, stearyl alcohol, and oleyl alcohol may be added. There is no problem even if a group alcohol is blended.

The blending ratio of component (d) is usually 0.5 to 5 parts by weight based on 100 parts by weight of the total epoxy resin. If this blending ratio is less than 0.5 parts by weight, the effect as a mold release agent will not be sufficiently obtained, and if it exceeds 5 parts by weight, it will cause a decrease in the heat distortion temperature and mechanical properties of the cured product. Undesirable.

The epoxy resin composition for pressure molding of the present invention includes:

Furthermore, if necessary, a coupling agent such as an epoxy silane type, a vinyl silane type, or a titanate type; a deterioration inhibitor such as an antioxidant; and a coloring agent such as a bluing agent may be blended.

Next, the epoxy resin composition for pressure molding of the present invention can be prepared by melt-mixing the above-mentioned components using heated rolls, melt-kneading using a Ni-Goo, melt-kneading using an extruder, mixing with a special mixer after finely pulverizing, and mixing these components using a special mixer after pulverizing. It can be easily manufactured by appropriate combination of each method.

In order to improve the productivity during molding, the resin composition for pressure molding of the present invention is appropriately heat-ripened during production of the composition to partially advance the reaction and B-stage it. B
- The stage state can be controlled by controlling the kneading time during melt mixing, or by ripening at a temperature below the melting point, preferably from 50°C to around room temperature, after mixing.

The epoxy resin composition for pressure molding of the present invention has excellent storage stability in the B-stage state at room temperature or at temperatures below room temperature if necessary, and is extremely suitable as a resin for pressure molding such as transfer molding and compression molding. suitable.

In the following, the present invention will be further explained in detail with reference to Examples and Comparative Examples. In addition, in Examples and Comparative Examples, all parts r and j indicate "parts by weight."

[Examples of the Invention] The composition components and proportions shown in Table 1 were mixed to prepare an epoxy resin composition for pressure molding of the present invention.

In order to evaluate the properties of the obtained composition, the following measurements were performed.

The melt viscosity of the molding powder for shelf life was measured after a certain period of time, and the time was determined as the time until the melt viscosity reached twice the initial melt viscosity.

Light transmittance: Measured at 500 nm using a spectrophotometer (UVD [-510 model: manufactured by JASCO Corporation).

Using the obtained composition, a light emitting element was sealed by a transfer molding method to prepare a sample.

The following thermal shock test was conducted using the obtained sample.

Thermal shock test: -40℃ and 125℃, respectively.
The process of alternately heating and cooling for 30 minutes was defined as one cycle, and those with abnormal operation or wire breakage were treated as defective products, and the defective rate after 500 cycles was investigated.

The results are shown in Table 1.

A comparative composition was prepared by mixing the components and proportions shown in Table 1. Evaluation tests similar to those in Examples 1 and 2 were conducted using the obtained compositions.

The results are shown in Table 1.

An epoxy resin composition for pressure molding of the present invention was prepared by mixing the composition components and proportions shown in Table 2. Using the obtained composition, evaluation tests similar to those in Examples 1 and 2 and further measurement of heat distortion temperature (ASTMo 848-58) were performed. The results are shown in Table 2.

A comparative composition was prepared by mixing the composition components and proportions shown in Table 2. Using the obtained compositions, the same evaluation tests and measurements as in Examples 3 to 5 were performed.

The results are shown in Table 2.

The epoxy resin composition for pressure molding of the present invention was prepared by mixing the composition components and proportions as shown in Table 3 of Table 2, JL Medicinal. Evaluation tests similar to Examples 3 to 5 were conducted using the obtained compositions. The results are shown in Table 3.

A comparative composition was prepared by mixing the composition components and proportions shown in Table 3. Using the obtained compositions, the same evaluation tests and measurements as in Examples 3 to 5 were performed.

The results are shown in Table 3.

A composition of the present invention was prepared by mixing the composition components and proportions shown in Table 3. Using the obtained compositions, the same evaluation tests and measurements as in Examples 3 to 5 were performed. The results are shown in Table 3.

The triglycidyl isocyanurate derivative was obtained by subjecting 586 parts of triglycidyl isocyanurate and 432 parts of bisphenol A to a melt reaction at 150° C. for 2 hours in a nitrogen atmosphere.

[Effects of the Invention] As detailed above, the epoxy resin composition of the present invention has extremely good transparency and heat resistance, as well as excellent storage properties, compared to conventional ones. It has great industrial value, especially for pressure molding.

Claims (1)

Scope of Claims: (a) 100 parts by weight of a mixed epoxy resin consisting of 50 to 80 parts by weight of a bisphenol A epoxy resin having a melting point of 60 to 170°C and 20 to 50 parts by weight of triglycidyl isocyanurate or a derivative thereof (b) Acid anhydride curing agent 30 to 150 parts by weight (c) Imidazole compound, 1,8-diaza-bicyclo(5,4,
0) At least one curing accelerator selected from the group consisting of undecene-7 or a salt thereof and an organic phosphine compound 0.1 to 10 parts by weight (d) Saturated monovalent fatty acid having 16 or more carbon atoms and 18 carbon atoms
An epoxy resin composition comprising 0.5 to 5 parts by weight of at least one compound selected from the group consisting of the above oxyfatty acids.