JPH11140069A - Epoxy resin, production of the epoxy resin, composition containing the epoxy resin, and epoxy resin composition for sealing semiconductor comprising the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new resin capable of reducing a stress without damaging characteristics of the hardened product of the resin such as heat resistance and moisture resistance and useful for a semiconductor sealing mate rial, a molding material, a laminated sheet or the like. SOLUTION: This epoxy resin is the one of formula I [R1 and R2 are each H or CH3 ; R3 to R6 are each H, a 1-10C alkyl or bromine; (n) is a repeating unit of 0-5]. The epoxy resin for formula I is obtained by allowing epichlorohydrin and/or β-methylepichlorohydrin to react with a dihydric phenol- bis(2-hydroxyethyl) ether of formula II. The compound of formula II is obtained by allowing hydroquinone and/or a dihydric hydroquinone derivative having a phenolic hydroxy group or the like to react with ethylene oxide and/or propylene oxide in the presence or absence of the catalyst such as an alkali metal salt at -10 to 300 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel epoxy resin, a method for producing the epoxy resin, a composition containing the epoxy resin, and a semiconductor encapsulant composition comprising the epoxy resin composition comprising the composition. Specifically, low viscosity,
The present invention relates to a novel epoxy resin which gives a cured product having excellent properties such as heat resistance and low stress, a method for producing the same, and an epoxy resin composition. Therefore, the epoxy resin composition using the epoxy resin of the present invention is a semiconductor sealing material, a molding material, a laminate,
Useful for a wide range of applications such as adhesives and paints.

[0002]

2. Description of the Related Art Epoxy resins are widely used in various fields such as electricity, paints, architecture, civil engineering, and adhesion due to their excellent properties. However, in recent years, more specialized and strict characteristics have been required in each field. For example, in the electric / electronic field, a bare chip is sealed using a liquid epoxy resin composition instead of a conventional transfer molding resin such as TAB (tape automated bonding) and COB (chip on board). Attention has been paid to the surface mounting method.

The most widely used conventional liquid sealing resin compositions include liquid or low melting crystalline bisphenol A type and bisphenol F type epoxy resins, as well as epoxy resin curing agents, silica, alumina and the like. There is one in which a low-viscosity resin having an epoxy group is blended as a filler and a reactive diluent.

In particular, with the recent increase in the density and miniaturization of electronic elements, even in the field of liquid sealing materials, better heat resistance, moisture resistance and the like have been demanded. As a method for improving these properties, a filler such as silica is used as in the case of the epoxy resin composition for transfer molding.
There is a method of filling a large amount of. However, when the filler is filled in a large amount, the liquid encapsulant composition has a high viscosity, and there has been a problem that molding defects and fine circuit damage occur.

[0005]

As means for solving this problem, aliphatic epoxy resins such as 1,1 have been used.
Using 6-hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether, or the like as a reactive diluent, to increase the filling of filler by lowering the viscosity of the liquid encapsulant resin composition and to lower the elastic modulus of the cured resin. Although there is a method of preventing package cracks and the like due to so-called reduced stress of a cured resin, a liquid resin composition in which an aliphatic epoxy resin is blended with a bisphenol-type epoxy resin has been used as a reactive diluent when stored for a long period of time. Aliphatic epoxy resins tend to bleed out and become non-uniform compositions, and their cured product properties have fundamental defects such as reduced heat resistance and increased water absorption, which is a practical problem. . In addition, the liquid encapsulant composition using resorcin diglycidyl ether as a reactive diluent is effective in solving the problem that heat resistance is reduced when a reactive diluent is used. It is not enough to reduce the stress. As described above, in the related art, it is extremely difficult to reduce the stress of the cured resin while maintaining heat resistance and moisture resistance.

[0006]

The present invention has been made in view of the above-mentioned circumstances, and as a result of an intensive study for an epoxy resin having low stress without impairing the properties of a cured resin such as heat resistance and moisture resistance, The composition using the epoxy resin represented by the general formula (I) has a low viscosity, and it has been surprisingly found that a cured product of the epoxy resin has heat resistance, moisture resistance and low stress. Since the invention has been completed, an object of the present invention is to provide an epoxy resin represented by the general formula (I) and a method for producing the same. A novel epoxy resin composition characterized by containing an epoxy resin represented by the general formula (I) as the epoxy resin component, and a semiconductor encapsulation comprising the epoxy resin. There is provided a wood composition.

[0007]

Embedded image

In the formula, R ₁ and R ₂ represent H or CH _{3 and} may be the same or different. R _{3 to} R ₆ represent H or a C _{1 to} C ₁₀ alkyl group or bromine and may be the same or different, and n represents a 0 to 5 repeating unit.

That is, the gist of the present invention is a novel epoxy resin represented by the general formula (I).

[0010]

Embedded image In the formula, R _{1 to} R ₆ and n are as described above.

The epoxy resin represented by the general formula (I) of the present invention can be obtained by adding epichlorohydrin and / or epichlorohydrin to divalent phenol-bis (2-hydroxyethyl) ether represented by the following general formula (II). , Β-methylepichlorohydrin.

[0012]

Embedded image In the formula, R ₂ represents H or CH ₃ , and R _{3 to} R ₆ represent H or a C _{1 to} C ₁₀ alkyl group or bromine, and may be the same or different.

The divalent phenol-bis (2-hydroxyethyl) ether represented by the general formula (II) according to the present invention comprises hydroquinone and a hydroquinone derivative having a divalent phenolic hydroxyl group, resorcinol and A resorcinol derivative having a divalent phenolic hydroxyl group, catechol and a catechol derivative having a divalent phenolic hydroxyl group and ethylene oxide and / or propylene oxide in the presence of a catalyst such as an alkali metal salt or in the absence of a catalyst. It can be obtained relatively easily at a temperature of 300 ° C.

Specific examples of the compounds obtained by the above method and applicable to the present invention are listed below, but are not particularly limited thereto. Hydroquinone-bis (2-hydroxyethyl) ether, hydroquinone-bis (2-hydroxypropyl) ether, monomethylhydroquinone-bis (2-hydroxyethyl) ether, monomethylhydroquinone-bis (2-hydroxypropyl) ether, mono-tert- Butyl hydroquinone-bis (2-hydroxyethyl) ether, mono-
tert-butylhydroquinone-bis (2-hydroxypropyl) ether, di-tert-butylhydroquinone-
Bis (2-hydroxyethyl) ether, di-tert-butylhydroquinone-bis (2-hydroxypropyl)
Ether, di-tert-amylhydroquinone-bis (2
Hydroquinones such as -hydroxyethyl) ether, di-tert-amylhydroquinone-bis (2-hydroxypropyl) ether, brominated hydroquinone-bis (2-hydroxyethyl) ether and brominated hydroquinone-bis (2-hydroxypropyl) ether And a hydroquinone derivative having a divalent phenolic hydroxyl group,
as well as,

Resorcin-bis (2-hydroxyethyl) ether, resorcin-bis (2-hydroxypropyl) ether, monomethylresorcin-bis (2-hydroxyethyl) ether, monomethylresorcin-bis (2-hydroxypropyl) ether, mono -Tert-
Butyl resorcin-bis (2-hydroxyethyl) ether, mono-tert-butyl resorcin-bis (2-hydroxypropyl) ether, di-tert-butyl resorcin-bis (2-hydroxyethyl) ether, di-tert
-Butylresorcin-bis (2-hydroxypropyl)
Ether, di-tert-amyl resorcin-bis (2-hydroxyethyl) ether, di-tert-amyl resorcin-bis (2-hydroxypropyl) ether, brominated resorcin-bis (2-hydroxyethyl) ether,
Resorcinol such as brominated resorcinol-bis (2-hydroxypropyl) ether and a resorcinol derivative having a divalent phenolic hydroxyl group, and

Catechol-bis (2-hydroxyethyl) ether, catechol-bis (2-hydroxypropyl) ether, monomethylcatechol-bis (2-hydroxyethyl) ether, monomethylcatechol-bis (2-hydroxypropyl) ether, mono -Tert-
Butyl catechol-bis (2-hydroxyethyl) ether, mono-tert-butyl catechol-bis (2-hydroxypropyl) ether, di-tert-butyl catechol-bis (2-hydroxyethyl) ether, di-tert
-Butylcatechol-bis (2-hydroxypropyl)
Ether, di-tert-amylcatechol-bis (2-hydroxyethyl) ether, di-tert-amylcatechol-bis (2-hydroxypropyl) ether, brominated catechol-bis (2-hydroxyethyl) ether,
Catechol such as brominated catechol-bis (2-hydroxypropyl) ether and catechol derivatives having a divalent phenolic hydroxyl group.

In the general formula (I), n is preferably 5 or less. When n is larger than 5, the viscosity is increased and the heat resistance is decreased, which is not preferable. N in the general formula (I) is an average value 0
To 5, and preferably an average value of 0 to 1 indicates good physical properties. The method of reacting epichlorohydrin with divalent phenol-bis (2-hydroxyethyl) ether in the present invention can be a conventionally known method and is not particularly limited. That is, 1 to 20 mol of epichlorohydrin and / or β-methyl epichlorohydrin is added to 1 mol of hydroxyl group of divalent phenol-bis (2-hydroxyethyl) ether, and alkali metal hydroxide such as sodium hydroxide is added. The reaction can be carried out at 10 to 120 ° C in the presence of a substance. At that time, an aprotic polar solvent, a ketone solvent, an aromatic hydrocarbon solvent or the like may be used. If necessary, quaternary ammonium salts such as tetramethylammonium chloride or Lewis acids such as BF ₃ ether complex may be used. May be used. Further, the reaction can be carried out while removing the water produced by the reaction from the reaction system under reduced pressure or normal pressure.

After the reaction with epichlorohydrin and / or β-methylepichlorohydrin, it is preferable to further carry out a dehydrochlorination reaction. If dehydrochlorination is not performed, hydrolyzable chlorine will increase and adversely affect the properties of the cured product.
The content is preferably 0 ppm or less, more preferably 500 ppm or less. A conventionally known method can be used for the dehydrochlorination reaction, and there is no particular limitation. For example, after reacting with epichlorohydrin, excess epichlorohydrin is removed, and the reaction can be carried out at 10 to 100 ° C. in a hydrophobic solvent in the presence of an aqueous solution of an alkali metal hydroxide such as sodium hydroxide. At that time, an aprotic polar solvent may be used, and if necessary, a catalyst such as a quaternary ammonium salt may be used. The hydrolyzable chlorine in the present invention refers to a potential difference due to silver nitrate obtained by dissolving an epoxy resin in dioxane, adding a 0.1N potassium hydroxide-methanol solution, and heating at 70 ° C. for 30 minutes. This is the value determined by the titration method.

In the present invention, the epoxy resin represented by the general formula (I) may be a divalent phenol represented by the general formula (II) as long as its physical properties such as heat resistance, moisture resistance and low stress are not impaired.
It can be produced by using a compound having two or more hydroxyl groups in addition to ru- (2-hydroxyethyl) ether. Representative compounds having two or more hydroxyl groups include, for example, bisphenols such as bisphenol A, bisphenol F and brominated bisphenol A, novolak resins such as cresol novolak resin and phenol novolak resin, 2,5-ditert-butylhydroquinone,
Polyhydric phenols such as 2,5-di-tert-amylhydroquinone and the like; dialcohols such as 1,6-hexanediol and cyclohexanedimethanol; and polyalcohols such as trimethylolpropane and glycerin. Examples include, but are not limited to, these.

Hereinafter, the epoxy resin composition of the present invention will be described. In the epoxy resin composition of the present invention, the epoxy resin of the present invention can be used alone or in combination with another epoxy resin. When used in combination, the proportion occupied by the epoxy resin of the present invention is preferably at least 2% by weight, particularly preferably at least 5% by weight, of the total epoxy resin. Other epoxy resins that can be used in combination with the epoxy resin of the present invention include bisphenol A, bisphenol F,
Bisphenol type epoxy resins which are diglycidyl ethers such as brominated bisphenol A and bisphenol S,
Or phenol, cresol, bisphenol A,
Polyglycidyl ether of novolak type phenolic resin obtained by condensation reaction of phenols such as naphthol and naphthalene diol with aldehydes and ketones such as formaldehyde and phenols such as phenol, cresol, bisphenol A, naphthol and naphthalene diol and xylyl. Epoxy resin of polyphenolic compounds such as aralkyl-type phenolic resin polyglycidyl ether obtained by condensation reaction with lenglycol, or 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, etc. Polyglycidyl ether of polyhydric phenols, or alicyclic epoxy resin or biphenyl type epoxy resin or glycidylamine epoxy resin or glycidyl ester epoxy Fat and the like but not particularly limited thereto.

Various curing agents can be used in the present invention. For example, diaminodiphenylmethane,
Diamine triamine, triethylene tetramine, isophorone diamine, amine compounds such as polyamidoamine which is a condensate of polyamines with acids such as dimer acid,
Acid anhydride compounds such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, hexahydrophthalic anhydride, phenols such as phenol, cresol, bisphenol A, naphthol and naphthalene diol and aldehydes such as formaldehyde Novolak type phenolic resin obtained by condensation reaction with ketones and
Also, phenolic compounds such as aralkyl-type phenolic resins obtained by condensation reaction of phenols such as phenol, cresol, bisphenol A, naphthol, and naphthalene diol with xylylene glycol, dicyandiamide and derivatives thereof, 2-methylimidazo-
And imidazoles such as 2-ethyl-4-methylimidazole and derivatives thereof, hydrazides such as adipic dihydrazide and isophthalic dihydrazide, and BF ₃ complexes, but are not particularly limited thereto.
These curing agents may be used alone or in combination of two or more. In the resin composition of the present invention, a curing accelerator can be used as needed. For example, various known curing accelerators such as phosphines, imidazoles, tertiary amines, and BF ₃ complexes can be used and are not particularly limited. When a curing accelerator is used, the amount is preferably in the range of 0.01 to 10% by weight based on the epoxy resin.

The resin composition of the present invention can be further blended with other resin or rubber components to exhibit its properties. Thermoplastic resins such as phenolic resin, urea resin, melamine resin, furan resin, diallyl phthalate resin, silicon resin and urethane resin, or thermoplastic resins such as polyester resin, polyamide resin, ABS resin and polyolefin resin It is. Examples of the rubber component include a silicone rubber, a carboxyl group-containing modified nitrile rubber, an amino group-containing modified nitrile rubber, and a styrene-butadiene copolymer, but are not particularly limited thereto.

The resin composition of the present invention can be mixed with various fillers to further exhibit its characteristics.
Metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate and magnesium carbonate, fused silica, crystalline silicium, mica, kaolin, clay, Alternatively, antimony trioxide and the like can be mentioned, but it is not particularly limited thereto. If necessary, a diluent, a colorant, a pigment, a flame retardant, and the like may be added to the resin composition of the present invention. As a method for preparing the resin composition of the present invention, a method of kneading using a commercially available kneader, roll, single-screw or twin-screw extruder at room temperature or under heating is applied.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the following examples, “parts” means “parts by weight” unless otherwise specified, and the viscosity is a value measured at 25 ° C. by a BH-type rotational viscometer (manufactured by Tokimec) unless otherwise specified. . Example 1 A separable flask equipped with a thermometer, a condenser, and an oil-water separation tube was charged with 200 parts of hydroquinone- (2-hydroxyethyl) ether and 1100 epichlorohydrin.
And 110 parts of diethylene glycol dimethyl ether, and the mixture was heated to 65 ° C. and then 99% sodium hydroxide 1
12 parts were charged and reacted at the same temperature with stirring for 6 hours. After completion of the reaction, a part of epichlorohydrin and produced water were recovered under conditions of 110 mmHg and 65 ° C., and the product was filtered with a filter filled with diatomaceous earth to perform solid-liquid separation. Epichlorohydrin and a solvent were recovered from the obtained filtrate under the conditions of 5 mmHg and 170 ° C. to obtain 250 parts of a target resin. The properties of the obtained resin were 172 g / epoxy equivalent.
eq, viscosity 250mPa · s, hydrolyzable chlorine 120p
pm. FIG. 1 shows the analysis data of the gel permeation chromatograph of the resin, FIG. 2 shows the analysis data of the infrared spectroscopic analysis, and FIG. 3 shows the analysis result of the electric field desorption mass spectrometry.

Example 2 200 parts of hydroquinone- (2-hydroxyethyl) ether and 1100 epichlorohydrin were placed in a separable flask equipped with a thermometer, a condenser and an oil-water separator.
And 110 parts of diethylene glycol dimethyl ether, the mixture was heated to 65 ° C., and then 99% sodium hydroxide 9
Five parts were charged and reacted at the same temperature for 6 hours with stirring. After completion of the reaction, a part of epichlorohydrin and produced water were recovered under conditions of 110 mmHg and 65 ° C., and the product was filtered with a filter filled with diatomaceous earth to perform solid-liquid separation. Epichlorohydrin and the solvent were recovered from the obtained filtrate under the conditions of 5 mmHg and 170 ° C., and 350 parts of methyl isobutyl ketone was added to the obtained product to dissolve the product. Thereafter, 30 parts of 10% by weight sodium hydroxide was added, and the mixture was reacted at 85 ° C. for 2 hours, and 200 parts of water was added to dissolve the salts.
After standing, the lower aqueous phase was separated and removed. After neutralization with a phosphoric acid solution, the resin solution was washed with water until the washing solution became neutral, and filtered. Under a condition of 5 mmHg and 170 ° C., methyl isobutyl ketone was removed to obtain 270 parts of a target resin. The properties of the obtained resin were epoxy equivalent 178 g / eq, viscosity 270 mPa · s, and hydrolyzable chlorine 160 ppm.

Examples 3 and 4 and Comparative Examples 1 and 2 The epoxy resin obtained in Example 1 (hereinafter referred to as "epoxy resin A")
And the epoxy resin obtained in Example 2 (hereinafter referred to as “epoxy resin B”) and as Comparative Example 1 resorcin diglycidyl ether Epodil 679 (epoxy equivalent 126 g / e
q, viscosity 420 mPa · s Air Product Co., Ltd.) As Comparative Example 2, polypropylene glycol diglycidyl ether PG-207S (epoxy equivalent 312 g /
eq, a viscosity of 60 mPa · s, manufactured by Toto Kasei Co., Ltd.) were adjusted according to the formulations shown in Table 1, and the mixture was kneaded at 60 ° C. with a hot roll to obtain an epoxy resin composition.
The epoxy resin used as the main component has the same viscosity (2700 c
ps), and the fused silica was blended so as to be 70% by weight based on the total amount of the epoxy resin, the curing agent and the fused silica. Further, as the epoxy resin, a molecular distillation type bisphenol A type epoxy resin YD-
8125 (epoxy equivalent 175 g / eq, viscosity 3900
mPa · s, manufactured by Toto Kasei Co., Ltd.) and a phenol novolak resin BRG-555 (having a hydroxyl equivalent of 104 g /
eq, softening point 66 ° C., manufactured by Showa Polymer Co., Ltd.) triphenylphosphine (manufactured by TPP Wako Pure Chemical Industries, Ltd.) as a curing accelerator, silane coupling agent A-187 (manufactured by Nippon Unicar), fused silica FB as filler -35 (manufactured by Tatsumori) was used.

The obtained resin composition was heated at 120 ° C. for 1 hour,
Next, the test piece was cured at 150 ° C. for 2 hours and further at 180 ° C. for 5 hours to obtain a test piece, and the flexural strength and flexural modulus were measured in accordance with JIS K-6911. In addition, the water absorption was measured at a temperature of 4 mm for a disc-shaped test piece having a diameter of 50 mm and a thickness of 2 mm.
It was determined from the change in weight when treated for 200 hours at 0 ° C. and 85% RH. The glass transition temperature was measured using a thermomechanical measuring device (manufactured by Seiko Denshi) at a heating rate of 5 ° C. /
Minutes. Table 1 also shows the above measurement results.

[0028]

[Table 1]

[0029]

As described in Examples 1 and 2, the novel epoxy resin of the present invention has a low viscosity, and the cured product using the novel epoxy resin of the present invention is clearly shown in Table 1. As described above, it has good heat resistance, low water absorption, and low elasticity, and thus is excellent in reducing stress. Therefore, the epoxy resin composition using the epoxy resin of the present invention is useful for a wide range of applications such as semiconductor encapsulants, molding materials, laminates, adhesives, and paints.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01L 23/31 (72) Inventor Seigo Tawawa 3-17-14 Higashikasai, Edogawa-ku, Tokyo Inside the Tokyo Metropolitan Chemical Research Laboratory

Claims (4)

[Claims] 1. A novel epoxy resin represented by the general formula (I). Embedded image In the formula, R ₁ and R ₂ represent H or CH _{3 and} may be the same or different. R _{3 to} R ₆ represent H or a C _{1 to} C ₁₀ alkyl group or bromine, and may be the same or different;
Represents a repeating unit of 0 to 5. 2. A divalent phenol represented by the following formula (II):
The method for producing an epoxy resin according to claim 1, wherein epichlorohydrin and / or β-methylepichlorohydrin are reacted with ru-bis (2-hydroxyethyl) ether. Embedded image In the formula, R ₂ represents H or CH ₃ , and R _{3 to} R ₆ represent H or a C _{1 to} C ₁₀ alkyl group or bromine, and may be the same or different. 3. An epoxy resin composition comprising an epoxy resin, a curing agent and, if necessary, a curing accelerator, wherein the epoxy resin according to claim 1 is contained as the epoxy resin component. Resin composition. 4. An epoxy resin semiconductor encapsulant composition comprising an epoxy resin composition comprising an epoxy resin, a curing agent and, if necessary, a curing accelerator, wherein the epoxy resin according to claim 1 is used as the epoxy resin component. A novel epoxy resin semiconductor encapsulant composition characterized by being at least 5% by weight of the epoxy resin contained in the composition.