JPH11255867A - Epoxy resin, epoxy resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To decrease the viscosity of or to reduce or clear the solvent contained in an epoxy resin composition and to realize low hygroscopicity of a cured product therefrom by preparing an epoxy resin of low crystallinity despite of low viscosity and employing it as a component of the epoxy resin composition. SOLUTION: A compound represented by the formula (wherein plural R's are independently H, 1-10C alkyl, aryl or allyl and 25-100% of the whole is allyl; i is the actual number of 2-3; and j is the actual number of 3-4) is glycidylated to give an epoxy resin, which is employed as a component material of an epoxy resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating material for electric and electronic parts such as a high-reliability semiconductor encapsulation, and various kinds of materials such as a laminate (printed wiring board) and CFRP (carbon fiber reinforced plastic). The present invention relates to an epoxy resin useful for various adhesives, paints, and the like for composite materials and die bonding pastes, an epoxy resin composition containing the epoxy resin, and a cured product thereof.

[0002]

2. Description of the Related Art Epoxy resins are used in electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesiveness and moisture resistance (water resistance) of the cured product. Widely used in the field. However, in recent years, in the electric and electronic fields, with its development, high purity, low viscosity for high filler filling, heat resistance of cured products,
Further improvements in various properties such as moisture resistance and adhesion are required. In addition, as structural materials and adhesives, materials that are lightweight and have excellent mechanical properties and high adhesiveness in aerospace materials, leisure and sports equipment applications, civil engineering and construction applications, etc. There is a need for a resin that has a low viscosity and, if possible, can be operated without using an organic solvent. In order to meet these demands, liquid epoxy resins such as bisphenol A and bisphenol F are generally used. However, epoxy resins that have lower viscosity and are less likely to crystallize even at low temperatures are required.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an epoxy resin having low viscosity and low crystallinity.

[0004]

That is, the present invention provides (1)
Equation (1)

[0005]

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(Wherein, a plurality of Rs independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an allyl group, and 25 to 100% of the whole is an allyl group. An epoxy resin obtained by glycidylation of a compound represented by the following formula (2):

[0007]

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(Wherein, n represents an average value and is a real number of 0 to 20 and can be measured, for example, by gel permeation chromatography. X is each independently a hydrogen atom or a carbon number of 1 to 4) Represents an alkyl group.
A plurality of Rs are each independently a hydrogen atom,
(1) an alkyl group, an aryl group or an allyl group, wherein 25 to 100% of the total is an allyl group);
(1) The epoxy resin according to (1) or (2), wherein 5% is an allyl group; (4) The compound of formula (1) wherein two kinds of diallylhydroquinones which are substituted isomers are mixed and used as the compound of the formula (1). The epoxy resin according to any one of (2) and (3). (5) The epoxy resin according to any one of (1), (2) and (3), wherein two kinds of diallyl resorcinols which are substituted isomers are mixed and used as the compound of the formula (1), (6) The epoxy resin according to any one of the above (1), (2), (3), (4) and (5), which is liquid at ordinary temperature, (7) the (1),
(2) An epoxy resin composition comprising the epoxy resin according to any one of (3), (4), (5) and (6), (8) for semiconductor encapsulation. The prepared epoxy resin composition of (7), (9) the epoxy resin composition of (7) prepared for a die bonding paste, (10) the (7), (8) and (9) A) a cured product obtained by curing the epoxy resin composition according to any one of the above items.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin of the present invention can be obtained by reacting a compound represented by the above formula (1) with epihalohydrins (glycidylation reaction). The compound of the formula (1) can be obtained by reacting various polyhydroxybenzenes with allyl halide, subjecting to allyl etherification, and then subjecting the allyl group to Claisen rearrangement. The raw material polyhydroxybenzenes and monoallylpolyhydroxybenzenes, It is a diallyl polyhydroxybenzene, a triallyl polyhydroxybenzene, or a tetraallyl polyhydroxybenzene, alone or in a mixture, wherein allyl groups in all Rs are 25 to 100% on average. Examples of the above polyhydroxybenzenes include hydroquinone, resorcin, catechol, methylhydroquinone, tert-butylhydroquinone, t
tert-amylhydroquinone, tert-hexylhydroquinone, tert-octylhydroquinone, phenylhydroquinone, 2,5-dimethylhydroquinone, 2,3
-Dimethylhydroquinone, trimethylhydroquinone,
2,6-dimethylhydroquinone, 2-isopropylhydroquinone, 2-ethyl-5-methylhydroquinone, 2-
Methyl-5-isopropylhydroquinone, 2,5-di-
n-propylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-tert-amylhydroquinone, 2,5-tert-hexylhydroquinone, 2,
5-di-tert-octylhydroquinone, 2,5-dinonylhydroquinone, 2-methylresorcin, 2-isopropylresorcin, 2-tert-butylresorcin, 2-tert-amylresorcin, 2-tert-
Hexyl resorcinol, 2-tert-octyl resorcinol, 2-nonyl resorcinol, 2-cyclohexyl resorcinol, 2- (2-phenylisopropyl) resorcinol,
2,5-dimethylresorcinol, phloroglucinol,
Examples thereof include 1,2,4-benzenetriol and pyrogallol, but are not limited thereto. When diallyl hydroquinone or diallyl resorcinol is used as the polyhydroxybenzene, it is preferable to use a mixture of two compounds each of which is a substituted isomer. Further, as the compound of the formula (2), not only a compound obtained by allylating polyhydroxybenzenes alone as described above, but also a compound obtained by allylating two or more kinds in the same system may be used. Two or more allylated compounds may be used as a mixture.

Specific examples of the epihalohydrins that can be used in the glycidylation reaction include epichlorohydrin, β-methylepichlorohydrin, epibromhydrin, β-methylepibromohydrin, epiiodohydrin, β-ethylepichlorohydrin and the like. But
Epichlorohydrin or epibromohydrin, which is industrially available and inexpensive, is preferred.

The reaction is carried out, for example, by reacting a mixture of the compound of the formula (1) and epihalohydrins with sodium hydroxide as a catalyst,
While adding the solid of alkali metal hydroxide such as potassium hydroxide all at once or gradually adding the solid, the solution is added at 0.2 to 120 ° C. at 0.degree.
Incubate for 5 to 10 hours. At this time, an aqueous solution of the alkali metal hydroxide may be used. In such a case, the alkali metal hydroxide is continuously added, and water and epihalohydrin are continuously added to the reaction mixture under reduced pressure or normal pressure. A method may be employed in which the water is removed by distilling the water and then separating the water, and the epihalohydrin is continuously returned to the reaction mixture (the solid alkali metal hydroxide may be dehydrated under reduced pressure). When an epoxy resin having a low total halogen content is obtained, it is preferable to gradually add an alkali metal hydroxide and keep the temperature in the reaction system at 20 to 50 ° C. The water content in the reaction system is 0.1% with respect to epihalohydrin.
It is preferable to keep it at 5 to 10% by weight. When the content is 0.5% by weight or less, the reaction hardly proceeds, and when the content is 10% by weight or more, the total halogen content tends to increase.

In the above reaction, the amount of the epihalohydrin used is usually from 1.0 to 20 mol, preferably from 2.0 to 15 mol, more preferably from 3. to 20 mol of the hydroxyl group of the compound of the formula (1).
0 to 10 mol. The amount of the alkali metal hydroxide to be used is generally 0.5 to 1 equivalent of the hydroxyl group of the compound of the formula (1).
1.5 mol, preferably 0.7 to 1.2 mol.

It is particularly preferable that the compound of the formula (1) has an allyl group substituted at the ortho position of the hydroxyl group.
In this case, the reactivity between the hydroxyl group and epihalohydrin is poor as compared with the hydroxyl groups of ordinary phenols and cresols. Accordingly, the reaction is preferably carried out using an aprotic polar solvent or a solvent having a catalytic ability such as alcohols.
Specific examples of the aprotic polar solvent that can be used include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone,
1,4-dioxane and the like can be mentioned. The amount of the aprotic polar solvent used is usually 5 to the weight of the epihalohydrin.
It is from 200 to 200% by weight, preferably from 10 to 150% by weight. Specific examples of alcohols that can be used include methanol, ethanol, and the like. The amount of the alcohol used is usually 5 to 100% by weight, preferably 5 to 50% by weight, based on the weight of the epihalohydrin. The use of alcohols facilitates the reaction, and the total halogen content is higher than when an aprotic polar solvent is used, but lower than when these solvents are not used.

In the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride can be used as a catalyst. In this case, the amount of the quaternary ammonium salt used is usually 0.001 to 1 equivalent of the hydroxyl group of the compound of the formula (1).
To 0.2 mol, preferably 0.05 to 0.1 mol. These may be used in combination with the above solvents.

[0015] Usually, these reaction products are washed with water or without water, and the excess epihalohydrins,
After removing the used solvent and the like, the mixture is dissolved in a solvent such as toluene, methyl isobutyl ketone, and methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added thereto, and the whole reaction is performed again. An epoxy resin having a low halogen content can be obtained. In this case, the amount of the alkali metal hydroxide used is expressed by the formula (1)
0.01 to 0.2 relative to 1 equivalent of hydroxyl group of the compound
Mole, preferably 0.05 to 0.15 mole. The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2
Time. After the completion of the reaction, salts produced as by-products are removed by filtration, washing with water, and the like, and the solvent such as toluene, methyl isobutyl ketone, and methyl ethyl ketone is distilled off under reduced pressure under heating to obtain the epoxy resin of the present invention.

Next, 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 at an arbitrary ratio. In addition, since the epoxy resin of the present invention can have a very low viscosity, it can be used as a reactive diluent, so that the range of the use ratio with other epoxy resins is not particularly limited. .

Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention include bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes. With phenols and various diene compounds, polycondensates with phenols and aromatic dimethylol,
Biphenols, glycidyl ether-based epoxy resin obtained by glycidylation of alcohols, alicyclic epoxy resin, glycidylamine-based epoxy resin, glycidyl ester-based epoxy resin, brominated epoxy resin, and the like, but are not limited thereto. They may be used alone or in combination of two or more.

In a preferred embodiment of the epoxy resin composition of the present invention, a curing agent is contained. As a curing agent, amine compounds, acid anhydride compounds, amide compounds,
Phenol compounds and the like can be used. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, and trianhydride. Mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, or bisphenols, phenols (phenol, alkyl Polycondensates of substituted phenols, naphthols, alkyl-substituted naphthols, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes, phenols and various diene compounds , Polycondensates of phenols and aromatic dimethylols, biphenols and modified products thereof, polyhydric phenol compounds such as compounds of the formula (1) and allylated phenols, imidazole, BF3 -Amine complexes, guanidine derivatives, compounds having a maleimide group, compounds having a cyanate ester group, and the like. In particular, when used in the field of electronics and electricity, phenol-based and acid anhydride-based curing agents are preferred. The amount of the curing agent used is usually 0.1 to 1 equivalent of the epoxy group of the epoxy resin.
It is 5 to 1.5 equivalents, preferably 0.6 to 1.2 equivalents. If the amount is less than 0.5 equivalents or more than 1.5 equivalents with respect to 1 equivalent of the epoxy group, curing may be incomplete and good cured physical properties may not be obtained.

When the above curing agent is used, a curing accelerator may be used in combination. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol,
1,8-diaza-bicyclo (5,4,0) undecene-
Tertiary amines such as 7, phosphines such as triphenylphosphine, and organometallic compounds such as tin octylate, zinc naphthenate and cobalt naphthenate.
The curing accelerator is 0.0 to 100 parts by weight of the epoxy resin.
1 to 15 parts by weight is used as needed. Further, the epoxy resin composition of the present invention may contain various compounding agents such as fillers such as silica, alumina, talc, and silver powder, silane coupling agents, release agents, and pigments, if necessary. it can.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components at a predetermined ratio.
The epoxy resin composition of the present invention is preferably used for semiconductor encapsulation or for die bonding paste.
The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin of the present invention, preferably a curing agent, and, if necessary, a curing accelerator, a filler, and a compounding agent are sufficiently mixed by using an extruder, a kneader, or the like, if necessary, until the mixture becomes uniform. The epoxy resin composition of the present invention is obtained, and the epoxy resin composition is molded by a (melt) casting method, a transfer molding method, an injection molding method, a compression molding method, or the like. .00
By heating for 1 to 20 hours, the cured product of the present invention can be obtained. Room temperature curing is also possible if the activity of the curing agent and the curing accelerator is high.

If necessary, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone to obtain glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper. The cured product of the present invention can be obtained by hot press molding a prepreg obtained by impregnating a substrate such as the above and heating and drying.

[0022]

The present invention will be described in more detail with reference to the following examples. Note that the present invention is not limited to these examples. In addition, the measurement of the physical property value was performed by the following method.・ Epoxy equivalent Value measured by a method according to JIS K-7236 ・ Viscosity E-type rotational viscometer (25 ° C.)

Example 1 <Synthesis of allylated polyhydroxybenzenes> 55 parts by weight of hydroquinone and 330 parts by weight of isopropanol were charged into a reaction vessel, stirred and dissolved, and sodium hydroxide 41
Parts by weight were added and stirring continued. Next, 40
100 g of allyl chloride was added dropwise over 1 hour while maintaining the temperature at 0 ° C, and the reaction was carried out at 40 ° C for 1 hour and at 70 ° C for 5 hours. After completion of the reaction, by-produced sodium chloride was removed by filtration, isopropanol was distilled off from the reaction solution under heating and reduced pressure, and 200 parts by weight of methyl isobutyl ketone (MIBK, hereinafter the same) was added to the residue and dissolved. After washing the MIBK solution several times with water, the MIBK was distilled off under reduced pressure under heating to obtain a crude allyl etherified hydroquinone, and further, molecular distillation was performed to obtain 61 parts by weight of purified allyl etherified hydroquinone at room temperature. . This allyl etherified hydroquinone was charged into a reaction vessel and subjected to a transfer reaction at 190 ° C. for 10 hours under a nitrogen atmosphere to obtain an allylated hydroquinone. This allylated hydroquinone is a crystalline solid at room temperature,
2,3-diallylhydroquinone and 2,5-diallylhydroquinone were the main components. <Synthesis of Epoxy Resin> Allylated hydroquinone 5
7 parts by weight, epichlorohydrin (ECH, hereinafter the same) 5
55 parts by weight and 280 parts by weight of dimethyl sulfoxide (DMSO, the same applies hereinafter) are charged into a reaction vessel, heated, stirred, dissolved, and then maintained at 45 ° C. while maintaining the inside of the reaction system at 45 Torr. 63 parts by weight to 4
It was dropped continuously over time. At this time, the ECH and water distilled off by azeotropic distillation are cooled and separated, and the organic layer E
The reaction was performed while returning only CH into the reaction system. After the completion of the dropwise addition of the aqueous sodium hydroxide solution, the reaction was further continued under reduced pressure at 45 ° C. for 2 hours and at 70 ° C. for 60 minutes. Subsequently, washing with water was repeated to remove the produced salt and DMSO, and then excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 200 parts by weight of MIBK was added to the residue and dissolved. Further, the MIBK solution was heated to 70 ° C.
After adding 6 parts by weight of a 2% aqueous sodium hydroxide solution and reacting for 2 hours, washing with water was repeated until the washing liquid of the solution became neutral. Subsequently, MIBK was distilled off from the oil layer under reduced pressure under heating, and the residue was subjected to molecular distillation under reduced pressure under heating to obtain 54 parts by weight of the epoxy resin (E1) of the present invention. The epoxy equivalent of the obtained epoxy resin (E1) is 1
53, viscosity was 75 centipoise.

Example 2 <Synthesis of Allylated Polyhydroxybenzenes> Example 1
In the above, the same operation was carried out except that hydroquinone was replaced by 55 parts by weight of resorcinol and sodium hydroxide by 50 parts by weight. As a result, purified allyl etherified resorcinol which was liquid at room temperature was obtained. This allyl etherified resorcinol was charged into a reaction vessel, and heated at 190 ° C. under a nitrogen atmosphere.
Allylated resorcinol was obtained by performing a transfer reaction for 4 hours. This allylated hydroquinone is liquid at room temperature,
The main components were 2,4-diallyl resorcin and 4,6-diallyl resorcin. <Synthesis of Epoxy Resin> The same operation was carried out in Example 1 except that the allylated hydroquinone was replaced with 57 parts by weight of the above-mentioned allylated resorcinol to obtain 52 parts by weight of the epoxy resin (E2) of the present invention. The obtained epoxy resin (E2) had an epoxy equivalent of 155 and a viscosity of 85 centipoise.

Comparative Example 1 The procedure of Example 1 was repeated except that allylated hydroquinone was added to 33 parts by weight of hydroquinone to obtain 63 parts by weight of an epoxy resin (R1). The epoxy equivalent of the obtained epoxy resin (R1) is 1
23. A crystalline solid having a melting point of 103 ° C.

Comparative Example 2 An epoxy resin (R) was prepared in the same manner as in Comparative Example 1 except that hydroquinone was changed to 33 parts by weight of resorcinol.
2) 64 parts by weight were obtained. The obtained epoxy resin (R2)
Had an epoxy equivalent of 120 and a viscosity of 500 centipoise.

Comparative Example 3 Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.) (R
When the physical properties of 3) were measured, the epoxy equivalent was 185,
The viscosity was 12000 centipoise.

Examples 3 to 4, Comparative Examples 4 to 6 Epoxy resins (E1) to (E1) obtained in Examples 1 and 2
2) and the epoxy resin (R1) obtained in Comparative Examples 1 to 3
To (R3), 0.9 mol of methyltetrahydrophthalic anhydride was added as a curing agent to 1 equivalent of the epoxy group of these epoxy resins, and a curing accelerator (2-ethyl-4-methylimidazole) was further added. One part by weight per 100 parts by weight of the epoxy resin was quickly melt-mixed on a hot plate, poured into a mold, and cured in an oven at 80 ° C. for 2 hours, 120 ° C. for 2 hours, and 180 ° C. for 4 hours. .

The results of measuring the physical properties of the cured product thus obtained are shown in Table 1. In addition, the measurement of the physical property value was performed by the following method. -Glass transition temperature (TMA): TM-7000, manufactured by Vacuum Riko Co., Ltd. Rate of temperature rise 2 ° C / mjn · Water absorption: A disk-shaped test piece having a diameter of 5 cm and a thickness of 4 mm was boiled in water at 100 ° C for 24 hours. Weight increase after (%)

[0030]

Table 1 Example Comparative Example 3 4 4 5 6 Epoxy resin E1 E2 R1 R2 R3 Glass transition temperature (° C) 158 153 163 159 167 167 Water absorption (%) 1.2 1.2 1.5 1.4 1.2

As is apparent from Table 1, the epoxy resin of the present invention does not impair the cured physical properties of an epoxy resin having a similar structure and not being allylated.

[0032]

As described above, the epoxy resin of the present invention has a low viscosity and extremely low crystallinity at a low temperature, so that it can be used not only as a base resin in an epoxy resin composition but also as a reactive diluent. it can. for that reason,
By using this epoxy resin, it becomes possible to make the epoxy resin composition low in solvent, no solvent, low in viscosity, and highly filled with filler, and workability is also improved. Therefore, the epoxy resin composition of the present invention is used for electric / electronic parts, paints,
It is useful for various objects such as adhesives, civil engineering and architectural applications, but is extremely useful especially for electrical and electronic component-related applications.

Claims (10)

[Claims] (1) Formula (1) (Wherein, a plurality of Rs are each independently a hydrogen atom,
It represents an alkyl group, an aryl group or an allyl group having 1 to 10 carbon atoms, and 25 to 100% of the whole is an allyl group. i
Is a real number of 2 to 3, and j is a real number of 3 to 4). (2) Formula (2) (Where n represents an average value and is a real number from 0 to 20. X
Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A plurality of Rs each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an allyl group, and 25 to 100% of the whole is an allyl group). Epoxy resin. 3. The epoxy resin according to claim 1, wherein 40 to 75% of R is an allyl group. 4. The epoxy resin according to claim 1, wherein the compound of formula (1) is a mixture of two kinds of diallyl hydroquinones which are substituted isomers. 5. The epoxy resin according to claim 1, wherein the compound of formula (1) is a mixture of two kinds of diallyl resorcin which are substituted isomers. 6. The epoxy resin according to claim 1, which is in a liquid state at normal temperature. 7. An epoxy resin composition comprising the epoxy resin according to any one of claims 1, 2, 3, 4, 5, and 6. 8. The epoxy resin composition according to claim 7, which is prepared for encapsulating a semiconductor. 9. The epoxy resin composition according to claim 7, which is prepared for a die bonding paste. 10. A cured product obtained by curing the epoxy resin composition according to any one of claims 7, 8 and 9.