JPH11147929A - Epoxy resin, method for producing epoxy resin, epoxy resin composition and cured product thereof - Google Patents

Abstract

(57) [Problem] To provide an epoxy resin having low viscosity, low crystallinity and low mutagenicity. In addition, an epoxy resin composition containing the same is obtained, and in a cured product, low moisture absorption and high adhesion are realized, which is particularly useful for applications such as a semiconductor sealing material and a die bonding paste. SOLUTION: Formula (1) (Where n represents an average value and is a real number from 0 to 1. X
Are each independently a single bond, a hydrocarbon group having 1 to 7 carbon atoms, or a sulfur atom, an oxygen atom, -SO-, -SO
_{2 -, - CO -, -} CO 2 - or -Si (CH _{3) 2}
Indicates-. Y 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 6 carbon atoms, an aryl group, or an allyl group, and 26 to 50% of the whole is an allyl group. )) To produce an epoxy resin having a low halogen concentration, which is used as a constituent material of the 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 such as a composite material and a die bonding paste, and a paint, a method for producing the epoxy resin, 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.

[0003]

However, in recent years, in the electric and electronic fields, with the development thereof, high purity, low viscosity for high filling of filler, heat resistance of cured product, moisture resistance, adhesion, etc. There is a demand for further improvement of the various characteristics.
In addition, as a structural material, a resin that is lightweight and has excellent mechanical properties in aerospace materials, leisure and sports equipment applications, and the like, and at the same time, a low-viscosity resin is required to improve workability. In order to meet these demands, liquid epoxy resins such as bisphenol A and bisphenol F are generally used. However, crystallization at a low temperature, mutagenicity for living organisms has recently become a problem, There are considerations such as the need to increase the viscosity. .

[0004]

DISCLOSURE OF THE INVENTION The present inventors have developed an epoxy resin and an epoxy resin composition having low viscosity but low crystallinity and low mutagenicity (negative in the Ames test), and having low water absorption and high adhesion. As a result of intensive studies on the cured product of the present invention, the present invention was completed. That is, the present invention provides the following equation (1):

[0005]

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(Where n represents an average value and is a real number of 0 to 1, preferably a real number of 0 to 0.2. X
Are each independently a single bond, a hydrocarbon group, or a sulfur atom 1 to 7 carbon atoms, an oxygen _{atom, -SO -, - SO 2 -} ,
—CO—, —CO ₂ —, or —Si (CH ₃ ) ₂ — is shown. Y is each independently a hydrogen atom or a carbon atom
And represents alkyl groups 4 to 4. A plurality of Rs each independently represent a hydrogen atom, an alkyl or aryl group having 1 to 6 carbon atoms, or an allyl group, and 26 to 50% of the whole is an allyl group. (2) the epoxy resin according to the above (1), wherein the total halogen content is 0.000023 mol / g or less, (3) the following formula (2):

[0007]

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Wherein X and R have the same meanings as in formula (1) and epihalohydrins are glycidylated in an aprotic polar solvent in the presence of a catalyst. Epoxy resin manufacturing method,
(4) The production method according to the above (3), wherein the catalyst is an alkali metal hydroxide, and the inside of the reaction system is maintained at 20 to 50 ° C. at the time of the addition. The process according to the above (3) or (4), wherein the content of the epihalohydrin is within the range of 0.5 to 10% by weight. .
(6) It contains the epoxy resin of the above (1) or (2) and / or the epoxy resin obtained by the production method according to any one of the above (3), (4) and (5). (7) an epoxy resin composition according to the above (6), which contains an ordinary temperature liquid polyhydric phenol compound having an allyl group as a curing agent; (6) The epoxy resin composition of (6) or (7), which is prepared for use in a die bonding paste, and (9) the epoxy resin composition of (6) or (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 (6), (7), (8) and (9).

The epoxy resin of the present invention has the following formula (2)

[0010]

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(Where X and R have the same meanings as in formula (1)) and an epihalohydrin can be reacted (epoxidation reaction). The compound of the formula (2) can be obtained by reacting various bisphenols with allyl halide, subjecting them to allyl etherification, and then subjecting the allyl group to Claisen rearrangement. Bisphenols,
Tetraallyl bisphenols are used alone or as a mixture, and the average value of R is 26 to 50%. Examples of the bisphenols include bisphenol A, bisphenol F, bisphenol AD, biphenol, cyclohexylidenebisphenol, bisphenol S, bis (4-hydroxyphenyl) sulfide,
Bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) methanone, 4,4 ′-(dimethylsilylene) bisphenol, 4,4′-oxybisphenol and the like can be mentioned. As the compound of the formula (2), not only a compound obtained by allylating bisphenols alone as described above but also a compound obtained by allylating two or more kinds in the same system may be used. These compounds may be used as a mixture of two or more.

Specific examples of the epihalohydrins that can be used in the epoxidation reaction include epichlorohydrin, β-methylepichlorohydrin, epibromohydrin, β-methylepibromohydrin, epiiodohydrin, and β-ethylepichlorohydrin. However, epichlorohydrin or epibromohydrin which is easily available industrially and is inexpensive is preferable.

The epoxidation reaction is carried out, for example, by adding sodium hydroxide to a mixture of a compound of the formula (2) and epihalohydrins.
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. May be further distilled off, water may be removed, and epihalohydrins may be continuously returned to the reaction mixture (when using a solid alkali metal hydroxide, dehydration may be carried out under reduced pressure). To obtain a low total halogen epoxy resin,
It is preferable that the alkali metal hydroxide is gradually added and the temperature in the reaction system is kept at 20 to 50 ° C. The water in the reaction system is preferably 0.5 to 10 with respect to epihalohydrin.
It is preferred to keep the 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 per 1 equivalent of the hydroxyl group of the compound of the formula (2) increases as the number of repeating units decreases and the viscosity becomes lower. 1.0-20 mol, preferably 2.0-15 mol, more preferably 3.0-1 mol
0 mol. The amount of the alkali metal hydroxide to be used is generally 0.5 to 1 to 1 equivalent of the hydroxyl group of the compound of the formula (2).
It is 5 mol, preferably 0.7 to 1.2 mol.

Further, as the formula (2), a compound in which an allyl group is substituted at the ortho position of a hydroxyl group is preferable. In this case, the reactivity between the hydroxyl group and epihalohydrin is poor as compared with the hydroxyl groups of ordinary phenols and cresols. Therefore, the reaction is preferably performed using a solvent having a catalytic ability, such as an aprotic polar solvent or an alcohol. Specific examples of the aprotic polar solvent that can be used include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone,
4-dioxane and the like. The amount of the aprotic polar solvent used is usually 5 to 2 with respect to the weight of the epihalohydrin.
00% by weight, preferably 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 particular, when the epoxy resin of the present invention is used for electronic and electric parts such as semiconductors, the total halogen content is preferably 0.00000.
It is preferably at most 23 mol / g, and in order to obtain such an epoxy resin, it is preferable to use an aprotic polar solvent for production.

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 (2).
To 0.2 mol, preferably 0.05 to 0.1 mol. These may be used in combination with the above solvents.

In general, these reaction products are used after washing with or without washing with water, and 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 given by the formula (2)
Is 0.01 to 0.2 mol, preferably 0.05 to 0.15 mol, per 1 equivalent of the hydroxyl group of the compound of the formula (1). The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours. 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 and methyl isobutyl ketone is distilled off under reduced pressure under heating to obtain the epoxy resin of the present invention.

The epoxy resin of the present invention thus obtained has a total halogen content of usually 0.00005 mol
/ G or less, 0.000 / g obtained under preferable conditions.
023 mol / g or less. The total halogen content is
1N-KOH in butyl carbitol solution of epoxy resin
The amount (mol) of halogen released by adding a propylene glycol solution and refluxing for 10 minutes is measured by a silver nitrate titration method, and is a value obtained by dividing by the weight of the epoxy resin.

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. When used together, the proportion of the epoxy resin of the present invention in the total epoxy resin is 30% by weight.
More preferably, it is more preferably 40% by weight or more.

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 glycidylated alcohols, etc., alicyclic epoxy resin, glycidylamine-based epoxy resin, glycidyl ester-based epoxy resin brominated epoxy resin and the like, but are not limited thereto , Preferably those having low mutagenicity. These may be used alone,
More than one species may be used.

[0021] 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, bisphenols, phenols (phenol, alkyl substitution Polycondensates of phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes, polymerization of phenols with various diene compounds , Polycondensates of phenols with aromatic dimethylol, biphenols and modified products thereof, allylated compound and the phenol compound of formula (2), imidazo - Le, BF ₃ - amine complex, guanidine derivatives Among them, compounds having low mutagenicity are more preferable.
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 to be used is usually 0.5 to 1 to 1 equivalent of the epoxy group of the epoxy resin.
It is 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. In particular, when used for semiconductor encapsulation or die bonding paste, use of a polyhydric phenol compound having an allyl group and being liquid at room temperature is preferable in terms of viscosity, storage stability and adhesion of the cured product of the composition. It is preferable from the viewpoints of properties and low hygroscopicity.

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 metal compounds such as tin octylate. The hardening accelerator is used in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the epoxy resin as required. 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. Although it is possible, substances with high mutagenicity such as antimony trioxide are preferably not mixed. .

The epoxy resin composition of the present invention is obtained by uniformly mixing the above components at a predetermined ratio, and is preferably used for sealing a semiconductor or for a 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 and preferably a curing agent, and if necessary a curing accelerator, a filler,
And an excipient, if necessary, by using an extruder, a kneader or the like, and sufficiently mixed until uniformity is obtained to obtain the epoxy resin composition of the present invention. Transfer molding method and injection molding method,
Molded by compression molding, etc., 80 to 20 if necessary
The cured product of the present invention can be obtained by heating at 0 ° C. for 0.001 to 20 hours.

Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like, and is used to prepare glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. The prepreg obtained by impregnating the substrate with heat and drying can be subjected to hot press molding to obtain the cured product of the present invention.

In this case, the solvent is used in such an amount that the solvent accounts for usually 10 to 70% by weight, preferably 15 to 65% by weight, based on the total weight of the epoxy resin composition of the present invention and the solvent.

[0026]

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.

The measurement of the physical properties of the epoxy resins in the following Examples and Comparative Examples was performed by the following methods. Total chlorine amount A value obtained by adding a 1N-KOH propylene glycol solution to a butyl carbitol solution of a sample and refluxing for 10 minutes to measure a chlorine amount (mol) released by a silver nitrate titration method and dividing by a weight of the sample. Epoxy equivalent Value measured by a method according to JIS K-7236, unit is g / eq.Viscosity E-type rotational viscometer (25 ° C)

Embodiment 1 Equation (3)

[0029]

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(Wherein R represents a hydrogen atom or an allyl group, and 37.5% is an allyl group)
74 parts by weight, epichlorohydrin (ECH, hereinafter the same)
650 parts by weight and 400 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.
, And 105 parts by weight of a 40% aqueous sodium hydroxide solution was continuously added dropwise over 4 hours. At this time, after cooling and separating the ECH and water distilled off by azeotropic distillation, the reaction was performed while returning only the organic layer, ECH, into the reaction system. After the completion of the aqueous sodium hydroxide solution, 45
The reaction was further carried out at 70 ° C. for 2 hours and at 70 ° C. for 30 minutes. Then, washing with water was repeated to remove generated salts and DMSO, and then excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 500 parts by weight of methyl isobutyl ketone (MIBK, hereinafter the same) was added to the residue and dissolved. Further, the MIBK solution was heated to 70 ° C., 15 parts by weight of a 30% aqueous sodium hydroxide solution was added, and the mixture was allowed to react for 2 hours. Then, water washing was repeated until the washing liquid of the solution became neutral. Then, MIBK was distilled off from the oil layer under heating and reduced pressure to obtain 214 parts by weight of the epoxy resin (E1) of the present invention. The epoxy equivalent of the obtained epoxy resin (E1) is 2
47, viscosity 27 poise, total chlorine amount 0.000017
mol / g.

Comparative Example 1 A compound of the formula (3) was prepared in the same manner as in Example 1 except that 1 part by weight of tetramethylammonium chloride (hereinafter referred to as TMAC) was added to 114 parts by weight of bisphenol A instead of using DMSO. As a result of the operation, 160 parts by weight of the epoxy resin (R1) was obtained. The obtained epoxy resin (R1) had an epoxy equivalent of 173, a viscosity of 80 poise, and a total chlorine amount of 0.00003 mol / g.

Example 2, Comparative Example 2 The epoxy resin (E1) of Example 1 and the epoxy resin (R1) of Comparative Example 1 were used, and a phenol novolak resin was used as a curing agent for one equivalent of the epoxy group of these epoxy resins. (ICI of 0.1 poise at 150 ° C., softening point of 62 ° C., hydroxyl equivalent of 105 g / eq) (hereinafter PN) and 1 hydroxyl equivalent, and a curing accelerator (triphenylphosphine) in an amount of 100 parts by weight of epoxy resin One part by weight was quickly melt-mixed on a hot plate, poured into a mold and cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.

The results of measuring the physical properties of the cured product thus obtained are shown in Table 1 in the column of physical properties of the cured product. In addition, the measurement of the physical property value was performed by the following method.・ Copper foil peel strength: 180 ° C. peel test Measurement temperature; 30 ° C. Pulling speed: 200 mm / min Copper foil; JTC foil manufactured by Nikko Gould Co., Ltd. Thickness: 70 μm Was humidified at 85 ° C and 85% RH for 24 hours before and after humidification (%).

[0034]

[Table 1]

[0035]

The epoxy resin of the present invention has low viscosity, very low crystallinity at low temperature, and low mutagenicity.
Further, the cured product of the epoxy resin composition of the present invention is excellent in adhesiveness and low hygroscopicity. Further, the epoxy resin composition of the present invention using the epoxy resin of the present invention having a small total halogen content obtained by the production method of the present invention is extremely excellent in workability in electronic and electric fields such as semiconductors. ,
And high reliability can be ensured.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 23/31

Claims (10)

[Claims] (1) Formula (1) (Where n represents an average value and is a real number from 0 to 1. X
Are each independently a single bond, a hydrocarbon group, or a sulfur atom 1 to 7 carbon atoms, an oxygen _{atom, -SO -, - SO 2 -} ,
-CO -, - CO ₂ - or -Si (CH _{3) 2} - shows a. Y is each independently a hydrogen atom or carbon number 1 to
4 represents an alkyl group. A plurality of Rs each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or an allyl group, and 26 to 50% of the whole is an allyl group. Epoxy resin represented by). 2. The total halogen content is 0.000023 mol /
The epoxy resin according to claim 1, which is not more than g. (3) The following formula (2): (Wherein X and R have the same meanings as in formula (1)) and an epoxy characterized by glycidylation of epihalohydrins in an aprotic polar solvent in the presence of a catalyst. Method of manufacturing resin. 4. The process according to claim 3, wherein the catalyst is an alkali metal hydroxide, and the reaction system is maintained at 20 to 50 ° C. during the addition. 5. The process according to claim 3, wherein the water content in the reaction system is within the range of 0.5 to 10% by weight of the epihalohydrins. 6. An epoxy resin comprising the epoxy resin according to claim 1 or 2 and / or the epoxy resin obtained by the production method according to any one of claims 3, 4 and 5. Composition. 7. The epoxy resin composition according to claim 6, which contains a normal temperature liquid polyhydric phenol compound having an allyl group as a curing agent. 8. The epoxy resin composition according to claim 6, which is prepared for encapsulating a semiconductor. 9. The epoxy resin composition according to claim 6, 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 6, 7, 8 and 9.