JPH11140163A - Epoxy resin, epoxy resin production, epoxy resin composition, and cured article prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin which has a low viscosity, a low low-temp. crystallinity, and low mutagenic properties by glycidylating a specific compd. with an epihalohydrin in the presence of a catalyst in an aprotic polar solvent. SOLUTION: A compd. of formula I [wherein X is a single bond, a 1-7C hydrocarbon group, S, O, SO, SO2 , CO, CO2 , or Si(CH3 )2 ; and R is H, 1-6C alkyl, aryl, or allyl provided 13-25% of total R's are allyl] is glycidylated with an epihalohydrin in an amt. of 1.0-20 mol, pref. 2.0-15 mol, still pref. 3.0-10 mol, based on 1 equivalent of hydroxyl group of the above compd. in the presence of an alkali metal hydroxide catalyst in an amt. of 0.5-1.5 mol based on 1 equivalent of hydroxyl group of the above compd. in an aprotic polar solvent in an amt. of 5-200 wt.% of the epihalohydrin at 20-120 deg.C for 0.5-10 hr, thus giving an epoxy resin of formula II (wherein (n) is a mean number, being 0-1; and Y is H or 1-4C alkyl).

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]

Embedded image

(Wherein, n represents an average value and is a real number of 0 to 1. X is each independently a single bond, 1 to 7 carbon atoms.
A hydrocarbon group or a sulfur atom, an oxygen atom, -SO-,-
SO ₂ —, —CO—, —CO ₂ — or —Si (C
H ₃ ) _2- . Y each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Multiple R
Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or an allyl group;
5% are allyl groups. ) Epoxy resin,
(2) In the formula (1), the epoxy resin of the above (1), wherein X is a hydrocarbon group having 1 to 2 carbon atoms, (3) the above (1), wherein the total halogen content is 0.000023 mol / g or less.
Or (2) an epoxy resin, (4) the following formula (2)

Embedded image

(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 an alkali metal hydroxide. And (5) adding an alkali metal hydroxide,
The method according to the above (4), wherein the inside of the reaction system is maintained at 20 to 50 ° C. (6) The method according to the above (4) or (5), wherein the water in the reaction system is contained within a range of 0.5 to 10% by weight of the epihalohydrins. The epoxy resin according to any one of 2) and (3) and / or (4), (5) and (6).
An epoxy resin composition comprising an epoxy resin obtained by the production method according to any one of the above,
(8) The epoxy resin composition of (7), which contains a room temperature liquid polyhydric phenol compound having an allyl group as a curing agent, and (9) the epoxy resin composition prepared for semiconductor encapsulation. (7) or (8) the epoxy resin composition, (10) the epoxy resin composition according to (7) or (8), which is prepared for a die bonding paste, (11) the (7) or (8) , (9) and (10)
A cured product obtained by curing the epoxy resin composition according to any one of the above.

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

[0009]

Embedded image (Wherein X and R have the same meanings as in formula (1)) and epihalohydrins can be reacted (epoxidation reaction). Equation (2)
Is obtained by reacting various bisphenols with allyl halide, allyl etherification and then Claisen rearrangement of the allyl group, and the starting materials bisphenols, monoallyl bisphenols, diallyl bisphenols, triallyl bisphenols, tetra Allyl bisphenols are used alone or as a mixture, and the average value of R is 13 to 25%. Examples of the bisphenols include bisphenol A, bisphenol F, bisphenol AD, biphenol, cyclohexylidenebisphenol, bisphenol S, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, and bis (4-hydroxy Phenyl) methanone, 4,4 '-(dimethylsilylene) bisphenol, 4,4'-oxybisphenol and the like. X in the compound of the formula (2) has 1 carbon atom
Preferred are those having from 2 to 2 hydrocarbon groups. 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, 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 (2) 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. The epihalohydrins may be continuously distilled back to the reaction mixture by distilling off the components and separating water to remove water (the solid alkali metal hydroxide may also 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 per 1 equivalent of the hydroxyl group of the compound of the formula (2) increases as the number of repeating units (n) decreases and the viscosity becomes lower. If considered, it is usually 1.0 to 20 mol, preferably 2.0 to 15 mol, more preferably 3.
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 (2).
1.5 mol, preferably 0.7 to 1.2 mol.

As the compound of the formula (2), those in which X is a hydrocarbon group having 1 to 2 carbon atoms are preferable, and those in which an allyl group is substituted at the ortho position of the hydroxyl group are particularly preferable. In this case, the reactivity between the hydroxyl group and epihalohydrin
Bad compared to 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 aprotic polar solvents that can be used include:
Examples thereof include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, and 1,4-dioxane. The amount of the aprotic polar solvent to be used is generally 5-200% by weight, preferably 10-150% by weight, based on the weight of epihalohydrins. 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 obtained epoxy resin is used for electronic and electronic parts such as semiconductors, the total halogen content is 0.00
It is preferably at most 0023 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.

Usually, these reaction products are used under washing with or without washing under heating and reduced pressure to obtain an excess of 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)
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.

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 was determined by adding a 1N-KOH propylene glycol solution to a butyl carbitol solution of an epoxy resin and refluxing for 10 minutes to measure the amount (mol) of the halogen released by a silver nitrate titration method. Divided by The value of n in the above formula (1) is usually 1.0 or less, preferably 0.2 or less.

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 Those having low mutagenicity are preferred. These may be used alone or in combination of two or more.

[0020] 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 with aromatic dimethylol, biphenols and modified products thereof, polyhydric phenol compounds such as the compound of the formula (2) and allylic products of the phenol compounds, imidazole, BF ₃ −
Examples thereof include an amine complex and a guanidine derivative, and a compound having low mutagenicity is 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 generally 0.5 to 1.5 equivalents, preferably 0.6 to 1.2 equivalents, per equivalent of the epoxy group of the epoxy resin. 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, for semiconductor encapsulation and for die bonding paste, the use of a polyhydric phenolic compound that is liquid at normal temperature, the viscosity of the composition,
It is preferable in terms of storage stability, adhesion of the cured product, 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, etc., 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 ratio of the solvent to the total weight of the epoxy resin composition of the present invention and the solvent is usually 10 to 70% by weight, preferably 15 to 65% by weight.

[0025]

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.

Example 1 154 parts by weight of 4,4'-isopropylidenebis (2-allylphenol), 650 parts by weight of epichlorohydrin (ECH, hereinafter the same), dimethyl sulfoxide (DMS)
O, hereinafter the same) 400 parts by weight are charged into a reaction vessel, heated,
After stirring and dissolving, the reaction system is maintained at 45 ° C. for 45 minutes.
Torr, 40% aqueous sodium hydroxide solution 10
5 parts by weight were 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 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 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 228 parts by weight of the epoxy resin (E1) of the present invention. The obtained epoxy resin (E1) was negative in the Ames test.

Example 2 The same operation as in Example 1 was carried out except that 4,4'-isopropylidenebis (2-allylphenol) was replaced by 149 parts by weight of 4,4'-ethylidenebis (2-allylphenol). The epoxy resin (E2) 18 of the present invention
7 parts by weight were obtained.

Example 3 In Example 1, 4,4'-isopropylidenebis (2-allylphenol) was replaced with diallylbisphenol F
(Purity: 85%) The same operation was performed except that 138 parts by weight was used, to obtain 175 parts by weight of the epoxy resin (E3) of the present invention.

Comparative Example 1 In Example 1, 4,4'-isopropylidenebis (2-allylphenol) was replaced with bisphenol A114.
The same operation was performed except that 1 part by weight of tetramethylammonium chloride (hereinafter referred to as TMAC) was used instead of DMSO without using DMSO.
Parts by weight were obtained.

Comparative Example 2 155 parts by weight of an epoxy resin (R2) was obtained in the same manner as in Comparative Example 1, except that bisphenol A was changed to 107 parts by weight of 4,4'-ethylidenebisphenol.

Comparative Example 3 An epoxy resin (R3) (149 parts by weight) was obtained in the same manner as in Comparative Example 1 except that bisphenol A was changed to 100 parts by weight of bisphenol F.

Table 1 shows the measurement results of the physical properties of the epoxy resins in the above Examples and Comparative Examples. In addition, the measurement of the physical property value was performed by the following method. Amount of total chlorine 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 in accordance with JIS K-7236 ・ Viscosity E-type rotational viscometer (25 ° C)

[0033]

Table 1 Epoxy resin E1 E2 E3 R1 R2 R3 Epoxy equivalent (g / eq) 220 211 212 173 168 162 Viscosity (poise) 19 11 188 80 35 45 Total chlorine concentration (10-5 mol / g) 1.8 1.7 2.0 3.0 2.8 3.1

Examples 4 to 6, Comparative Examples 4 to 6 Epoxy resins (E1) to (E1) obtained in Examples 1 to 3
3) and the epoxy resin (R1) obtained in Comparative Examples 1 to 3
To (R3), and a phenol novolak resin (ICI viscosity at 150 ° C. 0.1 poise, softening point 6
2 ° C., hydroxyl equivalent 105 g / eq; hereinafter PN) was mixed with 1 hydroxyl equivalent, and 1 part by weight of a curing accelerator (triphenylphosphine) per 100 parts by weight of epoxy resin was melted and mixed quickly in a hot plate. Was 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 2 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 ・ Hygroscopicity: Disk-shaped test piece of 5 cm in diameter × 4 mm in thickness Was humidified under the conditions of 85 ° C. and 85% RH for 24 hours before and after weight increase (%).

[0036]

Table 2 Example Comparative Example 4 5 6 4 5 6 Epoxy resin E1 E2 E3 R1 R2 R3 Physical properties of cured product Copper foil peel strength (Kg / cm) 3.9 3.9 3.8 3.5 3 0.6 3.4 Moisture absorption (%) 0.60 0.65 0.70 0.85 0.90 0.10

[0037]

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.

Claims (11)

[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 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or an allyl group, and 13 to 25% of the whole is an allyl group. Epoxy resin represented by). 2. The epoxy resin according to claim 1, wherein in the formula (1), X is a hydrocarbon group having 1 to 2 carbon atoms. 3. The total halogen content is 0.000023 mol /
The epoxy resin according to claim 1, which is not more than g. 4. 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. 5. The process according to claim 4, wherein the catalyst is an alkali metal hydroxide, and the temperature inside the reaction system is maintained at 20 to 50 ° C. during the addition. 6. The process according to claim 4, wherein the water content in the reaction system is within the range of 0.5 to 10% by weight of the epihalohydrins. 7. An epoxy resin according to any one of claims 1, 2 and 3, and / or an epoxy resin obtained by the production method according to any one of claims 4, 5 and 6. An epoxy resin composition characterized in that: 8. The epoxy resin composition according to claim 7, which contains a normal temperature liquid polyhydric phenol compound having an allyl group as a curing agent. 9. The epoxy resin composition according to claim 7, which is prepared for encapsulating a semiconductor. 10. The epoxy resin composition according to claim 7, which is prepared for a die bonding paste. 11. The method of claim 7, 8, 9, or 10
A cured product obtained by curing the epoxy resin composition according to the above item.