JPH09316170A - Epoxy resin, epoxy resin composition, and its cured item - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin which has a separable halogen content of 600ppm or lower and can be used with a high reliability in semiconductor fields by reacting 1,1-bis(4-hydroxyphenyl)ethane with an epihalohydrin in a specific solvent. SOLUTION: This resin is represented by the formula (wherein n is a mean value and is 1.0 or lower; and R is H or a 1-5O alkyl), has a separable halogen content of 600ppm or lower, and is produced by reacting 1,1-bis(4-hydroxyphenyl) ethane with an epihalohydrin (pref. epichlorohydrin) in an aprotic polar solvent, an alcohol, or an ether, if necessary in the presence of a quaternary ammonium salt as the catalyst, removing the solvent after the reaction, and reducing the total halogen content by using NaOH, etc. This resin has a low viscosity and a low crystallinity, gives a cured item with high adhesive properties, and can be used in electronic and electric applications, such as semiconductor fields, with a high reliability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various types of insulating materials such as highly reliable semiconductor encapsulating materials for electric and electronic parts, and laminated boards (printed wiring boards) and CFRP (carbon fiber reinforced plastic). The present invention relates to an epoxy resin useful for various adhesives including composite materials and die bonding pastes, paints, etc., 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 cured products' excellent electrical characteristics, heat resistance, adhesiveness, moisture resistance (water resistance), etc. Widely used in the field.

[0003]

However, in recent years, along with the development thereof in the electric and electronic fields, various characteristics such as high purity, heat resistance, moisture resistance, adhesiveness, and low viscosity for high filler filling have been achieved. Further improvement is required. Further, as a structural material, it is required to be an aerospace material, a material that is lightweight and has excellent mechanical properties in applications such as leisure and sports equipment, and at the same time, a low-viscosity resin is required to improve workability. In order to meet these requirements, bisphenol A and bisphenol F epoxy resins having a small number of repeating units have been proposed, but they have a drawback that they are crystallized at room temperature.
Although the aliphatic epoxy resin has a low viscosity, the epoxy resin is inferior to the aromatic epoxy resin in terms of heat resistance and strength. Especially in the recent semiconductor field, high frequency is progressing,
As a result, a large amount of heat is generated, so that the materials used in this field require heat resistance.

[0004]

The present inventors have completed the present invention as a result of earnest research on an epoxy resin having the above characteristics. That is, the present invention is based on the formula (1)

[0005]

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(In the formula, n represents an average value and represents a real number of 1.0 or less. R independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and can be released. Epoxy resin whose total halogen content is 600 ppm or less,
(2) The value of n in the formula (1) is 0.2 or less, (1)
Epoxy resin described, (3) Total halogen content is 400 pp
The epoxy resin according to (1) or (2), which is m or less, (4) the epoxy resin composition containing the epoxy resin according to any one of (1), (2) or (3), (5) The epoxy resin composition according to (4) prepared for semiconductor encapsulation, (6) the epoxy resin composition according to (4) prepared for die bonding paste, (7) above. (4) A cured product obtained by curing the epoxy resin composition according to any one of (5) and (6).

The epoxy resin of the present invention is prepared by reacting 1,1-bis (4-hydroxyphenyl) ethane with epihalohydrins in a specific solvent or in the presence of a quaternary ammonium salt, or in the presence of both. Obtainable.

Specific examples of the epihalohydrins used in this epoxidation reaction include epichlorohydrin, β-methylepichlorohydrin, epibromhydrin, β-methylepibromohydrin, epiiodohydrin, β-ethylepichlorohydrin. Etc., but epichlorohydrin, which is industrially easily available and inexpensive, is preferable. This epoxidation reaction itself can be carried out according to a conventionally known method.

For example, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added all at once or gradually to a mixture of 1,1-bis (4-hydroxyphenyl) ethane and epihalohydrins as described above.
React at ~ 120 ° C for 0.5-10 hours. At this time, an aqueous solution may be used as the alkali metal hydroxide, and in that case, the alkali metal hydroxide is continuously added, and water and epihalohydrins are continuously added from the reaction mixture under reduced pressure or normal pressure. It is also possible to use a method in which distilling is carried out, liquid separation is carried out, water is removed, and epihalohydrins are continuously returned to the reaction mixture (when a solid alkali metal hydroxide is used, dehydration under reduced pressure is also possible).

In the above reaction, the amount of the epihalohydrin used will be smaller as the number of repeating units becomes larger with respect to 1 equivalent of the hydroxyl group of 1,1-bis (4-hydroxyphenyl) ethane. However, considering the production efficiency. Usually 1.0
-20 mol, preferably 2.0-10 mol, and more preferably 3.0-6.0 mol. The amount of the alkali metal hydroxide used is usually 0.5 to 1.5 mol, preferably 0.7 to 1.2 mol, per 1 equivalent of the hydroxyl group of 1,1-bis (4-hydroxyphenyl) ethane.

The reaction is preferably carried out in an aprotic polar solvent, alcohols or ethers. Specific examples of the aprotic polar solvent that can be used include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone and the like. The amount of the aprotic polar solvent used is usually 5 to 200% by weight, preferably 10 to 100% by weight, based on the weight of the epihalohydrin. Specific examples of alcohols that can be used include methanol and ethanol, and specific examples of ethers that can be used include cyclic or chain ethers such as 1,4-dioxane. The amount of alcohols or ethers used is usually 5 to 100% by weight, preferably 5 to 50% by weight, based on the weight of epihalohydrins. The reaction is facilitated by using alcohols or ethers, and the total halogen concentration is higher than that when an aprotic polar solvent is used, but lower than when these solvents are not used.

Further, in the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride can be used as a catalyst. In this case, the amount of quaternary ammonium salt used is 1,1
It is usually 0.001 to 0.2 mol, preferably 0.05 to 0.1 mol, per 1 equivalent of the hydroxyl group of -bis (4-hydroxyphenyl) ethane.

Usually, these reaction products are washed with water or without being washed with water, and an excess of epihalohydrins under heating and reduced pressure, and
After removing other used solvents, etc., dissolve in a solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, etc., add an aqueous solution of an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, etc. to carry out the reaction again. It is possible to obtain an epoxy resin having a low total releasable halogen amount (hereinafter, simply referred to as total halogen amount). In this case, the amount of the alkali metal hydroxide used is 0.01 to 0.2 mol, preferably 0.05 to 0.2 mol, relative to 1 equivalent of the hydroxyl group of 1,1-bis (4-hydroxyphenyl) ethane.
It is 1 mol. 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, the by-produced salt is removed by filtration, washing with water and the like, and the solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure 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 600 ppm or less, and one obtained under the preferable conditions is 400 ppm or less. Further, the epoxy resin of the present invention having a lower total halogen content can be obtained by subjecting the obtained epoxy resin to a vacuum distillation treatment. The total amount of halogen was determined by adding the 1N-KOH propylene glycol solution to the butyl carbitol solution of the epoxy resin and refluxing for 10 minutes to measure the amount of halogen liberated by the silver nitrate titration method and dividing by the weight of the epoxy resin. It is a value. 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 in combination, the ratio of the epoxy resin of the present invention to the total epoxy resin is 30% by weight.
The above is preferable, and 40% by weight or more is particularly preferable.

Specific examples of other epoxy resins which 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. A polycondensate with, a polymer of a phenol and various diene compounds, a polycondensate of a phenol and an aromatic dimethylol,
Examples thereof include, but are not limited to, glycidyl ether-based epoxy resins obtained by glycidylating biphenols and alcohols, alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like. These may be used alone or in combination of two or more.

A preferred embodiment of the epoxy resin composition of the present invention contains a curing agent. 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, trianhydride. Mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenols (phenol, alkyl-substituted) Polycondensate 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, imidazo -
And BF ₃ -amine complex, guanidine derivative 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.
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 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, to the epoxy resin composition of the present invention, if necessary, various compounding agents such as fillers such as silica, alumina, talc and silver powder, silane coupling agents, release agents and pigments may be added. it can.

The epoxy resin composition of the present invention is obtained by uniformly mixing the above components in a predetermined ratio, and is preferably used for semiconductor encapsulation or 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 optionally a curing accelerator, a filler,
And an additive, if necessary, using an extruder, a kneader, etc., to sufficiently mix until uniform to obtain an epoxy resin composition of the present invention, the epoxy resin composition, a melt casting method or Transfer molding method and injection molding method,
Molded by compression molding method, etc., if necessary 80 to 20
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 to prepare glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and the like. The cured product of the present invention can also be obtained by hot press molding a prepreg obtained by impregnating a base material and heating and drying.

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.

[0022]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to these examples.

Example 1 1,1-bis (4-hydroxyphenyl) ethane 107
Parts by weight, epichlorohydrin (ECH, the same below) 46
0 parts by weight and 400 parts by weight of dimethylsulfoxide (DMSO, the same below) were charged into a reaction vessel, heated, stirred and dissolved, and then kept at 45 ° C. while maintaining the reaction system at 45 Torr to prepare a 40% sodium hydroxide aqueous solution. 100 parts by weight 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 dropping the aqueous solution of sodium hydroxide, continue to reduce the pressure at 45 °
The reaction was further carried out for 2 hours at 70 ° C. for 30 minutes. Then, 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 350 parts by weight of methyl isobutyl ketone (MIBK, hereinafter the same) was added and dissolved. Furthermore, this MIBK solution was heated to 70 ° C., 15 parts by weight of a 30% aqueous sodium hydroxide solution was added, and the mixture was reacted for 1 hour, and then repeatedly washed with water until the washing solution of the solution became neutral. Then, MIBK was distilled off from the oil layer under heating and reduced pressure to obtain 155 parts by weight of the epoxy resin (E1) of the present invention in which R in the formula (1) was a hydrogen atom.

Example 2 Epoxy resin (E1) 100 obtained in Example 1
When parts by weight were distilled under the conditions of 0.005 mmHg and 180 to 200 ° C., 58 parts by weight of a fraction (epoxy resin (E2) was obtained.

Comparative Example 1 The epoxy resin (E1) used in Example 2 was the commercially available epoxy resin of bisphenol A (Epicoat 828).
The same operation as in Example 2 was carried out except that it was changed to Yuka Shell Epoxy Co., Ltd. (R1) to obtain 38 parts by weight of epoxy resin (R2).

Comparative Example 2 The epoxy resin (E1) used in Example 2 is a commercially available epoxy resin of bisphenol F (Epomic R-1).
10 Epoxy resin (R4) was obtained after the same operation was performed except that the oil was changed to Yuka Shell Epoxy Co., Ltd. (R3).
40 parts by weight were obtained.

Table 1 shows the results obtained by measuring 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.・ Total halogen content 1N-KOH propylene glycol solution was added to the sample butyl carbitol solution, and the amount of chlorine liberated by refluxing for 10 minutes was measured by the silver nitrate titration method and divided by the weight of the sample ・ Epoxy equivalent JIS Value measured by the method according to K-7236-Viscosity B type rotational viscometer (25 ° C) -Crystallinity at room temperature Presence of crystals after standing at 20 ° C for 3 days

[0028]

[Table 1] Table 1 Epoxy resin E1 E2 R1 R2 R3 R4 Epoxy equivalent (g / eq) 175 165 190 190 168 173 158 Viscosity (poise) 30 20 180 180 80 120 50 50 Total halogen concentration (ppm) 380 160 1800 850 1500 840 Normal temperature Crystalline No No Yes Yes Yes Yes Yes

Examples 3 and 4, Comparative Examples 3 to 6 The epoxy resins (E1) to (E2) of Examples 1 and 2 and the epoxy resins (R1) to (R4) of Comparative Examples 1 to 4 were used. A curing agent (phenol novolac resin, I at 150 ° C. per 1 equivalent of epoxy group of epoxy resin)
CI viscosity 0.1 poise, softening point 62 ° C, hydroxyl equivalent 10
5 g / eq) are mixed in an amount equivalent to 1 hydroxyl group, and 1 part by weight of a curing accelerator (triphenylphosphine) is melt-mixed in a hot plate form per 100 parts by weight of an epoxy resin, and the mixture is poured into a mold at 160 ° C. 2 hours, 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. -Glass transition temperature (TMA): manufactured by Vacuum Riko Co., Ltd. TM-7000 Temperature rising rate 2 ° C / min.・ Copper foil peeling strength: 180 ° C. peeling test Measurement temperature; 30 ° C. Pulling speed; 200 mm / min Copper foil; JTC foil manufactured by Nikko Gould Co., Ltd. Thickness 70 μm ・ PCT test; Crushed sample (100 mesh pass) 5 g Was treated in pure 50 g at 125 ° C. for 20 hours, and then the chloride ion concentration in the extracted water was measured by ion chromatography.

[0031]

Table 2 Example Comparative Example 3 4 3 4 5 6 Epoxy resin E1 E2 R1 R2 R3 R4 Physical properties of cured product Glass transition temperature (° C) 114 115 110 110 114 112 110 Copper foil peeling strength (Kg / cm) 3 .7 3.8 3.4 3.3 3.4 3.5 PCT; Cl ^- concentration (ppm) 13 5 130 50 140 140 45

[0032]

The epoxy resin of the present invention has a low viscosity but extremely low crystallinity at room temperature. In addition, the cured product of the epoxy resin composition of the present invention has excellent adhesiveness, and its heat resistance is not inferior to that of an epoxy resin composition using a normal liquid epoxy resin. Furthermore, since the total halogen content is small,
When the epoxy resin composition of the present invention is used in electronic and electrical fields including semiconductors, high reliability can be secured.

Claims (7)

[Claims] (1) Formula (1) (In the formula, n is an average value and represents a real number of 1.0 or less. R
Each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ), And the total amount of halogen that can be released is 600 ppm or less. 2. The epoxy resin according to claim 1, wherein the value of n in the formula (1) is 0.2 or less. 3. The epoxy resin according to claim 1, which has a total halogen content of 400 ppm or less. 4. An epoxy resin composition containing the epoxy resin according to any one of claims 1, 2 and 3. 5. The epoxy resin composition according to claim 4, which is prepared for semiconductor encapsulation. 6. The epoxy resin composition according to claim 4, which is prepared for a die bonding paste. 7. A cured product obtained by curing the epoxy resin composition according to any one of claims 4, 5 and 6.